Eisenstein Hecke algebras and Iwasawa theory

Science.gov (United States)

Wake, Preston

We show that if an Eisenstein component of the p-adic Hecke algebra associated to modular forms is Gorenstein, then it is necessary that the plus-part of a certain ideal class group is trivial. We also show that this condition is sufficient whenever a conjecture of Sharifi holds. We also formulate a weaker Gorenstein property, and show that this weak Gorenstein property holds if and only if a weak form of Sharifi's conjecture and a weak form of Greenberg's conjecture hold.

Matsuda–Heck reaction with arenediazonium tosylates in water

Directory of Open Access Journals (Sweden)

Ksenia V. Kutonova

2015-03-01

Full Text Available An environmentally friendly Matsuda–Heck reaction with arenediazonium tosylates has been developed for the first time. A range of alkenes was arylated in good to quantitative yields in water. The reaction is significantly accelerated when carried out under microwave heating. The arylation of haloalkylacrylates with diazonium salts has been implemented for the first time.

The Heck reaction in the production of fine chemicals

NARCIS (Netherlands)

Vries, Johannes G. de

2001-01-01

An overview is given of the use of the Heck reaction for the production of fine chemicals. Five commercial products have been identified that are produced on a scale in excess of 1 ton/year. The herbicide Prosulfuron™ is produced via a Matsuda reaction of 2-sulfonatobenzenediazonium on

Kneser-Hecke-operators in coding theory

OpenAIRE

Nebe, Gabriele

2005-01-01

The Kneser-Hecke-operator is a linear operator defined on the complex vector space spanned by the equivalence classes of a family of self-dual codes of fixed length. It maps a linear self-dual code $C$ over a finite field to the formal sum of the equivalence classes of those self-dual codes that intersect $C$ in a codimension 1 subspace. The eigenspaces of this self-adjoint linear operator may be described in terms of a coding-theory analogue of the Siegel $\\Phi $-operator.

Palladium-Catalyzed Heck Coupling Reaction of Aryl Bromides in Aqueous Media Using Tetrahydropyrimidinium Salts as Carbene Ligands

Directory of Open Access Journals (Sweden)

İsmail Özdemir

2010-01-01

Full Text Available An efficient and stereoselective catalytic system for the Heck cross coupling reaction using novel 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (1, LHX and Pd(OAc2 loading has been reported. The palladium complexes derived from the salts 1a-f prepared in situ exhibit good catalytic activity in the Heck coupling reaction of aryl bromides under mild conditions.

Mild and Efficient Nickel-Catalyzed Heck Reactions with Electron-Rich Olefins

DEFF Research Database (Denmark)

Gøgsig, Thomas; Kleimark, Jonatan; Lill, Sten O. Nilsson

2012-01-01

proved compatible, and the corresponding aryl methyl ketone could be secured after hydrolysis in yields approaching quantitative. Good functional group tolerance was observed matching the characteristics of the analogous Pd-catalyzed Heck reaction. The high levels of catalytic activity were explained...

Thermally decarboxylated sodium bicarbonate: Interactions with water vapour, calorimetric study

Directory of Open Access Journals (Sweden)

Natalia Volkova

2013-06-01

Full Text Available Isothermal titration calorimetry (ITC was used to study interactions between water vapour and the surface of thermally converted sodium bicarbonate (NaHCO3. The decarboxylation degree of the samples was varied from 3% to 35% and the humidity range was 54–100%. The obtained enthalpy values were all exothermic and showed a positive linear correlation with decarboxylation degrees for each humidity studied. The critical humidity, 75% (RHo, was determined as the inflection point on a plot of the mean−ΔHkJ/mole Na2CO3 against RH. Humidities above the critical humidity lead to complete surface dissolution. The water uptake (m was determined after each calorimetric experiment, complementing the enthalpy data. A mechanism of water vapour interaction with decarboxylated samples, including the formation of trona and Wegscheider’s salt on the bicarbonate surface is proposed for humidities below RHo. Keywords: Isothermal titration calorimetry, Sodium bicarbonate, Sodium carbonate, Trona salt, Wegscheider’s salt, Enthalpy, Relative humidity, Pyrolytic decarboxylation

Supported liquid phase catalyst coating in micro flow Mizoroki-Heck reaction

NARCIS (Netherlands)

Stouten, S.C.; Noël, T.; Wang, Q.; Hessel, V.

2015-01-01

A Supported Liquid Phase Catalyst (SLPC) coating was successfully applied for the Mizoroki–Heck reaction in micro flow. Foremost, extended on stream operation was enabled and the on stream performance stability was verified. Stable catalytic activity was achieved during two consecutive runs totaling

21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate-vinyl alcohol copolymers... for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1360 Ethylene-vinyl acetate-vinyl alcohol copolymers. Ethylene-vinyl acetate-vinyl alcohol copolymers (CAS Reg. No. 26221-27-2...

Studies on the decarboxylation of acetolactate in milk products

OpenAIRE

Mohr, Britta

1997-01-01

The effect of different parameters on the decarboxylation of acetolactate (ALA) to diacetyl and acetoin were studied. The distillation volume and the milk solids concentration had no significant effect on decarboxylation of ALA, whereas breakdown of ALA increased with decreasing pH and increasing temperature. Oxygenation increased diacetyl production from ALA, but diacetyl was lost from the model system. Oxygenation did not have an effect on acetoin production from ALA. Metal ions (Cu2+, Fe2+...

Synthesis of novel room temperature chiral ionic liquids: application as reaction media for the heck arylation of aza-endocyclic acrylates

Energy Technology Data Exchange (ETDEWEB)

Pastre, Julio C.; Correia, Carlos R.D., E-mail: genisson@chimie.ups-tlse.f, E-mail: roque@iqm.unicamp.b [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica; Genisson, Yves [Universite Paul Sabatier, Toulouse (France). Lab. de Synthese et Physicochimie des Molecules d' Interet Biologique; Saffon, Nathalie [Universite Paul Sabatier, Toulouse (France). Structure federative toulousaine en chimie moleculaire (SFTCM); Dandurand, Jany [Universite Paul Sabatier, Toulouse (France). Lab. de Physique des Polymeres

2010-07-01

New achiral and chiral RTILs were prepared using novel and/or optimized synthetic routes. These new series of imidazolinium, imidazolium, pyridinium and nicotine-derived ionic liquids were fully characterized including differential scanning calorimetry (DSC) analysis. The performance of these achiral and chiral room temperature ionic liquids (RTILs) was demonstrated by means of the Heck arylation of endocyclic acrylates employing arenediazonium salts and aryl iodides. The Heck arylations performed in the presence of these ionic entities, either as a solvent or as an additive, were effective leading to complete conversion of the substrate and good to excellent yield of the Heck adduct. In spite of the good performances, no asymmetric induction was observed in any of the cases studied. Two new diastereoisomeric NHC-palladium complexes were prepared in good yields from a chiral imidazolium salt and their structure characterized by X-ray diffraction. Overall, the Heck arylations employing arenediazonium tetrafluoroborates in RTILs were more effective than the traditional protocols employing aryl iodides in terms of reactivity and yields. (author)

Hiperplasia epitelial focal (doença de Heck em descendente de índios brasileiros: relato de caso Focal epithelial hyperplasia (Heck's disease in Brazilian indian descent: report of a case

Directory of Open Access Journals (Sweden)

Pedro Paulo de Andrade Santos

2007-12-01

Full Text Available A hiperplasia epitelial focal, ou doença de Heck, é uma enfermidade rara, benigna, que afeta a mucosa oral de crianças e adultos jovens de diversas regiões do mundo e em diferentes grupos étnicos, como indígenas e esquimós. Apresenta correlação com o papilomavírus humano (HPV no qual os tipos 13 e 32 têm sido consistentemente detectados nessas lesões. Este artigo relata um caso de uma paciente de 18 anos de idade, descendente de índios potiguares, que compareceu ao serviço de estomatologia da Universidade Federal do Rio Grande do Norte (UFRN, exibindo lesões bem definidas, arredondadas, planas, localizadas em cavidade oral, com tempo de evolução de aproximadamente dois anos. As lesões foram submetidas a biópsias incisionais, constatado-se no exame histopatológico alterações epiteliais, como acantose, cristas epiteliais em forma de "taco de golfe" além de células mitosóides. Esses achados histopatológicos foram compatíveis com a hipótese clínica de hiperplasia epitelial focal (doença de Heck.The focal epithelial hyperplasia or Heck's disease is a benign rare pathology, that affects children and young adults oral mucosal in many world regions, and different ethnic groups, for example Indians and Eskimos. Presents correlation with the subtypes 13 and 32 of human papillomavirus (HPV. This article report a case of an 18-year-old patient, descent of potiguar indian, attended in stomatology service of Federal University of Rio Grande do Norte (UFRN, presenting well defined lesions, round, plane, localized in oral cavity with an evolution of two years. The lesions were submitted to incisional biopsies, verifying in histopathologic exam, epithelial alterations, like acanthosis, epithelial projections in "parquet block of golf" beyond mitosoid cells. These histopathological findings were compatible with clinical hypothesis of focal epithelial hyperplasia (Heck's disease.

Iwahori-Hecke algebras and Schur algebras of the symmetric group

CERN Document Server

Mathas, Andrew

1999-01-01

This volume presents a fully self-contained introduction to the modular representation theory of the Iwahori-Hecke algebras of the symmetric groups and of the q-Schur algebras. The study of these algebras was pioneered by Dipper and James in a series of landmark papers. The primary goal of the book is to classify the blocks and the simple modules of both algebras. The final chapter contains a survey of recent advances and open problems. The main results are proved by showing that the Iwahori-Hecke algebras and q-Schur algebras are cellular algebras (in the sense of Graham and Lehrer). This is proved by exhibiting natural bases of both algebras which are indexed by pairs of standard and semistandard tableaux respectively. Using the machinery of cellular algebras, which is developed in Chapter 2, this results in a clean and elegant classification of the irreducible representations of both algebras. The block theory is approached by first proving an analogue of the Jantzen sum formula for the q-Schur algebras. T...

Oxidative Decarboxylation of Levulinic Acid by Silver(I/Persulfate

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Yan Gong

2011-03-01

Full Text Available The oxidative decarboxylation of levulinic acid (LA by silver(I/persulfate [Ag(I/S2O82−] has been investigated in this paper. The effects of buffer solution, initial pH value, time and temperature and dosages of Ag(I/S2O82− on the decarboxylation of LA were examined in batch experiments and a reaction scheme was proposed on basis of the reaction process. The experimental results showed that a solution of NaOH-KH2PO4 was comparatively suitable for the LA decarboxylation reaction by silver(I/persulfate. Under optimum conditions (temperature 160 °C, pH 5.0, and time 0.5 h, the rate of LA conversion in NaOH-KH2PO4 solutions with an initial concentration of 0.01 mol LA reached 70.2%, 2-butanone (methyl ethyl ketone was the single product in the gas phase and the resulted molar yield reached 44.2%.

Oxidative Decarboxylation of Levulinic Acid by Cupric Oxides

Directory of Open Access Journals (Sweden)

Lu Lin

2010-11-01

Full Text Available In this paper, cupric oxides was found to effectively oxidize levulinic acid (LA and lead to the decarboxylation of levulinic acid to 2-butanone. The effects of cupric oxide dosage, reaction time and initial pH value were investigated in batch experiments and a plausible mechanism was proposed. The results showed that LA decarboxylation over cupric oxides at around 300 °C under acidic conditions produced the highest yield of butanone (67.5%. In order to elucidate the catalytic activity of cupric oxides, XRD, AFM, XPS and H2-TPR techniques was applied to examine their molecular surfaces and their effects on the reaction process.

An Intramolecular Heck reaction that Prefers a 5-endo- to a 6-exo-trig Cyclization Pathway

DEFF Research Database (Denmark)

Vital, Paulo; Norrby, Per-Ola; Tanner, David Ackland

2006-01-01

A regioselective aromatic Claisen rearrangement was used to prepare 17a, the precursor of triflate 17e. The intramolecular Heck reaction of 17e is promoted only by bidentate phosphine ligands, giving exclusively and in excellent yield 20, the product of a 5-endo-trig cyclization, despite the poss......A regioselective aromatic Claisen rearrangement was used to prepare 17a, the precursor of triflate 17e. The intramolecular Heck reaction of 17e is promoted only by bidentate phosphine ligands, giving exclusively and in excellent yield 20, the product of a 5-endo-trig cyclization, despite...

On the fourth moment of Hecke Maass forms and the Random Wave Conjecture

OpenAIRE

Buttcane, Jack; Khan, Rizwanur

2016-01-01

Conditionally on the Generalized Lindel\\"of Hypothesis, we obtain an asymptotic for the fourth moment of Hecke Maass cusp forms of large Laplacian eigenvalue for the full modular group. This lends support to the Random Wave Conjecture.

Breaking the regioselectivity rule for acrylate insertion in the Mizoroki-Heck reaction.

Science.gov (United States)

Wucher, Philipp; Caporaso, Lucia; Roesle, Philipp; Ragone, Francesco; Cavallo, Luigi; Mecking, Stefan; Göttker-Schnetmann, Inigo

2011-05-31

In modern methods for the preparation of small molecules and polymers, the insertion of substrate carbon-carbon double bonds into metal-carbon bonds is a fundamental step of paramount importance. This issue is illustrated by Mizoroki-Heck coupling as the most prominent example in organic synthesis and also by catalytic insertion polymerization. For unsymmetric substrates H(2)C = CHX the regioselectivity of insertion is decisive for the nature of the product formed. Electron-deficient olefins insert selectively in a 2,1-fashion for electronic reasons. A means for controlling this regioselectivity is lacking to date. In a combined experimental and theoretical study, we now report that, by destabilizing the transition state of 2,1-insertion via steric interactions, the regioselectivity of methyl acrylate insertion into palladium-methyl and phenyl bonds can be inverted entirely to yield the opposite "regioirregular" products in stoichiometric reactions. Insights from these experiments will aid the rational design of complexes which enable a catalytic and regioirregular Mizoroki-Heck reaction of electron-deficient olefins.

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

Science.gov (United States)

2010-10-01

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

Matrix units and Schur elements for the degenerate cyclotomic Hecke algebras

OpenAIRE

Zhao, Deke

2011-01-01

The paper uses the cellular basis of the (semi-simple) degenerate cyclotomic Hecke algebras to investigate these algebras exhaustively. As a consequence, we describe explicitly the "Young's seminormal form" and a orthogonal bases for Specht modules and determine explicitly the closed formula for the natural bilinear form on Specht modules and Schur elements for the degenerate cyclotomic Hekce algebras.

Copper-Catalyzed Decarboxylative Trifluoromethylation of Propargyl Bromodifluoroacetates.

Science.gov (United States)

Ambler, Brett R; Peddi, Santosh; Altman, Ryan A

2014-07-15

The development of efficient methods for accessing fluorinated functional groups is desirable. Herein, we report a two-step method that utilizes catalytic Cu for the decarboxylative trifluoromethylation of propargyl bromodifluoroacetates. This protocol affords a mixture of propargyl trifluoromethanes and trifluoromethyl allenes.

Magnetically Separable Fe3O4@DOPA-Pd: A Heterogeneous Catalyst for Aqueous Heck Reaction

Science.gov (United States)

Magnetically separable Fe3O4@DOPA-Pd catalyst has been synthesized via anchoring of palladium over dopamine-coated magnetite via non-covalent interaction and the catalyst is utilized for expeditious Heck coupling in aqueous media.

Carbon-13 fractionation observed in thermal decarboxylation of pure phenylpropiolic acid (PPA) dissolved in phenylacetylene

International Nuclear Information System (INIS)

Zielinska, A.; Zielinski, M.; Papiernik-Zielinska, H.

2003-01-01

The determinations of the 13 C fractionation in the decarboxylation of pure phenylpropiolic acid (PPA) above its melting point has been extended to higher degrees of decomposition of PPA by carrying out two-step decarboxylations to establish the maximum possible yield of carbon dioxide in the temperature interval of 423-475 K (58%). The result was compared with the yields of CO 2 for decarboxylation of PPA in phenylacetylene solvent (PA) (much smaller, temperature dependent, and equal to 11% at 406 K). The ratios of carbon isotope ratios, R so /R pf , all smaller than 1.009 in the temperature interval 405-475 K, have been analyzed formally within the branched decomposition scheme of PPA, providing carbon dioxide and a decarboxylation resistant solid chemical compound enriched in 13 C with respect to CO 2 . A general discussion of the 13 C fractionation in the decarboxylation of pure PPA and PPA dissolved in PA is supplemented by the model calculation of the maximized skeletal 13 C KIEs, in the linear chain propagation of the acetylene polymerization process. Further studies of the 13 C fractionation in condensed phases and in different hydrogen deficient and hydrogen rich media have been suggested. (author)

Reactivity and Regioselectivity in the Heck Reaction - A Hammett Study of 4-Substituted Styrenes

DEFF Research Database (Denmark)

Fristrup, Peter; Le Quement, Sebastian; Tanner, David Ackland

2004-01-01

The regioselectivity in the cationic Heck reaction of 4-substituted styrenes was addressed by a Hammett study. In this branching reaction, plots based on the substrate reactivity did not give meaningful data, whereas the product distribution was variable due to differing preferences for further...

Gas-Phase Infrared Spectra of Vinyl Selenol and Vinyl Tellurol

Science.gov (United States)

Benidar, Abdessamad; Khater, Brahim; Guillemin, Jean-Claude; Gámez, José A.; Yáñez, Manuel

2009-10-01

The infrared spectra (3500-500 cm-1) of gaseous vinyl selenol and vinyl tellurol have been recorded at 0.1 cm-1 resolution. For the latter the spectra were obtained at room temperature, but for the former a temperature of -40 °C was required because of the chemical instability of vinyl selenol at room temperature. To compensate the very weak vapor pressure of vinyl tellurol at room temperature, a long optical path up to 136 m was necessary to record its spectrum. B3LYP density functional theory (DFT) calculations have been performed to assign the different absorption bands. Since an unambiguous assignment of the absorption bands requires a precise knowledge on the relative abundance of the syn and gauche rotamers of these compounds, their relative energies and their anharmonic vibrational frequencies were obtained using a very extended Def2-QZVP basis set. Two rotamers, the syn, which is planar, and a nonplanar gauche, were found to be local minima for both compounds. The gauche rotamer presents two degenerate conformers, which differ by the position of the SeH (TeH) hydrogen atom above or below the molecular plane. Our theoretical results are in good agreement with the main features of the experimental spectra. Fundamental bands and some combination bands of vinyl selenol and vinyl tellurol were assigned and compared with those of vinyl alcohol and vinyl thiol, whose spectra had been reported previously in the literature.

R-matrix arising from affine Hecke algebras and its application to Macdonald's difference operators

International Nuclear Information System (INIS)

Kato, Shinichi

1994-01-01

We shall give a certain trigonometric R-matrix associated with each root system by using affine Hecke algebras. From this R-matrix, we derive a quantum Knizhnik-Zamolodchikov equation after Cherednik, and show that the solutions of this KZ equation yield eigenfunctions of Macdonald's difference operators. (orig.)

Studies on the Simultaneous Formation of Aroma-Active and Toxicologically Relevant Vinyl Aromatics from Free Phenolic Acids during Wheat Beer Brewing.

Science.gov (United States)

Langos, Daniel; Granvogl, Michael

2016-03-23

During the brewing process of wheat beer, the desired aroma-active vinyl aromatics 2-methoxy-4-vinylphenol and 4-vinylphenol as well as the undesired and toxicologically relevant styrene are formed from their respective precursors, free ferulic acid, p-coumaric acid, and cinnamic acid, deriving from the malts. Analysis of eight commercial wheat beers revealed high concentrations of 2-methoxy-4-vinylphenol and 4-vinylphenol always in parallel with high concentrations of styrene or low concentrations of the odorants in parallel with low styrene concentrations, suggesting a similar pathway. To better understand the formation of these vinyl aromatics, each process step of wheat beer brewing and the use of different strains of Saccharomyces cerevisiae were evaluated. During wort boiling, only a moderate decarboxylation of free phenolic acids and formation of desired and undesired vinyl aromatics were monitored due to the thermal treatment. In contrast, this reaction mainly occurred enzymatically catalyzed during fermentation with S. cerevisiae strain W68 with normal Pof(+) activity (phenolic off-flavor) resulting in a wheat beer eliciting the typical aroma requested by consumers due to high concentrations of 2-methoxy-4-vinylphenol (1790 μg/L) and 4-vinylphenol (937 μg/L). Unfortunately, also a high concentration of undesired styrene (28.3 μg/L) was observed. Using a special S. cerevisiae strain without Pof(+) activity resulted in a significant styrene reduction (beer aroma.

Two-rowed Hecke algebra representations at roots of unity

International Nuclear Information System (INIS)

Welsh, T.A.

1996-01-01

The explicit construction of irreducible representations of the Hecke algebra H n (q) of type A n-1 was studied for the non-generic case where q is a root of unity. The approach is via the Specht modules of H n (q) which are irreducible in the generic case and possess a natural basis indexed by Young tableaux. The general framework in which the non-generic H n (q)-modules are to be constructed is set up and, in particular, the full set of modules corresponding to two-part partitions is described. Many examples are given. 12 refs

Regiospecific decarboxylative allylation of nitriles

Science.gov (United States)

Recio, Antonio; Tunge, Jon A.

2009-01-01

Palladium-catalyzed decarboxylative α-allylation of nitriles readily occurs using Pd2(dba)3 and rac-BINAP. This catalyst mixture also allows the highly regiospecific α-allylation of nitriles in the presence of much more acidic α-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement. PMID:19921827

Decarboxylation-based traceless linking with aroyl acrylic acids

DEFF Research Database (Denmark)

Nielsen, John

1998-01-01

beta-Keto carboxylic acids are known to decarboxylate readily. In our pursuit to synthesize beta-indolinyl propiophenones, we have exploited this chemistry as a mean of establishing a traceless handle. 2-Aroyl acrylic acids have been esterified to a trityl resin, after which Michael-type addition...

Decarboxylation Study of Acidic Cannabinoids: A Novel Approach Using Ultra-High-Performance Supercritical Fluid Chromatography/Photodiode Array-Mass Spectrometry

Science.gov (United States)

Wang, Mei; Wang, Yan-Hong; Avula, Bharathi; Radwan, Mohamed M.; Wanas, Amira S.; van Antwerp, John; Parcher, Jon F.; ElSohly, Mahmoud A.; Khan, Ikhlas A.

2016-01-01

Abstract Introduction: Decarboxylation is an important step for efficient production of the major active components in cannabis, for example, Δ9-tetrahydrocannabinol (Δ9-THC), cannabidiol (CBD), and cannabigerol (CBG). These cannabinoids do not occur in significant concentrations in cannabis but can be formed by decarboxylation of their corresponding acids, the predominant cannabinoids in the plant. Study of the kinetics of decarboxylation is of importance for phytocannabinoid isolation and dosage formulation for medical use. Efficient analytical methods are essential for simultaneous detection of both neutral and acidic cannabinoids. Methods: C. sativa extracts were used for the studies. Decarboxylation conditions were examined at 80°C, 95°C, 110°C, 130°C, and 145°C for different times up to 60 min in a vacuum oven. An ultra-high performance supercritical fluid chromatography/photodiode array-mass spectrometry (UHPSFC/PDA-MS) method was used for the analysis of acidic and neutral cannabinoids before and after decarboxylation. Results: Decarboxylation at different temperatures displayed an exponential relationship between concentration and time indicating a first-order or pseudo-first-order reaction. The rate constants for Δ9-tetrahydrocannabinolic acid-A (THCA-A) were twice those of the cannabidiolic acid (CBDA) and cannabigerolic acid (CBGA). Decarboxylation of THCA-A was forthright with no side reactions or by-products. Decarboxylation of CBDA and CBGA was not as straightforward due to the unexplained loss of reactants or products. Conclusion: The reported UHPSFC/PDA-MS method provided consistent and sensitive analysis of phytocannabinoids and their decarboxylation products and degradants. The rate of change of acidic cannabinoid concentrations over time allowed for determination of rate constants. Variations of rate constants with temperature yielded values for reaction energy. PMID:28861498

Regularized inner products and weakly holomorphic Hecke eigenforms

Science.gov (United States)

Bringmann, Kathrin; Kane, Ben

2018-01-01

We show that the image of repeated differentiation on weak cusp forms is precisely the subspace which is orthogonal to the space of weakly holomorphic modular forms. This gives a new interpretation of weakly holomorphic Hecke eigenforms. The research of the first author is supported by the Alfried Krupp Prize for Young University Teachers of the Krupp foundation and the research leading to these results receives funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013) / ERC Grant agreement n. 335220—AQSER. The research of the second author was supported by grants from the Research Grants Council of the Hong Kong SAR, China (project numbers HKU 27300314, 17302515, and 17316416).

Encaging palladium(0 in layered double hydroxide: A sustainable catalyst for solvent-free and ligand-free Heck reaction in a ball mill

Directory of Open Access Journals (Sweden)

Wei Shi

2017-08-01

Full Text Available In this paper, the synthesis of a cheap, reusable and ligand-free Pd catalyst supported on MgAl layered double hydroxides (Pd/MgAl-LDHs by co-precipitation and reduction methods is described. The catalyst was used in Heck reactions under high-speed ball milling (HSBM conditions at room temperature. The effects of milling-ball size, milling-ball filling degree, reaction time, rotation speed and grinding auxiliary category, which would influence the yields of mechanochemical Heck reactions, were investigated in detail. The characterization results of XRD, ICP–MS and XPS suggest that Pd/MgAl-LDHs have excellent textural properties with zero-valence Pd on its layers. The reaction results indicate that the catalyst could be utilized in HSBM systems to afford a wide range of Heck coupling products in satisfactory yields. Furthermore, this catalyst could be easily recovered and reused for at least five times without significant loss of catalytic activity.

Vinyl Record

DEFF Research Database (Denmark)

Bartmanski, Dominik; Woodward, Ian

2018-01-01

. This relational process means that both the material affordances and entanglements of vinyl allow us to feel, handle, experience, project, and share its iconicity. The materially mediated meanings of vinyl enabled it to retain currency in independent and collector’s markets and thus resist the planned......In this paper, we use the case of the vinyl record to show that iconic objects become meaningful via a dual process. First, they offer immersive engagements which structure user interpretations through various material experiences of handling, use, and extension. Second, they always work via...

Design, Testing and Kinetic Analysis of Bulky Monodentate Phosphorus Ligands in the Mizoroki-Heck Reaction

NARCIS (Netherlands)

Dodds, Deborah L.; Boele, Maarten D. K.; van Strijdonck, Gino P. F.; de Vries, Johannes G.; van Leeuwen, Piet W. N. M.; Kamer, Paul C. J.

A series of new monodentate phosphane ligands 2 have been evaluated in the MizorokiHeck arylation reaction of iodobenzene and styrene and compared with our previously reported ligands, 1, 3 and 4. The concept of rational ligand design is discussed, and we describe how the performance of this new

Palladium(II-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

Directory of Open Access Journals (Sweden)

Tanveer Mahamadali Shaikh

2013-08-01

Full Text Available A series of general and selective Pd(II-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO ligated palladium complex (6 as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety of substrates, both electron-rich and electron-poor olefins, were converted smoothly to the targeted products in high yields. Compared with the existing approaches employing SPO–Pd complexes in a Heck reaction, the current strategy features mild reaction conditions and broad substrate scope. Furthermore, we described the coupling of arylboronic acids with olefins, which were catalyzed by Pd(OAc2 and employed N-bromosuccinimide as an additive under ambient conditions. The resulted biaryls have been obtained in moderate to good yields.

Carbonylative Heck Reactions Using CO Generated ex Situ in a Two-Chamber System

DEFF Research Database (Denmark)

Hermange, Philippe; Gøgsig, Thomas; Lindhardt, Anders Thyboe

2011-01-01

A carbonylative Heck reaction of aryl iodides and styrene derivatives employing a two-chamber system using a stable, crystalline, and nontransition metal based carbon monoxide source is reported. By applying near-stoichiometric amounts of the carbon monoxide precursor, an effective exploitation o...... of the hazardous CO gas is obtained affording chalcone derivatives in good yields. Application to isotope labeling, incorporating 13CO, was further established....

Decarboxylation of Δ 9-tetrahydrocannabinol: Kinetics and molecular modeling

Science.gov (United States)

Perrotin-Brunel, Helene; Buijs, Wim; van Spronsen, Jaap; van Roosmalen, Maaike J. E.; Peters, Cor J.; Verpoorte, Rob; Witkamp, Geert-Jan

2011-02-01

Efficient tetrahydrocannabinol (Δ 9-THC) production from cannabis is important for its medical application and as basis for the development of production routes of other drugs from plants. This work presents one of the steps of Δ 9-THC production from cannabis plant material, the decarboxylation reaction, transforming the Δ 9-THC-acid naturally present in the plant into the psychoactive Δ 9-THC. Results of experiments showed pseudo-first order reaction kinetics, with an activation barrier of 85 kJ mol -1 and a pre-exponential factor of 3.7 × 10 8 s -1. Using molecular modeling, two options were identified for an acid catalyzed β-keto acid type mechanism for the decarboxylation of Δ 9-THC-acid. Each of these mechanisms might play a role, depending on the actual process conditions. Formic acid proved to be a good model for a catalyst of such a reaction. Also, the computational idea of catalysis by water to catalysis by an acid, put forward by Li and Brill, and Churchev and Belbruno was extended, and a new direct keto-enol route was found. A direct keto-enol mechanism catalyzed by formic acid seems to be the best explanation for the observed activation barrier and the pre-exponential factor of the decarboxylation of Δ 9-THC-acid. Evidence for this was found by performing an extraction experiment with Cannabis Flos. It revealed the presence of short chain carboxylic acids supporting this hypothesis. The presented approach is important for the development of a sustainable production of Δ 9-THC from the plant.

Nekrasov and Argyres–Douglas theories in spherical Hecke algebra representation

Energy Technology Data Exchange (ETDEWEB)

Rim, Chaiho, E-mail: rimpine@sogang.ac.kr; Zhang, Hong, E-mail: kilar@itp.ac.cn

2017-06-15

AGT conjecture connects Nekrasov instanton partition function of 4D quiver gauge theory with 2D Liouville conformal blocks. We re-investigate this connection using the central extension of spherical Hecke algebra in q-coordinate representation, q being the instanton expansion parameter. Based on AFLT basis together with intertwiners we construct gauge conformal state and demonstrate its equivalence to the Liouville conformal state, with careful attention to the proper scaling behavior of the state. Using the colliding limit of regular states, we obtain the formal expression of irregular conformal states corresponding to Argyres–Douglas theory, which involves summation of functions over Young diagrams.

Nekrasov and Argyres-Douglas theories in spherical Hecke algebra representation

Science.gov (United States)

Rim, Chaiho; Zhang, Hong

2017-06-01

AGT conjecture connects Nekrasov instanton partition function of 4D quiver gauge theory with 2D Liouville conformal blocks. We re-investigate this connection using the central extension of spherical Hecke algebra in q-coordinate representation, q being the instanton expansion parameter. Based on AFLT basis together with intertwiners we construct gauge conformal state and demonstrate its equivalence to the Liouville conformal state, with careful attention to the proper scaling behavior of the state. Using the colliding limit of regular states, we obtain the formal expression of irregular conformal states corresponding to Argyres-Douglas theory, which involves summation of functions over Young diagrams.

Citrus Peel Additives for One-Pot Triazole Formation by Decarboxylation, Nucleophilic Substitution, and Azide-Alkyne Cycloaddition Reactions

Science.gov (United States)

Mendes, Desiree E.; Schoffstall, Allen M.

2011-01-01

This undergraduate organic laboratory experiment consists of three different reactions occurring in the same flask: a cycloaddition reaction, preceded by decarboxylation and nucleophilic substitution reactions. The decarboxylation and cycloaddition reactions occur using identical Cu(I) catalyst and conditions. Orange, lemon, and other citrus fruit…

Silica supported palladium nanoparticles for the decarboxylation of high-acid feedstocks: Design, deactivation and regeneration

Science.gov (United States)

Ping, Eric Wayne

2011-12-01

The major goals of this thesis were to (1) design and synthesize a supported catalyst with well-defined monodisperse palladium nanoparticles evenly distributed throughout an inorganic oxide substrate with tunable porosity characteristics, (2) demonstrate the catalytic activity of this material in the decarboxylation of long chain fatty acids and their derivatives to make diesel-length hydrocarbons, (3) elucidate the deactivation mechanism of supported palladium catalysts under decarboxylation conditions via post mortem catalyst characterization and develop a regeneration methodology thereupon, and (4) apply this catalytic system to a real low-value biofeedstock. Initial catalyst designs were based on the SBA-15 silica support, but in an effort to maximize loading and minimize mass transfer limitations, silica MCF was synthesized as catalyst support. Functionalization with various silane ligands yielded a surface that facilitated even distribution of palladium precursor salts throughout the catalyst particle, and, after reduction, monodisperse palladium nanoparticles approximately 2 nm in diameter. Complete characterization was performed on this Pd-MCF catalyst. The Pd-MCF catalyst showed high one-time activity in the decarboxylation of fatty acids to hydrocarbons in dodecane at 300°C. Hydrogen was found to be an unnecessary reactant in the absence of unsaturations, but was required in their presence---full hydrogenation of the double bonds occurs before any decarboxylation can take place. The Pd-MCF also exhibited good activity for alkyl esters and glycerol, providing a nice hypothetical description of a stepwise reaction pathway for catalytic decarboxylation of acids and their derivatives. As expected, the Pd-MCF catalyst experienced severe deactivation after only one use. Substantial effort was put into elucidating the nature of this deactivation via post mortem catalyst characterization. H2 chemisorption confirmed a loss of active surface area, but TEM and

FACTORS AFFECTED DECARBOXYLATION ACTIVITY OF ENTEROCOCCUS FAECIUM ISOLATED FROM RABBIT

Directory of Open Access Journals (Sweden)

František Buňka

2012-04-01

Full Text Available Normal 0 21 false false false SK JA X-NONE Biogenic amines (BA are basic nitrogenous compounds formed mainly by decarboxylation of amino acids. There are generated in course of microbial, vegetable and animal metabolisms. The aim of the study was to monitor factors affected production of biogenic amines by Enterococcus faecium, which is found in rabbit meat. Biogenic amines were analyzed by means of UPLC (ultrahigh performance liquid chromatography equipped with a UV/VIS DAD detector. Decarboxylation activity of E. faecium was mainly influenced by the cultivation temperature and the amount of NaCl in this study. E. faecium produced most of the monitored biogenic amines levels: tyramine ˂2500 mg.l-1; putrescine ˂30 mg.l-1; spermidine ˂10 mg.l-1 and cadaverine ˂5 mg.l-1.doi:10.5219/182

Preparation and Characterization of Pd Modified TiO2 Nanofiber Catalyst for Carbon–Carbon Coupling Heck Reaction

Directory of Open Access Journals (Sweden)

Leah O. Nyangasi

2017-01-01

Full Text Available TiO2 fibers were prepared through electrospinning of poly methyl methacrylate (PMMA and titanium isopropoxide (TIP solution followed by calcination of fibers in air at 500°C. Cetyltrimethylammonium bromide (CTAB protected palladium nanoparticles (Pd NPs prepared through reduction method were successfully adsorbed on the TiO2 nanofibers (NF. Combined studies of X-ray diffraction (XRD, scanning electron microscope (SEM, and transmission electron microscope (TEM indicated that the synthesized Pd/TiO2 had anatase. BET indicated that the synthesized TiO2 and Pd/TiO2 had a surface area of 53.4 and 43.4 m2/g, respectively. The activity and selectivity of 1 mol% Pd/TiO2 in the Heck reaction have been investigated towards the Mizoroki-Heck carbon–carbon cross-coupling of bromobenzene (ArBr and styrene. Temperature, time, solvent, and base were optimized and catalyst was recycled thrice. 1H NMR and 13C NMR indicated that stilbene, a known compound from literature, was obtained in various Heck reactions at temperatures between 100°C and 140°C but the recyclability was limited due to some palladium leaching and catalyst poisoning which probably arose from some residual carbon from the polymer. The catalyst was found to be highly active under air atmosphere with reaction temperatures up to 140°C. Optimized reaction condition resulted in 89.7% conversions with a TON of 1993.4 and TOF value of 332.2 hr−1.

Copper-catalyzed decarboxylative trifluoromethylation of allylic bromodifluoroacetates.

Science.gov (United States)

Ambler, Brett R; Altman, Ryan A

2013-11-01

The development of new synthetic fluorination reactions has important implications in medicinal, agricultural, and materials chemistries. Given the prevalence and accessibility of alcohols, methods to convert alcohols to trifluoromethanes are desirable. However, this transformation typically requires four-step processes, specialty chemicals, and/or stoichiometric metals to access the trifluoromethyl-containing product. A two-step copper-catalyzed decarboxylative protocol for converting allylic alcohols to trifluoromethanes is reported. Preliminary mechanistic studies distinguish this reaction from previously reported Cu-mediated reactions.

Preparation of Thermoplastic Poly (vinyl Alcohol), Ethylene Vinyl Acetate and Vinyl Acetate Versatic Ester Blends for Exterior Masonry Coating

International Nuclear Information System (INIS)

EL-Nahas, H.H.; Gad, Y.H.; Magida, M.M.

2013-01-01

Blend systems including ethylene vinyl acetate (EVA), poly (vinyl alcohol) (PVA) and vinyl acetate versatic copolymer latex (VAcVe) were prepared and used as exterior coatings. Mechanical and thermal properties of the blends were investigated using a testo meter, shore hardness tester, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The water resistance of the samples was measured. Effect of ionizing irradiation on gel content, tensile strength and surface hardness were also followed. The blend offers binder base for exterior masonry coating systems having superior water resistant and mechanical properties

21 CFR 177.1970 - Vinyl chloride-lauryl vinyl ether copolymers.

Science.gov (United States)

2010-04-01

... in powder form having a particle size such that 100 percent will pass through a U.S. Standard Sieve No. 40 and such that not more than 10 percent will pass through a U.S. Standard Sieve No. 200. (1... analysis. (e) Other specifications and limitations. The vinyl chloride-lauryl vinyl ether copolymers...

Diphosphinoazine Palladium(II) Complexes as Catalysts for the Heck Reaction of Bromides and an Activated Chloride

Czech Academy of Sciences Publication Activity Database

Včelák, Jaroslav; Storch, Jan; Czakoová, Marie; Čermák, Jan

2004-01-01

Roč. 222, 1-2 (2004), s. 121-126 ISSN 1381-1169 R&D Projects: GA ČR GA203/01/0554; GA AV ČR IAA4072205 Institutional research plan: CEZ:AV0Z4072921 Keywords : heck reaction * amido complex es * palladium Subject RIV: CA - Inorganic Chemistry Impact factor: 2.316, year: 2004

Graft polymerization of vinyl acetate onto starch. Saponification to starch-g-poly(vinyl alcohol)

International Nuclear Information System (INIS)

Fanta, G.F.; Burr, R.C.; Doane, W.M.; Russell, C.R.

1979-01-01

Graft polymerizations of vinyl acetate onto granular cornstarch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinyl acetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. Over half of the polymer was present as ungrafted poly(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficency. Grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate--methyl methacrylate was carried out near 0 0 C; although conversion of monomers to polymer was low and grafted polymer contained 40 to 50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch-g-poly(vinyl acetate) to starch-g-poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch-g-poly(vinyl alcohol) in hot water was less than 50; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch-g-poly

Pharmacokinetics of vinyl chloride in the rat

International Nuclear Information System (INIS)

Bolt, H.M.; Laib, R.J.; Kappus, H.; Buchter, A.

1977-01-01

When rats are exposed to [ 14 C]vinyl chloride in a closed system, the vinyl chloride present in the atmosphere equilibrates with the animals' organism within 15 min. The course of equilibration could be determined using rats which had been given 6-nitro-1,2,3-benzothiadiazole. This compound completely blocks metabolism of vinyl chloride. The enzymes responsible for metabolism of vinyl chloride are saturated at an atmospheric concentration of vinyl chloride of 250 ppm. Pharmacokinetic analysis shows that no significant cumulation of vinyl chloride or its major metabolites is to be expected on repeated administration of vinyl chlorides. This may be consistent with the theory that a reactive, shortly living metabolite which occurs in low concentration only, may be responsible for the toxic effects of vinyl chloride

Hydrocarbon fuels from gas phase decarboxylation of hydrolyzed free fatty acid

KAUST Repository

Wang, Weicheng; Roberts, William L.; Stikeleather, Larry F.

2012-01-01

Gas phase decarboxylation of hydrolyzed free fatty acid (FFA) from canola oil has beeninvestigated in two fix-bed reactors by changing reaction parameters such as temperatures,FFA feed rates, and H 2-to-FFA molar ratios. FFA, which contains mostly C

Spherical Hecke algebra in the Nekrasov-Shatashvili limit

Energy Technology Data Exchange (ETDEWEB)

Bourgine, Jean-Emile [Asia Pacific Center for Theoretical Physics (APCTP),Pohang, Gyeongbuk 790-784 (Korea, Republic of)

2015-01-21

The Spherical Hecke central (SHc) algebra has been shown to act on the Nekrasov instanton partition functions of N=2 gauge theories. Its presence accounts for both integrability and AGT correspondence. On the other hand, a specific limit of the Omega background, introduced by Nekrasov and Shatashvili (NS), leads to the appearance of TBA and Bethe like equations. To unify these two points of view, we study the NS limit of the SHc algebra. We provide an expression of the instanton partition function in terms of Bethe roots, and define a set of operators that generates infinitesimal variations of the roots. These operators obey the commutation relations defining the SHc algebra at first order in the equivariant parameter ϵ{sub 2}. Furthermore, their action on the bifundamental contributions reproduces the Kanno-Matsuo-Zhang transformation. We also discuss the connections with the Mayer cluster expansion approach that leads to TBA-like equations.

A Class of Effective of Decarboxylative Perfluoroalkylating Reagents: [(phen)2Cu](O2CRF)

KAUST Repository

Huang, Yangjie; Ajitha, Manjaly John; Huang, Kuo-Wei; Zhang, Zhongxing; Weng, Zhiqiang

2016-01-01

This article describes the invention of a class of effective reagents [(phen)2Cu](O2CRF) (1) for the decarboxylative perfluoroalkylation of aryl and heteroaryl halides. Treatment of the copper tert-butyloxide with phenanthroline ligands, with subsequent addition of perfluorocarboxylic acids afforded the air-stable copper(I) perfluorocarboxylato complexes 1. These complexes reacted with a variety of aryl and heteroaryl halides to form perfluoroalkyl(hetero)arenes in moderate to high yields. Computational studies suggested that the coordination of the second phen ligand may reduce the energy barrier for the decarboxylation of perfluorocarboxylate to facilitate the perfluoroalkylation.

A Class of Effective of Decarboxylative Perfluoroalkylating Reagents: [(phen)2Cu](O2CRF)

KAUST Repository

Huang, Yangjie

2016-04-13

This article describes the invention of a class of effective reagents [(phen)2Cu](O2CRF) (1) for the decarboxylative perfluoroalkylation of aryl and heteroaryl halides. Treatment of the copper tert-butyloxide with phenanthroline ligands, with subsequent addition of perfluorocarboxylic acids afforded the air-stable copper(I) perfluorocarboxylato complexes 1. These complexes reacted with a variety of aryl and heteroaryl halides to form perfluoroalkyl(hetero)arenes in moderate to high yields. Computational studies suggested that the coordination of the second phen ligand may reduce the energy barrier for the decarboxylation of perfluorocarboxylate to facilitate the perfluoroalkylation.

Enhancement in the Catalytic Activity of Pd/USY in the Heck Reaction Induced by H2 Bubbling

Directory of Open Access Journals (Sweden)

Miki Niwa

2010-12-01

Full Text Available Pd was loaded on ultra stable Y (USY zeolites prepared by steaming NH4-Y zeolite under different conditions. Heck reactions were carried out over the prepared Pd/USY. We found that H2 bubbling was effective in improving not only the catalytic activity of Pd/USY, but also that of other supported Pd catalysts and Pd(OAc2. Moreover, the catalytic activity of Pd/USY could be optimized by choosing appropriate steaming conditions for the preparation of the USY zeolites; Pd loaded on USY prepared at 873 K with 100% H2O gave the highest activity (TOF = 61,000 h−1, which was higher than that of Pd loaded on other kinds of supports. The prepared Pd/USY catalysts were applicable to the Heck reactions using various kinds of substrates including bromo- and chloro-substituted aromatic and heteroaromatic compounds. Characterization of the acid properties of the USY zeolites revealed that the strong acid site (OHstrong generated as a result of steaming had a profound effect on the catalytic activity of Pd.

Enhancement in the catalytic activity of Pd/USY in the heck reaction induced by H2 bubbling.

Science.gov (United States)

Okumura, Kazu; Tomiyama, Takuya; Moriyama, Sayaka; Nakamichi, Ayaka; Niwa, Miki

2010-12-24

Pd was loaded on ultra stable Y (USY) zeolites prepared by steaming NH(4)-Y zeolite under different conditions. Heck reactions were carried out over the prepared Pd/USY. We found that H₂ bubbling was effective in improving not only the catalytic activity of Pd/USY, but also that of other supported Pd catalysts and Pd(OAc)₂. Moreover, the catalytic activity of Pd/USY could be optimized by choosing appropriate steaming conditions for the preparation of the USY zeolites; Pd loaded on USY prepared at 873 K with 100% H₂O gave the highest activity (TOF = 61,000 h⁻¹), which was higher than that of Pd loaded on other kinds of supports. The prepared Pd/USY catalysts were applicable to the Heck reactions using various kinds of substrates including bromo- and chloro-substituted aromatic and heteroaromatic compounds. Characterization of the acid properties of the USY zeolites revealed that the strong acid site (OH(strong)) generated as a result of steaming had a profound effect on the catalytic activity of Pd.

Alanine/epr pellet dosimeter using poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) copolymer as a binder for radiation dosimetry

International Nuclear Information System (INIS)

Beshir, W.B.; Ezz El-Din, H.M.; Abdel-fatth, A.A.; Ebraheem, S.

2005-01-01

A new alanine pellet dosimeter was developed for gamma and electron beam radiation dosimetry. Alanine powder was mixed with a new binding material, poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) copolymer. Pellets were prepared by pressing fine powder alanine with 60% copolymer binder by using hydraulic press and a specially designed pressing die. The radiation-formed stable free radicals were analysed by using electron paramagnetic resonance (EPR) spectroscopy. The useful dose range of these pellets was found to ranges from 1 to 80 kGy. The stability of the radiation- induced response was also studied

Microbial reductive dehalogenation of vinyl chloride

Science.gov (United States)

Spormann, Alfred M [Stanford, CA; Muller, Jochen A [Baltimore, MD; Rosner, Bettina M [Berlin, DE; Von Abendroth, Gregory [Nannhein, DE; Meshulam-Simon, Galit [Los Altos, CA; McCarty, Perry L [Stanford, CA

2011-11-22

Compositions and methods are provided that relate to the bioremediation of chlorinated ethenes, particularly the bioremediation of vinyl chloride by Dehalococcoides-like organisms. An isolated strain of bacteria, Dehalococcoides sp. strain VS, that metabolizes vinyl chloride is provided; the genetic sequence of the enzyme responsible for vinyl chloride dehalogenation; methods of assessing the capability of endogenous organisms at an environmental site to metabolize vinyl chloride; and a method of using the strains of the invention for bioremediation.

Decarboxylative Hydroalkylation of Alkynes.

Science.gov (United States)

Till, Nicholas A; Smith, Russell T; MacMillan, David W C

2018-05-02

The merger of open- and closed-shell elementary organometallic steps has enabled the selective intermolecular addition of nucleophilic radicals to unactivated alkynes. A range of carboxylic acids can be subjected to a CO 2 extrusion, nickel capture, migratory insertion sequence with terminal and internal alkynes to generate stereodefined functionalized olefins. This platform has been further extended, via hydrogen atom transfer, to the direct vinylation of unactivated C-H bonds. Preliminary studies indicate that a Ni-alkyl migratory insertion is operative.

Group characters, symmetric functions, and the Hecke algebra

CERN Document Server

Goldschmidt, David M

1993-01-01

Directed at graduate students and mathematicians, this book covers an unusual set of interrelated topics, presenting a self-contained exposition of the algebra behind the Jones polynomial along with various excursions into related areas. The book is made up of lecture notes from a course taught by Goldschmidt at the University of California at Berkeley in 1989. The course was organized in three parts. Part I covers, among other things, Burnside's Theorem that groups of order p^aq^b are solvable, Frobenius' Theorem on the existence of Frobenius kernels, and Brauer's characterization of characters. Part II covers the classical character theory of the symmetric group and includes an algorithm for computing the character table of S^n ; a construction of the Specht modules; the "determinant form" for the irreducible characters; the hook-length formula of Frame, Robinson, and Thrall; and the Murnaghan-Nakayama formula. Part III covers the ordinary representation theory of the Hecke algebra, the construction of the ...

Unusual selectivity-determining factors in the phosphine-free Heck arylation of allyl ethers

DEFF Research Database (Denmark)

Ambrogio, I.; Fabrizi, G.; Cacchi, S.

2008-01-01

The Heck reaction of aryl iodides and bromides with allyl ethers has been investigated. Using phosphinefree Pd(OAc)(2) in DNIF at 90 degrees C in the presence of Bu4NOAc, the reaction gave cinnamyl derivatives, usually in good to high yields, with a wide range of aryl halides. The reaction...... tolerates a variety of functional groups, including ether, amide, alcohol, aldehyde, ketone, ester, cyano, carboxylic acid, and nitro groups. Ortho-substituted arylating agents afforded moderate yields in some cases, though good to high yields were obtained with o-iodotoluene, iodovanillin, and 1...

A Family of Finite-Dimensional Representations of Generalized Double Affine Hecke Algebras of Higher Rank

Science.gov (United States)

Fu, Yuchen; Shelley-Abrahamson, Seth

2016-06-01

We give explicit constructions of some finite-dimensional representations of generalized double affine Hecke algebras (GDAHA) of higher rank using R-matrices for U_q(sl_N). Our construction is motivated by an analogous construction of Silvia Montarani in the rational case. Using the Drinfeld-Kohno theorem for Knizhnik-Zamolodchikov differential equations, we prove that the explicit representations we produce correspond to Montarani's representations under a monodromy functor introduced by Etingof, Gan, and Oblomkov.

Radiation-induced cationic curing of vinyl ethers

International Nuclear Information System (INIS)

Lapin, S.C.

1992-01-01

Recently there has been an increasing interest in nonacrylate radiation-curable coatings. Vinyl ethers are particularly reactive under cationic polymerization reaction conditions. The high efficiency of the photoacid initiators combined with the high reactivity of vinyl ether monomers makes this a potentially very useful system. This chapter discusses the preparation of vinyl ethers, introduces vinyl ether-functional monomers and oligomers, describes radiation-induced cationic polymerization of vinyl ethers, and discusses various coating systems. Throughout the chapter, an emphasis is placed on radiation-curable coating applications. 64 refs., 5 figs., 11 tabs

Gamma radiolysis and vinyl esters

International Nuclear Information System (INIS)

De Bruyn, H.; Balic, R.; Gilbert, R.G.

1998-01-01

The principle behind γ relaxation of free-radical polymerizations is that the source of initiating radicals can be switched off 'instantaneously'. In the absence of initiating radicals the only kinetic events remaining are propagation, transfer and termination. For monomers whose propagation rate coefficients have been determined, relaxation behaviour can be interpreted to determine radical-loss rate coefficients and test models of loss mechanisms. This technique has been employed successfully on styrene and MMA emulsion polymerizations. In the present study, vinyl acetate and vinyl neo-decanoate (a ten-carbon-branched homologue of vinyl acetate) were studied, with the propagation rate coefficients for both monomers being established by pulsed-laser polymerization. Both were found to exhibit rapid γ relaxation rates in emulsion polymerization. This is a surprising result because mechanisms for rapid relaxation in emulsion polymerizations require that chain transfer to monomer (which is rapid for both monomers) is followed by exit from the particle into the aqueous phase with subsequent re-entry into a radical-containing particle leading to bimolecular termination. It is not unreasonable to suppose that this may be possible for vinyl acetate which is fairly water soluble (∼0.3 M). However, vinyl neo-decanoate is virtually insoluble (∼0.00004 M) and hence desorption is extremely unlikely. The most likely explanation for the observed rapid relaxations is that some of the radicals produced by γ radiolysis are slow to initiate vinyl esters and hence act as radical traps. As vinyl esters are known to be particularly unreactive monomers. it is feasible that this experimental artifact affects them to a much greater extent than some of the monomers studied successfully with this technique in the past

Preparation of Syndiotactic Poly(vinyl alcohol)/Poly(vinyl pivalate/vinyl acetate) Microspheres with Radiopacity Using Suspension Copolymerization and Saponification

Science.gov (United States)

Seok Lyoo, Won; Wook Cha, Jin; Young Kwak, Kun; Jae Lee, Young; Yong Jeon, Han; Sik Chung, Yong; Kyun Noh, Seok

2010-06-01

To prepare Poly(vinyl pivalate/vinyl acetate) [P(VPi/VAc)] microspheres with radiopacity, the suspension copolymerization approach in the presence of aqueous radiopaque nanoparticles was used. After, The P(VPi/VAc) microspheres with radiopacity were saponified in heterogeneous system, and then P(VPi/VAc) microspheres without aggregates were converted to s-PVA/P(VPi/VAc) microspheres of skin/core structure through the heterogeneous surface saponification. Radiopacity of microspheres was confirmed with Computed tomography (CT).

Green diesel production via catalytic hydrogenation/decarboxylation of triglycerides and fatty acids of vegetable oil and brown grease

Science.gov (United States)

Sari, Elvan

Increase in the petroleum prices, projected increases in the world's energy demand and environmental awareness have shifted the research interest to the alternative fuel technologies. In particular, green diesel, vegetable oil/animal fat/waste oil and grease derived hydrocarbons in diesel boiling range, has become an attractive alternative to biodiesel---a mixture of fatty acid methyl esters, particularly due to its superior fuel properties that are similar to petroleum diesel. Hence, green diesel can be used as a drop-in fuel in the current diesel engines. The current technology for production of green diesel-hydrodeoxygenation of triglycerides and fatty acids over conventional hydrotreating catalysts suffers from fast catalyst deactivation in the absence of hydrogen combined with high temperatures and high fatty acid content in the feedstock. Additionally, excess hydrogen requirement for hydrodeoxygenation technique leads to high production costs. This thesis proposes a new technology-selective decarboxylation of brown grease, which is a mixture of fats and oils collected from waste water trap and rich in fatty acids, over a supported noble metal catalyst that overcomes the green diesel production challenges. In contrast to other feedstocks used for liquid biofuel production, brown grease is inexpensive and non-food competing feedstock, therefore the process finds solution to waste management issues, reduces the renewable fuel production cost and does not add to the global food shortage problems. Special catalyst formulations were developed to have a high activity and stability in the absence of hydrogen in the fatty acid decarboxylation process. The study shows how catalyst innovations can lead to a new technology that overcomes the process challenges. First, the effect of reaction parameters on the activity and the selectivity of brown grease decarboxylation with minimum hydrogen consumption over an activated carbon supported palladium catalyst were

Multicomponent, flow diazotization/Mizoroki-Heck coupling protocol: dispelling myths about working with diazonium salts.

Science.gov (United States)

Nalivela, Kumara S; Tilley, Michael; McGuire, Michael A; Organ, Michael G

2014-05-26

A single pass flow diazotization/Mizoroki-Heck protocol has been developed for the production of cinnimoyl and styryl products. The factors that govern aryl diazonium salt stability have been examined in detail leading to the development of a MeOH/DMF co-solvent system in which the diazonium salts can be generated in the presence of all other reaction components and then coupled selectively to give the desired products. Finally the key role of the reaction quench for flow reactions has been demonstrated. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid Access to Ortho-Alkylated Vinylarenes from Aromatic Acids by Dearomatization and Tandem Decarboxylative C-H Olefination/Rearomatization.

Science.gov (United States)

Tsai, Hung-Chang; Huang, Yen-Hsiang; Chou, Chih-Ming

2018-03-02

A two-step straightforward method for the preparation of ortho-alkylated vinylarenes from readily available benzoic acids is described. The synthetic route involves the dearomatization of benzoic acids by Birch reduction providing alkylated cyclohexa-2,5-dienyl-1-carboxylic acids. The diene subsequently undergoes a decarboxylative C-H olefination followed by rearomatization to deliver ortho-alkylated vinylarene. Mechanistic studies suggest that a Pd/Ag bimetallic catalytic system is important in the tandem decarboxylative C-H olefination/rearomatization step.

Reusable Polymer-Supported Terpyridine Palladium Complex for Suzuki-Miyaura, Mizoroki-Heck, Sonogashira, and Tsuji-Trost Reaction in Water

Directory of Open Access Journals (Sweden)

Takuya Nagamine

2011-03-01

Full Text Available A novel heterogeneous transition-metal catalyst comprising a polymer-supported terpyridine palladium(II complex was prepared and found to promote the Suzuki-Miyaura, Mizoroki-Heck, Sonogashira, and Tsuji-Trost, reactions in water under aerobic conditions with a high to excellent yield. The catalyst was recovered by simple filtration and directly reused several times without loss of catalytic activity.

MECHANICAL PROPERTIES OF BLENDS OF PAMAM DENDRIMERS WITH POLY(VINYL CHLORIDE) AND POLY(VINYL ACETATE)

Science.gov (United States)

Hybrid blends of poly(amidoamine) PAMAM dendrimers with two linear high polymers, poly(vinyl chloride), PVC, and poly(vinyl acetate), PVAc, are reported. The interaction between the blend components was studied using dynamic mechanical analysis, xenon nuclear magnetic resonacne ...

The Effects of Reaction Variables on Solution Polymerization of Vinyl Acetate and Molecular Weight of Poly(vinyl alcohol Using Taguchi Experimental Design

Directory of Open Access Journals (Sweden)

M.H. Navarchian

2009-12-01

Full Text Available Poly(vinyl acetate is synthesized via solution polymerization, and then it is converted to poly(vinyl alcohol by alkaline alcoholysis. The aim of the work study was to investigate statistically the  influence of reaction variables in vinyl acetate polymerization, the conversion of this monomer to polymer, degree of branching of acetyl group in poly(vinyl acetate, as well as the molecular weight of poly(vinyl alcohol, using Taguchi experimental design approach. The reaction variables were polymerization time, molar ratio of initiator to monomer, and volume ratio of monomer to solvent. The statistical analysis of variance of the results revealed that all factors have significantly influenced the conversion and degree of branching. Volume ratio of monomer to solvent is the only factor affecting the molecular weight of poly(vinyl alcohol, and has the greatest influence on all responses. By increasing this ratio, the conversion, degree of branching of acetyl group in poly(vinyl acetate, and molecular weight of poly(vinyl alcohol were increased.

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

International Nuclear Information System (INIS)

Ajji, A.; Ali, A.

2014-03-01

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

Generation of a proton motive force by histidine decarboxylation and electrogenic histidine/histamine antiport in Lactobacillus buchneri.

Science.gov (United States)

Molenaar, D; Bosscher, J S; ten Brink, B; Driessen, A J; Konings, W N

1993-05-01

Lactobacillus buchneri ST2A vigorously decarboxylates histidine to the biogenic amine histamine, which is excreted into the medium. Cells grown in the presence of histidine generate both a transmembrane pH gradient, inside alkaline, and an electrical potential (delta psi), inside negative, upon addition of histidine. Studies of the mechanism of histidine uptake and histamine excretion in membrane vesicles and proteoliposomes devoid of cytosolic histidine decarboxylase activity demonstrate that histidine uptake, histamine efflux, and histidine/histamine exchange are electrogenic processes. Histidine/histamine exchange is much faster than the unidirectional fluxes of these substrates, is inhibited by an inside-negative delta psi and is stimulated by an inside positive delta psi. These data suggest that the generation of metabolic energy from histidine decarboxylation results from an electrogenic histidine/histamine exchange and indirect proton extrusion due to the combined action of the decarboxylase and carrier-mediated exchange. The abundance of amino acid decarboxylation reactions among bacteria suggests that this mechanism of metabolic energy generation and/or pH regulation is widespread.

Antimalarial effects of vinyl sulfone cysteine proteinase inhibitors.

OpenAIRE

Rosenthal, P J; Olson, J E; Lee, G K; Palmer, J T; Klaus, J L; Rasnick, D

1996-01-01

We evaluated the antimalarial effects of vinyl sulfone cysteine proteinase inhibitors. A number of vinyl sulfones strongly inhibited falcipain, a Plasmodium falciparum cysteine proteinase that is a critical hemoglobinase. In studies of cultured parasites, nanomolar concentrations of three vinyl sulfones inhibited parasite hemoglobin degradation, metabolic activity, and development. The antimalarial effects correlated with the inhibition of falcipain. Our results suggest that vinyl sulfones or...

Hecke algebraic properties of dynamical R-matrices. Application to related quantum matrix algebras

International Nuclear Information System (INIS)

Khadzhiivanov, L.K.; Todorov, I.T.; Isaev, A.P.; Pyatov, P.N.; Ogievetskij, O.V.

1998-01-01

The quantum dynamical Yang-Baxter (or Gervais-Neveu-Felder) equation defines an R-matrix R cap (p), where p stands for a set of mutually commuting variables. A family of SL (n)-type solutions of this equation provides a new realization of the Hecke algebra. We define quantum antisymmetrizers, introduce the notion of quantum determinant and compute the inverse quantum matrix for matrix algebras of the type R cap (p) a 1 a 2 = a 1 a 2 R cap. It is pointed out that such a quantum matrix algebra arises in the operator realization of the chiral zero modes of the WZNW model

Ambient gold-catalyzed O-vinylation of cyclic 1,3-diketone: A vinyl ether synthesis

Directory of Open Access Journals (Sweden)

Yumeng Xi

2013-11-01

Full Text Available Gold-catalyzed O-vinylation of cyclic 1,3-diketones has been achieved for the first time, which provides direct access to various vinyl ethers. A catalytic amount of copper triflate was identified as the significant additive in promoting this transformation. Both aromatic and aliphatic alkynes are suitable substrates with good to excellent yields.

Palladium(II/Cationic 2,2’-Bipyridyl System as a Highly Efficient and Reusable Catalyst for the Mizoroki-Heck Reaction in Water

Directory of Open Access Journals (Sweden)

Fu-Yu Tsai

2010-01-01

Full Text Available A water-soluble and air-stable Pd(NH32Cl2/cationic 2,2’-bipyridyl system was found to be a highly-efficient and reusable catalyst for the coupling of aryl iodides and alkenes in neat water using Bu3N as a base. The reaction was conducted at 140 °C in a sealed tube in air with a catalyst loading as low as 0.0001 mol % for the coupling of activated aryl iodides with butyl and ethyl acrylates, providing the corresponding products in good to excellent yields with very high turnover numbers. In the case of styrene, Mizoroki-Heck coupling products were obtained in good to high yields by using a greater catalyst loading (1 mol % and TBAB as a phase-transfer agent. After extraction, the residual aqueous solution could be reused several times with only a slight decrease in its activity, making the Mizoroki-Heck reaction “greener”.

Cyclic aldimines as superior electrophiles for Cu-catalyzed decarboxylative Mannich reaction of β-ketoacids with a broad scope and high enantioselectivity.

Science.gov (United States)

Zhang, Heng-Xia; Nie, Jing; Cai, Hua; Ma, Jun-An

2014-05-02

A novel Cu-catalyzed enantioselective decarboxylative Mannich reaction of cyclic aldimines with β-ketoacids is described. The cyclic structure of these aldimines, in which the C═N bond is constrained in the Z geometry, appears to be important, allowing Mannich condensation to proceed in high yields with excellent enantioselectivities. A chiral chroman-4-amine was synthesized from the decarboxylative Mannich product in several steps without loss of enantioselectivity.

29 CFR 1910.1017 - Vinyl chloride.

Science.gov (United States)

2010-07-01

... employee exposure to vinyl chloride (chloroethene), Chemical Abstracts Service Registry No. 75014. (2) This section applies to the manufacture, reaction, packaging, repackaging, storage, handling or use of vinyl... this section by engineering, work practice, and personal protective controls as follows: (1) Feasible...

Differential calculi on quantum vector spaces with Hecke-type relations

International Nuclear Information System (INIS)

Baez, J.C.

1991-01-01

From a vector space V equipped with a Yang-Baxter operator R one may form the r-symmetric algebra S R V=TV/ , which is a quantum vector space in the sense of Manin, and the associated quantum matrix algebra M R V=T(End(V))/ -1 >. In the case when R satisfies a Hecke-type identity R 2 =(1-q)R+q, we construct a differential calculus Ω R V for S R V which agrees with that constructed by Pusz, Woronowicz, Wess, and Zumino when R is essentially the R-matrix of GL q (n). Elements of Ω R V may be regarded as differential forms on the quantum vector space S R V. We show that Ω R V is M R V-covariant in the sense that there is a coaction Φ * :Ω R V→M R VxΩ R V with Φ * d=(1xd)Φ * extending the natural coaction Φ:S R V→M R VxS R V. (orig.)

21 CFR 177.1350 - Ethylene-vinyl acetate copolymers.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate copolymers. 177.1350 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1350 Ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate copolymers may be safely used as articles or components of articles...

21 CFR 177.1950 - Vinyl chloride-ethylene copolymers.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-ethylene copolymers. 177.1950... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1950 Vinyl chloride-ethylene copolymers. The vinyl chloride-ethylene copolymers identified in paragraph (a) of this section may be safely...

Synthesis and characterisation of polymeric nanofibers poly (vinyl alcohol) and poly (vinyl alcohol)/silica using indigenous electrospinning set up

International Nuclear Information System (INIS)

Sasipriya, K.; Suriyaprabha, R.; Prabu, P.; Rajendran, V.

2013-01-01

Indigenous design and fabrication horizontal of electrospinning set up was developed to facilitate with double drum conveyor belt system to make ease in harvesting nanofibers rapidly. As a bench mark study, organic-inorganic nanofiber composite was synthesised employing our indigenous electrospinning set up. The aqueous solution of poly (vinyl alcohol) and poly (vinyl alcohol)/silica sol were employed to produce nanofiber mats in order to vary the experimental parameters such as voltage, solvent effect and the effect of catalyst. The synthesised pure electro spun poly (vinyl alcohol) and poly (vinyl alcohol)/silica sol fibers were characterized by Scanning electron microscopy (SEM), Atomic force microscopy (AFM) and Fourier transform infra red spectroscopy (FTIR). According to the results, the fine polymeric nanofibers were achieved in the size range of 100-500 nm for pure poly (vinyl alcohol) fiber and 100-700 nm for polyvinyl alcohol/silica and the constitution of silica in rendering better fiber mats with this double drum set up. (author)

Synthesis and characterisation of polymeric nanofibers poly (vinyl alcohol) and poly (vinyl alcohol)/silica using indigenous electrospinning set up

Energy Technology Data Exchange (ETDEWEB)

Sasipriya, K.; Suriyaprabha, R.; Prabu, P.; Rajendran, V., E-mail: veerajendran@gmail.com [Centre for Nanoscience and Technology, K. S. Rangasamy College of Technology, Tamil Nadu (India)

2013-11-01

Indigenous design and fabrication horizontal of electrospinning set up was developed to facilitate with double drum conveyor belt system to make ease in harvesting nanofibers rapidly. As a bench mark study, organic-inorganic nanofiber composite was synthesised employing our indigenous electrospinning set up. The aqueous solution of poly (vinyl alcohol) and poly (vinyl alcohol)/silica sol were employed to produce nanofiber mats in order to vary the experimental parameters such as voltage, solvent effect and the effect of catalyst. The synthesised pure electro spun poly (vinyl alcohol) and poly (vinyl alcohol)/silica sol fibers were characterized by Scanning electron microscopy (SEM), Atomic force microscopy (AFM) and Fourier transform infra red spectroscopy (FTIR). According to the results, the fine polymeric nanofibers were achieved in the size range of 100-500 nm for pure poly (vinyl alcohol) fiber and 100-700 nm for polyvinyl alcohol/silica and the constitution of silica in rendering better fiber mats with this double drum set up. (author)

Synthesis and characterisation of polymeric nanofibers poly (vinyl alcohol and poly (vinyl alcohol/silica using indigenous electrospinning set up

Directory of Open Access Journals (Sweden)

K. Sasipriya

2013-01-01

Full Text Available Indigenous design and fabrication horizontal of electrospinning set up was developed to facilitate with double drum conveyor belt system to make ease in harvesting nanofibers rapidly. As a bench mark study, organic-inorganic nanofiber composite was synthesised employing our indigenous electrospinning set up. The aqueous solution of poly (vinyl alcohol and poly (vinyl alcohol/silica sol were employed to produce nanofiber mats in order to vary the experimental parameters such as voltage, solvent effect and the effect of catalyst. The synthesised pure electro spun poly (vinyl alcohol and poly (vinyl alcohol/silica sol fibers were characterized by Scanning electron microscopy (SEM, Atomic force microscopy (AFM and Fourier transform infra red spectroscopy (FTIR. According to the results, the fine polymeric nanofibers were achieved in the size range of 100-500 nm for pure poly (vinyl alcohol fiber and 100-700 nm for polyvinyl alcohol/silica and the constitution of silica in rendering better fiber mats with this double drum set up.

Mechanism and stem-cell activity of 5-carboxycytosine decarboxylation determined by isotope tracing.

Science.gov (United States)

Schiesser, Stefan; Hackner, Benjamin; Pfaffeneder, Toni; Müller, Markus; Hagemeier, Christian; Truss, Matthias; Carell, Thomas

2012-06-25

Eraserhead: Stem cells seem to erase epigenetic information by decarboxylation of the newly discovered epigenetic base 5-carboxycytosine (caC; see picture). This reaction is likely to involve a nucleophilic attack of the C5-C6 double bond. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Similars of the Retinoic Acid with Anti-Cancer Potential

International Nuclear Information System (INIS)

Marin Cordoba, R.

2001-01-01

Three precursors were synthesized in the route toward new structures similar of the retinoic acid. They are the bromocetones 15, 35 and 36. Two new similar of the retinoic acid were synthesized; they are the acids 39 and 40. The mechanism for the formation of 1,1,4,4-tetramethyl-1, 2,3,4-tetrahydronaphthalene (17), starting from benzene and 2,5-dimethyl-2, 5-dichlorine-hexane was studied. This reaction intended to be carried out in four elementary reactions. Under the used conditions, the product is isolated in 95%. Also, the effect of the dilution in the yield of the tetramethyltehydro-naphthalene was studied; the good relationship of benzene to the compound dichloride was of 29:1. It is determined that the bromocetones 15, 35 and 36 are little reactive toward the joining of Heck when the crotonic acid is used. Probably, the presence of the groups metoxyle and hydroxyle to the halogen in the bromocetones 15 and 36, respectively, affect the reactivity. In the case of the bromocetone 35, to make this reaction, the group protective acilo gets lost before being made the vinylation of Heck, becoming the bromocetone 36. The joining of Heck between the acrylic acid and the bromocetone 15 in an isolated yield of 33% was possible to be made. It indicates that besides the electronic effects that affect to the bromocetone in this type of reaction, the vinyllic methyl in the crotonic acid causes a low reactivity in this joining, for this substrate in particular. (Author) [es

Thermal stability of homo- and copolymers of vinyl fluoride

International Nuclear Information System (INIS)

Raucher, D.; Levy, M.

1979-01-01

The thermal stability of poly(vinyl fluoride)(PVF) was studied by thermal gravimetry and mass spectrometry (TGA and TGA-MS). In low-molecular-weight polymers a two-step decomposition pattern was observed. It consisted of the dehydrofluorination to a polyene chain followed by decomposition of the resulting polyene at higher temperatures. Copolymers of vinyl fluoride-vinyl acetate (VF-VAc) and vinyl fluoride-vinyl chloride (VF-VCl) showed a simultaneous evolution of hydrofluoric acid and acetic acid and hydrofluoric acid and hydrochloric acid, respectively. This suggests that after the elimination of the weakest link a spontaneous elimination of neighboring HF molecules takes place

29 CFR 1915.1017 - Vinyl chloride.

Science.gov (United States)

2010-07-01

... 29 Labor 7 2010-07-01 2010-07-01 false Vinyl chloride. 1915.1017 Section 1915.1017 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1017 Vinyl chloride. Note: The requirements applicable to shipyard employment under this section...

Unusual differences in the reactivity of glutamic and aspartic acid in oxidative decarboxylation reactions

NARCIS (Netherlands)

But, Andrada; Wijst, van der Evie; Notre, le Jerome; Wever, Ron; Sanders, Johan P.M.; Bitter, Johannes H.; Scott, Elinor L.

2017-01-01

Amino acids are potential substrates to replace fossil feedstocks for the synthesis of nitriles via oxidative decarboxylation using vanadium chloroperoxidase (VCPO), H₂O₂ and bromide. Here the conversion of glutamic acid (Glu) and aspartic acid (Asp) was investigated. It was

Technoeconomic analysis of jet fuel production from hydrolysis, decarboxylation, and reforming of camelina oil

KAUST Repository

Natelson, Robert H.; Wang, Weicheng; Roberts, William L.; Zering, Kelly D.

2015-01-01

The commercial production of jet fuel from camelina oil via hydrolysis, decarboxylation, and reforming was simulated. The refinery was modeled as being close to the farms for reduced camelina transport cost. A refinery with annual nameplate capacity of 76,000 cubic meters hydrocarbons was modeled. Assuming average camelina production conditions and oil extraction modeling from the literature, the cost of oil was 0.31$kg-1. To accommodate one harvest per year, a refinery with 1 year oil storage capacity was designed, with the total refinery costing 283 million dollars in 2014 USD. Assuming co-products are sold at predicted values, the jet fuel break-even selling price was 0.80$kg-1. The model presents baseline technoeconomic data that can be used for more comprehensive financial and risk modeling of camelina jet fuel production. Decarboxylation was compared to the commercially proven hydrotreating process. The model illustrated the importance of refinery location relative to farms and hydrogen production site.

Technoeconomic analysis of jet fuel production from hydrolysis, decarboxylation, and reforming of camelina oil

KAUST Repository

Natelson, Robert H.

2015-04-01

The commercial production of jet fuel from camelina oil via hydrolysis, decarboxylation, and reforming was simulated. The refinery was modeled as being close to the farms for reduced camelina transport cost. A refinery with annual nameplate capacity of 76,000 cubic meters hydrocarbons was modeled. Assuming average camelina production conditions and oil extraction modeling from the literature, the cost of oil was 0.31$kg-1. To accommodate one harvest per year, a refinery with 1 year oil storage capacity was designed, with the total refinery costing 283 million dollars in 2014 USD. Assuming co-products are sold at predicted values, the jet fuel break-even selling price was 0.80$kg-1. The model presents baseline technoeconomic data that can be used for more comprehensive financial and risk modeling of camelina jet fuel production. Decarboxylation was compared to the commercially proven hydrotreating process. The model illustrated the importance of refinery location relative to farms and hydrogen production site.

DFT-Based Explanation of the Effect of Simple Anionic Ligands on the Regioselectivity of the Heck Arylation of Acrolein Acetals

DEFF Research Database (Denmark)

Henriksen, Signe Teuber; Tanner, David Ackland; Cacchi, Sandro

2009-01-01

The Heck arylation of acrolein acetal has been studied computationally and compared to the corresponding reaction with allyl ethers. The reaction can be controlled to give either cinnamaldehydes or arylpropanoic esters by addition of different coordinating anions, acetate, or chloride. The comput...... reaction conditions. The difference between the two substrate classes could be rationalized in terms of relative hydride donating power of the two substrates....

Statistical analysis of nitrogen-containing vinyl copolymers: radiation-induced copolymerization of vinyl acetate and N-vinyl-2-pyrrolidone

International Nuclear Information System (INIS)

Peppas, N.A.; Gehr, T.W.B.

1979-01-01

Radiation-induced copolymerization of vinyl acetate and N-vinyl-2-pyrrolidone was carried out at 5 0 C using γ-irradiation of 1450 rads/min. Copolymers prepared at conversions lower than 5% were analyzed by a saponification technique. Various linear and nonlinear statistical analysis techniques were used to determine the reactivity ratios of this system as r 1 = 0.348 and r 2 = 3.108. These data were examined and analyzed in relation to problems of elemental analysis involving nitrogen-containing copolymers and to discrepancies in the reactivity ratios obtained by previous investigators. The presence of oxygen and a higher dose rate did not affect the copolymer composition within statistical error. Hydrolyzed copolymers prepared by this method have potential applications as biocompatible materials

Radiation fixation of vinyl chloride in an insecticide aerosol container

International Nuclear Information System (INIS)

Kagiya, V.T.; Takemoto, K.

1975-01-01

Recently, a large quantity of vinyl chloride has been used as spraying additive for insecticide aerosols. Since January 1974 when the Food and Drug Administration of the United States of America announced that vinyl chloride causes liver cancer, it has been forbidden in Japan and the United States of America to market insecticide aerosol containers containing vinyl chloride. In Japan, following a government order, about 20 million insecticide aerosol containers have been collected and put into storage. A report is given on the radiation fixation of vinyl chloride as polyvinylchloride powder by gamma-ray-induced polymerization in the aerosol container. Insecticide aerosol containers containing vinyl chloride were irradiated by gamma rays from 60 Co at room temperature. Vinyl chloride polymerized to form powdered polymer in the container. Polymerization conversion increased with the irradiation dose, and after 10 Mrad irradiation, vinyl chloride was not found in the sprayed gas. This establishes that vinyl chloride can be fixed by gamma-ray irradiation in the aerosol container. To accelerate the reaction rate, the effect of various additives on the reaction was investigated. It was found that halogenated hydrocarbons, such as chloroform and carbon tetrachloride, accelerated the initiation of the polymerization, and that a vinyl monomer such as vinyl acetate accelerated the reaction rate due to the promotion of the initiation and the high reactivity of the polyvinylacetate radical to vinyl chloride. Consequently, the required irradiation dose for the fixation of vinyl chloride was decreased to less than 5 Mrad by the addition of various kinds of additives. Following the request of the Ministry of Public Welfare, various technical problems for large-scale treatment are being studied with the co-operation of the Federation of Insecticide Aerosols. (author)

Radiation induced copolymerization of N-vinyl-2-pyrrolidone with vinyl acetate [Paper No. RD-3

International Nuclear Information System (INIS)

Ramakrishna, M.S.; Dhal, P.K.; Deshpande, D.D.; Babu, G.N.

1982-01-01

Copolymerization of N-vinyl-2-pyrrolidone (NVP) with vinyl acetate (VAC) was carried out using gamma-ray radiation. The compositions of the copolymers were determined from elemental analysis and the monomer reactivity ratios have been calculated using YBR method. The glass transition temperature and the intrinsic viscosities of the copolymers have been determined. All the experimental results were discussed in terms of the nature of the monomers. (author)

MILLIMETER WAVE SPECTRUM AND ASTRONOMICAL SEARCH FOR VINYL FORMATE

Energy Technology Data Exchange (ETDEWEB)

Alonso, E. R.; Kolesniková, L.; Cabezas, C.; Alonso, J. L. [Grupo de Espectroscopia Molecular (GEM), Edificio Quifima, Área de Química-Física, Laboratorios de Espectroscopia y Bioespectroscopia, Parque Científico UVa, Unidad Asociada CSIC, Universidad de Valladolid, E-47011 Valladolid (Spain); Tercero, B.; Cernicharo, J. [Grupo de Astrofísica Molecular, ICMM-CSIC, C/Sor Juana Inés de la Cruz 3, E-28049 Cantoblanco (Spain); Guillemin, J.-C. [Institut des Sciences Chimiques de Rennes, École Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837, F-35708 Rennes Cedex 7 (France)

2016-11-20

Previous detections of methyl and ethyl formate make other small substituted formates potential candidates for observation in the interstellar medium. Among them, vinyl formate is one of the simplest unsaturated carboxylic ester. The aim of this work is to provide direct experimental frequencies of the ground vibrational state of vinyl formate in a large spectral range for astrophysical use. The room-temperature rotational spectrum of vinyl formate has been measured from 80 to 360 GHz and analyzed in terms of Watson’s semirigid rotor Hamiltonian. Two thousand six hundred transitions within J = 3–88 and K {sub a} = 0–28 were assigned to the most stable conformer of vinyl formate and a new set of spectroscopic constants was accurately determined. Spectral features of vinyl formate were then searched for in Orion KL, Sgr B2(N), B1-b, and TMC-1 molecular clouds. Upper limits to the column density of vinyl formate are provided.

Sorption of water vapor in partially hydrolyzed poly(vinyl acetate)

International Nuclear Information System (INIS)

Spencer, H.G.; Honeycutt, S.C.

1973-01-01

The sorption kinetics of H 2 O and D 2 O in copolymers of partially hydrolyzed poly(vinyl acetate) were studied and compared with the sorption kinetics of vinyl acetate--vinyl alcohol copolymers, and poly(vinyl alcohol). The special measurement problems presented by transient-state sorption studies in water vapor--polymer systems and their effects on the results are discussed

Vinyl acetate polymerization by ionizing radiation

International Nuclear Information System (INIS)

Mesquita, Andrea Cercan

2002-01-01

The aim of this work is the synthesis and characterization of the poly(vinyl acetate) using the ionizing radiation. Six polymerizations of vinyl acetate were carried out using three techniques of polymerization: in bulk, emulsion and solution. In the technique of solution polymerization were used two solvents, the alcohol ethyl and the methylethylketone, in two proportions 1:0.5 and 1:1 related to the monomer. The solutions were irradiated with gamma rays from a 60 Co source, with dose rate between 5.25 kGy/h and 6.26 kGy/h. The polymers obtained were characterized by Fourier Transform Infrared Spectroscopy (FTIR). The glass transition temperature (Tg) was investigated by Differential Scanning Calorimeter (DSC). The molecular weight was analyzed by the technique of Gel Permeation Chromatography (GPC). Tests of density, hardness and Vicat softening temperature were carried out. The infrared spectroscopy and others results confirmed that the polymers obtained by polymerization of vinyl acetate in bulk, emulsion and solution, using ionizing radiation, really correspond at poly(vinyl acetate). (author)

Hydrotelluration of alkynes: a unique route to Z-vinyl organometallics

Directory of Open Access Journals (Sweden)

Vieira Maurício L.

2001-01-01

Full Text Available The hydrotelluration reaction of alkynes is reviewed. The transformation of vinylic tellurides into reactive vinyl organometallics and the coupling reactions of vinylic tellurides with alkynes and organometallics are presented.

Decarboxylation of oxalacetate to pyruvate by purified avian liver phosphoenolpyruvate carboxykinase

Energy Technology Data Exchange (ETDEWEB)

Noce, P S; Utter, M F

1975-01-01

Phosphoenolpyruvate carboxykinase, which has been isolated from chicken liver mitochondria in essentially homogenous form, carries out the irreversible decarboxylation of oxalacetate to pyruvate in the presence of catalytic amounts of GDP or IDP, as well as the reversible decarboxylation of oxalacetate to phosphoenolpyruvate in the presence of substrate amounts of GTP or ITP. The pyruvate- and phosphoenolpyruvate-forming reactions are similar in their nucleoside specificity and appear to be carried out by the same protein. However, the two activities vary markedly in their response to added metal ions and sulfhydryl reagents. Phosphoenolpyruvate formation is completely dependent on the presence of a divalent metal ion, with Mn/sup 2 +/ the most effective species. This reaction is also stimulated by sulfhydryl reagents such as 2-mercaptoethanol. In contrast, the pyruvate-forming reaction is strongly inhibited by divalent metal ions, including Mn/sup 2 +/, and also by moderate concentrations of sulfhydryl reagents. These observations and the demonstration that pyruvate kinase-like activity is very low or absent make it unlikely that pyruvate formation proceeds via phosphoenolpyruvate as an intermediate. Although the pyruvate-forming reaction is inhibited by added metal ions, the reaction is also inhibited by metal-chelating agents such as 8-hydroxyquinoline and o-phenanthroline, suggesting that the reaction is dependent on the presence of a metal ion. It has not been possible, however, to demonstrate that the enzyme is a metalloprotein.

Decarboxylative Aminomethylation of Aryl- and Vinylsulfonates through Combined Nickel- and Photoredox-Catalyzed Cross-Coupling

KAUST Repository

Fan, Lulu

2016-09-23

A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the combination of photoredox and nickel catalysis through C−O bond cleavage is described for the first time. A wide range of aryl triflates as well as aryl mesylates, tosylates and alkenyl triflates afford the corresponding products in good to excellent yields.

Decarboxylative Aminomethylation of Aryl- and Vinylsulfonates through Combined Nickel- and Photoredox-Catalyzed Cross-Coupling

KAUST Repository

Fan, Lulu; Jia, Jiaqi; Hou, Hong; Lefebvre, Quentin; Rueping, Magnus

2016-01-01

A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the combination of photoredox and nickel catalysis through C−O bond cleavage is described for the first time. A wide range of aryl triflates as well as aryl mesylates, tosylates and alkenyl triflates afford the corresponding products in good to excellent yields.

Copolymers of Vinyl-Containing Benzoxazine with Vinyl Monomers as Precursors for High Performance Thermosets

Directory of Open Access Journals (Sweden)

Tsutomu Takeichi

2015-04-01

Full Text Available A benzoxazine containing a vinyl group (P-4va was prepared by the reaction of phenol, 4-vinylaniline, and paraformaldehyde. A differential scanning calorimetry (DSC study revealed that ring-opening polymerization of the benzoxazine and chain polymerization of the vinyl group occurred in the same temperature range. When 2,2'-azobisisobutyronitrile was added as a radical initiator to P-4va, however, only the vinyl groups were polymerized at lower temperature, giving oligo(P-4va that contains pendent benzoxazine units. Radical copolymerization of P-4va with various vinyl monomers such as styrene, methyl methacrylate (MMA, and n-butyl acrylate (BuA was examined. The chemical structure of the copolymers was confirmed by FT-IR and 1H-NMR to be one of polyolefins bearing benzoxazine units as the pendant groups. The weight-average molecular weights of the copolymers determined by size exclusion chromatography were to be in the range of 1900–51,500 depending on the comonomers. DSC of the copolymers showed that the maxima of the exothermic peaks corresponding to the ring-opening polymerization of the pendent benzoxazine units were observed in the temperature range of 229–250 °C. Thermal cure up to 240 °C of the copolymer films afforded homogenous transparent films with improved thermal properties. Tough cured film was obtained by the copolymerization with MMA, while a tough and flexible film was obtained by the copolymerization with BuA.

Williamson alkylation approach to the synthesis of poly(alkyl vinyl ether) copolymers

International Nuclear Information System (INIS)

Markova, D.; Christova, D.; Velichkova, R.

2008-01-01

A method for synthesis of poly(alkyl vinyl ether-co-vinyl alcohol) copolymers was developed based on the Williamson's alkylation of poly(vinyl acetate) (PVAc) with alkyl iodides. The influence of the alkylating agent and the reaction conditions on the efficiency of the modification reaction was investigated. The copolymers obtained were characterized by means of 1 H NMR and GPC. It was proved that by applying the proposed method copolymers of different composition and properties containing methyl vinyl ether, ethyl vinyl ether as well as n-butyl vinyl ether units could be prepared. Poly(methyl vinyl ether-co-vinyl alcohol)s of high degree of methylation exhibit sharp temperature response at 38-39 deg C in aqueous solution typical of the so-called smart polymers. (authors)

Tissue distribution of 1,2-14C-vinyl chloride in rats

International Nuclear Information System (INIS)

Buchter, A.; Bolt, H.M.; Kappus, H.; Bolt, W.

1977-01-01

Rats have been pretreatet with 6-nitro-1.2.3-benzothiadiazole which completely blocks the metabolism of vinyl chloride. If the animals are exposed to atmospheric vinyl chloride, the formation of an equilibrium between the compound in the gas phase and in the animal's organism is observed. Unmetabolized vinyl chloride is accumulated in the adipose tissue. The distribution pattern of vinyl in different organs of the rat is constant over the concentration range of 25-10,000 ppm of vinyl chloride in the exposure atmosphere. The distribution of metabolites of vinyl chloride contrasts to that of the original compound; metabolites primarily are concentrated in liver and in kidneys. (orig.) [de

Scope and limitations of the Heck-Matsuda-coupling of phenol diazonium salts and styrenes: a protecting-group economic synthesis of phenolic stilbenes.

Science.gov (United States)

Schmidt, Bernd; Elizarov, Nelli; Berger, René; Hölter, Frank

2013-06-14

4-Phenol diazonium salts undergo Pd-catalyzed Heck reactions with various styrenes to 4'-hydroxy stilbenes. In almost all cases higher yields and fewer side products were observed, compared to the analogous 4-methoxy benzene diazonium salts. In contrast, the reaction fails completely with 2- and 3-phenol diazonium salts. For these substitution patterns the methoxy-substituted derivatives are superior.

Viscometric investigation of compatibilization of the poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) blends by terpolymer of maleic anhydride styrene vinyl acetate

Science.gov (United States)

İmren, Dilek; Boztuğ, Ali; Yılmaz, Ersen; Zengin, H. Bayram

2008-11-01

In this study, a blend of poly(vinyl chloride) (PVC)/ethylene-co-vinyl acetate (EVA) was compatibilized by terpolymer of maleic anhydride-styrene-vinyl acetate (MAStVA) used as a compatibilizer. It was prepared the blends of 50/50 PVC/EVA containing 2-10% of the terpolymer. The compatibility experiences of these blends were investigated by using viscometric method in the range of concentrations (0.5-2.0 g dL -1) where tetrahydrofuran (THF) is the solvent. The interaction parameter (Δ b) was used to study the miscibility and compatibility of polymer blend in solution, obtained from the modified Krigbaum and Wall theory. Turbidity and FTIR measurements were also used to investigate the miscibility of this pair of polymers. The values of the relative viscosities of the each polymer solution and their blends were measured by a Cannon-Fenske type viscometer. In consequence of the study, it was observed that a considerable improvement was achieved in the miscibility of PVC/EVA blends by adding among 5 and 10 wt% of compatibilizer.

Radiation induced ionic polymerisation and grafting of vinyl monomers

International Nuclear Information System (INIS)

Stannett, V.T.

1981-01-01

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

Preparation of poly(vinyl alcohol) membranes grafted with N-vinyl imidazole/acrylic acid binary monomers

International Nuclear Information System (INIS)

Ajji, Zaki; Ali, Ali

2006-01-01

Poly(vinyl alcohol) films were grafted with two monomers using gamma radiation, acrylic acid and N-vinyl imidazole. The influence of different parameters on the grafting yield was investigated as: type of solvent and solvent composition, comonomer concentration and composition, addition of mineral acids, and irradiation dose. Water uptake in respect to the grafting yield was also evaluated. The ability of the grafted films to adsorb copper ions was elaborated and discussed for different grafting yields and ph values of the solution. (authors)

Direct Vinylation of Alcohols or Aldehydes Employing Alkynes as Vinyl Donors: A Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation

Science.gov (United States)

Patman, Ryan L.; Chaulagain, Mani Raj; Williams, Vanessa M.; Krische, Michael J.

2011-01-01

Under the conditions of ruthenium catalyzed transfer hydrogenation, 2-butyne couples to benzylic and aliphatic alcohols 1a–1i to furnish allylic alcohols 2a–2i, constituting a direct C-H vinylation of alcohols employing alkynes as vinyl donors. Under related transfer hydrogenation conditions employing formic acid as terminal reductant, 2-butyne couples to aldehydes 4a, 4b, and 4e to furnish identical products of carbonyl vinylation 2a, 2b, and 2e. Thus, carbonyl vinylation is achieved from the alcohol or the aldehyde oxidation level in the absence of any stoichiometric metallic reagents. Nonsymmetric alkynes 6a–6c couple efficiently to aldehyde 4b to provide allylic alcohols 2m–2o as single regioisomers. Acetylenic aldehyde 7a engages in efficient intramolecular coupling to deliver cyclic allylic alcohol 8a. PMID:19173651

Continuous-flow Heck synthesis of 4-methoxybiphenyl and methyl 4-methoxycinnamate in supercritical carbon dioxide expanded solvent solutions

Directory of Open Access Journals (Sweden)

Phei Li Lau

2013-12-01

Full Text Available The palladium metal catalysed Heck reaction of 4-iodoanisole with styrene or methyl acrylate has been studied in a continuous plug flow reactor (PFR using supercritical carbon dioxide (scCO2 as the solvent, with THF and methanol as modifiers. The catalyst was 2% palladium on silica and the base was diisopropylethylamine due to its solubility in the reaction solvent. No phosphine co-catalysts were used so the work-up procedure was simplified and the green credentials of the reaction were enhanced. The reactions were studied as a function of temperature, pressure and flow rate and in the case of the reaction with styrene compared against a standard, stirred autoclave reaction. Conversion was determined and, in the case of the reaction with styrene, the isomeric product distribution was monitored by GC. In the case of the reaction with methyl acrylate the reactor was scaled from a 1.0 mm to 3.9 mm internal diameter and the conversion and turnover frequency determined. The results show that the Heck reaction can be effectively performed in scCO2 under continuous flow conditions with a palladium metal, phosphine-free catalyst, but care must be taken when selecting the reaction temperature in order to ensure the appropriate isomer distribution is achieved. Higher reaction temperatures were found to enhance formation of the branched terminal alkene isomer as opposed to the linear trans-isomer.

Hydrocarbon fuels from gas phase decarboxylation of hydrolyzed free fatty acid

KAUST Repository

Wang, Weicheng

2012-01-01

Gas phase decarboxylation of hydrolyzed free fatty acid (FFA) from canola oil has beeninvestigated in two fix-bed reactors by changing reaction parameters such as temperatures,FFA feed rates, and H 2-to-FFA molar ratios. FFA, which contains mostly C 18 aswell as a few C 16, C 20, C 22, and C 24 FFA, was fed into the boiling zone, evaporated, carriedby hydrogen flow at the rate of 0.5-20 ml/min, and reacted with the 5% Pd/C catalystin the reactor. Reactions were conducted atmospherically at 380-450 °C and the products,qualified and quantified through gas chromatography-flame ionization detector(GC-FID), showed mostly n-heptadecane and a few portion of n-C 15, n-C 19, n-C 21, n-C 23 as well as some cracking species. Results showed that FFA conversion increased withincreasing reaction temperatures but decreased with increasing FFA feed rates and H 2-to-FFA molar ratios. The reaction rates were found to decrease with higher temperatureand increase with higher H 2 flow rates. Highly selective heptadecane was achieved byapplying higher temperatures and higher H 2-to-FFA molar ratios. From the results, ascatalyst loading and FFA feed rate were fixed, an optimal reaction temperature of 415 °C as well as H 2-to-FFA molar ratio of 4.16 were presented. These results provided goodbasis for studying the kinetics of decarboxylation process. © 2012 American Society of Mechanical Engineers.

Swelling and mechanical properties of physically crosslinked poly(vinyl alcohol) hydrogels.

Science.gov (United States)

Suzuki, Atsushi; Sasaki, Saori

2015-12-01

Physically crosslinked poly(vinyl alcohol) gels are versatile biomaterials due to their excellent biocompatibility. In the past decades, physically crosslinked poly(vinyl alcohol) and poly(vinyl alcohol)-based hydrogels have been extensively studied for biomedical applications. However, these materials have not yet been implemented due to their mechanical strength. Physically crosslinked poly(vinyl alcohol) gels consist of a swollen amorphous network of poly(vinyl alcohol) physically crosslinked by microcrystallites. Although the mechanical properties can be improved to some extent by controlling the distribution of microcrystallites on the nano- and micro-scales, enhancing the mechanical properties while maintaining high water content remains very difficult. It may be technologically impossible to significantly improve the mechanical properties while keeping the gel's high water absorbance ability using conventional fabrication methods. Physical and chemical understandings of the swelling and mechanical properties of physically crosslinked poly(vinyl alcohol) gels are considered here; some promising strategies for their practical applications are presented. This review focuses more on the recent studies on swelling and mechanical properties of poly(vinyl alcohol) hydrogels, prepared using only poly(vinyl alcohol) and pure water with no other chemicals, as potential biomedical materials. © IMechE 2015.

Muonium-containing vinyl radicals

International Nuclear Information System (INIS)

Rhodes, C.J.; Symons, M.C.R.; Roduner, E.; Heming, M.

1987-01-01

Exposure of trimethylsilylacetylene and bis(trimethylsilyl)acetylene to positive muons gave radicals whose muon-electron hyperfine coupling constants establish that the corresponding vinyl radicals were formed. (author)

Metodologies d’anulació en substrats heterocíclics: Reaccions de RCM i ciclacions de Heck

OpenAIRE

Alonso Serrano, Sandra

2010-01-01

[cat] La present Tesi Doctoral es situa en el context de l’estudi d’estratègies sintètiques per a la formació d’anells en l’àrea heterocíclica. En particular, s’han avaluat les possibilitats sintètiques de la combinació de dues reaccions d’eficàcia prou reconeguda per a la formació d’enllaços carboni-carboni, la reacció de RCM i la reacció intramolecular de Heck d’halurs vinílics, per a la construcció de les estructures policíliques amb pont característiques dels alcaloides ervitsina i apari...

Weissella halotolerans W22 combines arginine deiminase and ornithine decarboxylation pathways and converts arginine to putrescine

NARCIS (Netherlands)

Pereira, C. I.; San Romao, M. V.; Lolkema, J. S.; Barreto Crespo, M. T.; Baretto Crespo, M.

2009-01-01

Aims: To demonstrate that the meat food strain Weissella halotolerans combines an ornithine decarboxylation pathway and an arginine deiminase (ADI) pathway and is able to produce putrescine, a biogenic amine. Evidence is shown that these two pathways produce a proton motive force (PMF). Methods and

Clarification on the decarboxylation mechanism in KasA based on the protonation state of key residues in the acyl-enzyme state.

Science.gov (United States)

Lee, Wook; Engels, Bernd

2013-07-11

The β-ketoacyl ACP synthase I (KasA) is a promising drug target because it is essential for the survival of Mycobacterium tuberculosis , a causative agent of tuberculosis. It catalyzes a condensation reaction that comprises three steps. The resulting elongated acyl chains are subsequently needed for the cell wall construction. While the mechanism of the first step (acylation of Cys171 in the active site) is straightforward already, the second step (decarboxylation of malonyl substrate) has been controversial due to the difficulty in determining the correct protonation states of the involved residues (His311, His345, Lys340, Glu354). Available experimental data suggest three possible mechanisms which differ considerably. They are not consistent with each other because these studies could not be performed for KasA at the beginning of decarboxylation step (acyl-enzyme state of KasA). Instead, different mutants had to be used which are expected to resemble this situation. In this first computational study about this topic, we use the free energy perturbation (FEP) method to compute the relevant pKa values in the acyl-enzyme state of KasA and use molecular dynamics (MD) simulations to rationalize the results. Subsequent density functional theory (DFT)-based quantum mechanical/molecular mechanical (QM/MM) MD simulations and umbrella samplings have been used to disentangle the close relationships between the protonation states of the involved residues. By these simulations, we can address the preferred protonation states and roles of the residues involved in decarboxylation reaction, thereby suggesting the possible mechanism for the decarboxylation step.

Visible-Light Photocatalytic Decarboxylation of α,β-Unsaturated Carboxylic Acids: Facile Access to Stereoselective Difluoromethylated Styrenes in Batch and Flow

Science.gov (United States)

2017-01-01

The development of synthetic methodologies which provide access to both stereoisomers of α,β-disubstituted olefins is a challenging undertaking. Herein, we describe the development of an operationally simple and stereoselective synthesis of difluoromethylated styrenes via a visible-light photocatalytic decarboxylation strategy using fac-Ir(ppy)3 as the photocatalyst. Meta- and para-substituted cinnamic acids provide the expected E-isomer. In contrast, ortho-substituted cinnamic acids yield selectively the less stable Z-product, whereas the E-isomer can be obtained via continuous-flow processing through accurate control of the reaction time. Furthermore, our protocol is amenable to the decarboxylative difluoromethylation of aryl propiolic acids. PMID:29109904

Mutagenicity of vinyl chloride after metabolic activation

Energy Technology Data Exchange (ETDEWEB)

Rannug, U; Johansson, A; Ramel, C; Wachtmeister, C A

1974-01-01

Vinyl chloride has recently been shown to cause a malignant liver tumor disease in man after occupational exposure in PVC plants. This actualizes the problem of whether such hazards could be avoided or at least diminished in the future by a screening for mutagenicity of chemicals used in industries. The basis for such a screening procedure is the close correlation between carcinogenic and mutagenic effects of chemicals. Experiments with Salmonella bacteria showed that the carcinogenic hazard of vinyl chloride could have been traced by means of mutagenicity tests. The data indicate that vinyl chloride is not mutagenic per se but becomes mutagenic after a metabolic activation in the liver. 24 references, 1 figure, 4 tables.

Direct 13C-1H coupling constants in the vinyl group of 1-vinylpyrazoles

International Nuclear Information System (INIS)

Afonin, A.V.; Voronov, V.K.; Es'kova, L.A.; Domnina, E.S.; Petrova, E.V.; Zasyad'ko, O.V.

1987-01-01

In a continuation of a study of the rotational isomerism of 1-vinylpyrazoles, they studied the direct 13 C- 1 H coupling constants in the vinyl group of 1-vinylpyrazole, 1-vinyl-4-bromopyrazole, 1-vinyl-3-methylpyrazole, 1-vinyl-5-methylpyrazole, 1-vinyl-3,5-dimethylpyrazole, and 1-vinyl-4-nitro-3,5-dimethylpyrazole. The 13 C- 1 H direct coupling constants in the vinyl group of 1-vinylpyrazoles are stereo-specific and vary with change in the conformer ratio

Hydrolysis of strained bridgehead bicyclic vinyl ethers and sulfides

International Nuclear Information System (INIS)

Chwang, W.K.; Kresge, A.J.; Wiseman, J.R.

1979-01-01

Rates of hydrolysis of the bridgehead bicyclic vinyl ether 9-oxabicyclo[3.3.1]non-1-ene(6) and its vinyl sulfide counterpart 9-thiabicyclo[3.3.1]non-1-ene(7), catalyzed by the hydronium ion, were measured in H 2 O and in D 2 O solution. These data give isotope effects, k/sub H//k/sub D/ = 2.4 and 1.9 respectively, which show that these reactions occur by the normal, rate-determining carbon protonation, mechanism. The vinyl ether 6 is less reactive than its olefin analogue, bicyclo[3.3.1]non-1-ene (relative rate 1:1/1400), as may have been expected for a constrained bicyclic system such as this, where stabilization of the bridgehead carbocation intermediate by conjugation with oxygen is severely impaired. The vinyl sulfide 7, however, is even less reactive than the vinyl ether (relative rates 1:1/140); this is a remarkable result in view of the fact that conjugation between the sulfur atom and the cationic center is presumably also strongly inhibited. 1 figure, 3 tables

Solvent effects and secondary isotope effects for probing diradical character in the thermal decarboxylation of β-peroxylactones

International Nuclear Information System (INIS)

Adam, W.; Cueto, O.; Guedes, L.N.; Rodriguez, L.O.

1978-01-01

The lack of solvent effects in the activation parameters and product distribution and the lack of secondary deuterium isotope effects at the α-carbon and β-alkyl migrant substantiates that the thermal decarboxylation of β-peroxy lactones proceeds via a 1,5-diradical

Production of methyl-vinyl ketone from levulinic acid

Energy Technology Data Exchange (ETDEWEB)

Dumesic, James A [Verona, WI; West,; Ryan, M [Madison, WI

2011-06-14

A method for converting levulinic acid to methyl vinyl ketone is described. The method includes the steps of reacting an aqueous solution of levulinic acid, over an acid catalyst, at a temperature of from room temperature to about 1100 K. Methyl vinyl ketone is thereby formed.

Synthesis of Poly(vinyl ether) Thermoplastic Elastomers Having Functional Soft Segments

OpenAIRE

今枝, 嗣人; 漆崎, 美智遠; 阪口, 壽一; 橋本, 保; Tsuguto, IMAEDA; Michio, URUSHISAKI; Toshikazu, SAKAGUCHI; Tamotsu, HASHIMOTO

2013-01-01

The ABA-type triblock copolymers consisting of poly(2-adarnantyl vinyl ether) [poly(2-AdVE) as outer hard segments and poly(6-acetoxyhexyl vinyl ether) [poly(AcHVE)] poly(6-hydroxyhexyl vinyl ether) [poly(H HVE)], or poly(2-(2-methoxyethoxy)ethyl vinyl ether [poly(MOEOVE)] as inner soft segments were synthesized by sequential living cationic polymerization. Despite the presence of polar functional groups such as ester, hydroxy, and oxyethylene units in their soft segments, the two polymer seg...

Aerobic biodegradation of vinyl chloride in groundwater samples

International Nuclear Information System (INIS)

Davis, J.W.; Carpenter, C.L.

1990-01-01

Studies were conducted to examine the biodegradation of 14 C-labeled vinyl chloride in samples taken from a shallow aquifer. Under aerobic conditions, vinyl chloride was readily degraded, with greater than 99% of the labeled material being degraded after 108 days and approximately 65% being mineralized to 14 CO 2

Quantum Chemical Modeling of Enzymatic Reactions: The Case of Decarboxylation.

Science.gov (United States)

Liao, Rong-Zhen; Yu, Jian-Guo; Himo, Fahmi

2011-05-10

We present a systematic study of the decarboxylation step of the enzyme aspartate decarboxylase with the purpose of assessing the quantum chemical cluster approach for modeling this important class of decarboxylase enzymes. Active site models ranging in size from 27 to 220 atoms are designed, and the barrier and reaction energy of this step are evaluated. To model the enzyme surrounding, homogeneous polarizable medium techniques are used with several dielectric constants. The main conclusion is that when the active site model reaches a certain size, the solvation effects from the surroundings saturate. Similar results have previously been obtained from systematic studies of other classes of enzymes, suggesting that they are of a quite general nature.

Wearing ambidextrous vinyl gloves does not impair manual dexterity.

Science.gov (United States)

Drabek, Tomas; Boucek, Charles D; Buffington, Charles W

2013-01-01

Universal precautions mandate that health care workers wear gloves to prevent the unintended spread of bloodborne pathogens. Gloves may affect manual dexterity, generally delaying task completion. Our previous study showed that wearing the wrong size latex surgical glove degraded manual dexterity. The use of non-sterile and non-latex gloves may limit certain risks and be more cost-effective. However, such gloves may produce different results. We hypothesized that ambidextrous vinyl examination gloves would degrade manual dexterity compared with bare hands. We studied 20 random subjects from a medical environment. Subjects performed a standard battery of Grooved Pegboard tasks while bare-handed, wearing ambidextrous non-sterile vinyl gloves that were their preferred size, a size too small, and a size too large. The order was randomized with a Latin Square design to minimize the effects of time, boredom, and fatigue on the subjects. Subjects were also invited to comment on the fit of different size gloves. Wearing vinyl gloves of both the preferred size and a size up or down failed to affect manual dexterity vs. bare hands on time to insert pegs, and pegs dropped during insertion or removal. In contrast, the time to remove pegs was reduced by wearing preferred size vinyl gloves compared with performing the task with bare hands (Pgloves that were too small caused significant hand discomfort. Vinyl gloves surprisingly do not degrade manual dexterity even when worn in ill-fitting sizes. Wearing a preferred size vinyl glove vs. bare hands may improve dexterity in selected tasks. Choosing a comfortable, large size seems the best strategy when the preferred size is unavailable. Thinner vinyl gloves may improve grip and may not degrade touch as much as latex surgical gloves and may thus represent a reasonable choice for selected tasks.

PhI(OAc)2-mediated one-pot oxidative decarboxylation and aromatization of tetrahydro-β-carbolines: synthesis of norharmane, harmane, eudistomin U and eudistomin I.

Science.gov (United States)

Kamal, Ahmed; Tangella, Yellaiah; Manasa, Kesari Lakshmi; Sathish, Manda; Srinivasulu, Vunnam; Chetna, Jadala; Alarifi, Abdullah

2015-08-28

Iodobenzene diacetate was employed as a mild and efficient reagent for one-pot oxidative decarboxylation of tetrahydro-β-carboline acids and dehydrogenation of tetrahydro-β-carbolines to access the corresponding aromatic β-carbolines. To the best of our knowledge this is the first synthesis of β-carbolines via a one-pot oxidative decarboxylation at ambient temperature. The utility of this protocol has been demonstrated in the synthesis of β-carboline alkaloids norharmane (2o), harmane (2p), eudistomin U (9) and eudistomin I (12).

Method of modifying a vinyl chloride resin by utilizing radiation cross-linking polymerization

Energy Technology Data Exchange (ETDEWEB)

Kagiya, T; Fujimoto, T; Hosoi, F; Tsuneta, K; Atogawa, M

1970-08-26

The polyvinyl chloride is improved in its mechanical, thermal and chemical properties, with particular advantages gained in dimensional stability at temperatures higher than the plasticizing temperature. The process comprises irradiating a vinyl chloride resin with ionizing radiations in the presence of a vinyl acetate monomer. In this process, the irradiation of vinyl acetate effects cross-linking and the polymerization of the monomer simultaneously. The vinyl chloride resin may be a copolymer along with another monomer, a polyvinyl chloride derivative, a graft polymer of polyvinyl chloride, a mixture of vinyl chloride with another resin and a graft copolymer of vinyl chloride on another resin in any form. The addition of the vinyl acetate monomer to the vinyl chloride is not limited to any particular procedure. The vinyl acetate monomer may be added to the polyvinyl chloride in a quantity ranging from a trace to 200% by weight. The radiation dose may be 10/sup 2/ to 10/sup 9/, but preferably 10/sup 3/ roentgen. In one example, 36 parts by weight of market available vinyl acetate monomer immersed in 100 parts by weight of hard vinyl tube were placed in a stainless reacting vessel. After the replacement of inner air with nitrogen, the vessel was exposed to ..gamma.. beams of 4.8 x 10 roentgen from a Co-60 source. After dipping the exposed samples in boiled tetrahydrofuran for 48 hours, the insoluble substance in the samjle was 78.9% by weight. In addition, after heating at 180/sup 0/C for 30 minutes, the sample did not show any deformation.

Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition

International Nuclear Information System (INIS)

Zielinski, M.; Zielinska, A.; Papiernik-Zielinska, H.; McKenzie, J.A.; Bernasconi, S.; Paul, H.

1998-01-01

Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition above and below its melting temperature have been studied and compared with the primary (PKIE) and secondary kinetic isotope effects (SKIE) of 13 C and 18 O, respectively, in the decarboxylation of other heterocyclic acids. The temperature dependence of the secondary oxygen-18 isotope effects is negative in the total 221-255 deg C temperature interval investigated initially. The 13 C KIE measured above melting point of N.A. (temperature interval 235-270 deg C) are located in the range 1.007-1.009. Below melting point of nicotinic acid the 13 C KIE are larger and reveal the negative temperature dependence ( 13 C KIE decreases with decreasing the reaction temperature from 1.013/at 230 deg C to 1.0114/at 221 deg C). A discussion of the above isotopic results is presented. (author)

IRIS Toxicological Review of Vinyl Chloride (Final Report, 2000)

Science.gov (United States)

EPA is announcing the release of the final report, Toxicological Review of Vinyl Chloride: in support of the Integrated Risk Information System (IRIS). The updated Summary for Vinyl Chloride and accompanying Quickview have also been added to the IRIS Database.

Graft copolymerization of styrene onto poly(vinyl alcohol) initiated by potassium diperiodatocuprate (III)

International Nuclear Information System (INIS)

Bai, L.; Wang, Ch.; Jin, J.; Liu, Y.

2009-01-01

The graft copolymerization of styrene onto poly(vinyl alcohol) is studied by using a novel redox system of potassium diperiodatocuprate-poly(vinyl alcohol) (Cu(III)poly(vinyl alcohol) in alkaline medium. Cu(III)-poly(vinyl alcohol) redox pair is an efficient initiator for this graft copolymerization which is proved by high graft efficiency (>97%) and high percentage of graft (>300%). Reaction conditions (monomer-to-poly(vinyl alcohol) weight ratio, initiator concentration, p H, time and temperature) affect the graft parameters which have been investigated systematically. The optimum reaction conditions are found as St/poly(vinyl alcohol) = 5.4; [Cu(III)] = 1*10 -2 M; p H = 12.7; temperature = 50 d eg C ; time = 3.5 h. Further, the equation of the overall polymerization rate can be written as follows: R p = k C 1.9 (St) C 1.7 (Cu(III)). The overall activation energy was calculated to be 42.0 kJ/mol based on the experimental data of the relations between R p and C(St); R p and C(Cu(III)); and R p and temperature. A mechanism is proposed to explain the formation of radicals and the initiation. The structure of the graft copolymers is confirmed by Fourier transfer infrared spectroscopy. Some peaks were compared with poly(vinyl alcohol) at 3080.34-3001.79 cm -1 (=C-H stretching in the phenyl ring), 1600.34-1450.95 cm -1 (C=C stretching in the phenyl ring), 755.17 cm -1 and 698.64 cm -1 (=C-H out-off-plane bending in phenyl ring) which are considered to belong to the characteristic absorption bands of phenyl group of polystyrene. Therefore it proves that the graft copolymer is composed of poly(vinyl alcohol) and polystyrene. thermal gravimetric analysis thermo grams of poly(vinyl alcohol) and poly(vinyl alcohol)-graft-polystyrene are investigated as well. As it is shown the initial decomposition temperature of poly(vinyl alcohol)-g-polystyrene(377.3 d eg C ) is much higher than that of poly(vinyl alcohol) (241.8 d eg C ), which indicates that the thermal stability of the

The mechanism of the tyrosine transporter TyrP supports a proton motive tyrosine decarboxylation pathway in Lactobacillus brevis

NARCIS (Netherlands)

Wolken, WAM; Lucas, PM; Lonvaud-Funel, A; Lolkema, JS; Wolken, Wout A.M.; Lucas, Patrick M.

The tyrosine decarboxylase operon of Lactobacillus brevis IOEB9809 contains, adjacent to the tyrosine decarboxylase gene, a gene for TyrP, a putative tyrosine transporter. The two genes potentially form a proton motive tyrosine decarboxylation pathway. The putative tyrosine transporter gene of L.

Syntheses of protoporphyrin-IX regioselectivity carbon-13 labelled at the alpha-vinyl carbons

International Nuclear Information System (INIS)

Smith, K.M.; Fujinari, E.M.

1986-01-01

A method for transformation of readily available beta-vinyl 99% carbon-13 enriched derivatives of protoporphyrin-IX dimethyl ester into the less accessible alpha-vinyl labelled isomers is described. The procedure involves thallium(III) promoted vinyl carbon rearrangement, and proceeds through 2,2-dimethoxyethyl, formylmethyl, 2-hydroxyethyl and 2-chloroethyl porphyrins; the rearranged vinyl groups are regenerated from 2-chloroethyl in the last step by treatment with base. No evidence of vinyl carbon scrambling in the sequence is observed, and spectroscopic data of the products are given. (author)

Effect of gamma ray on poly(lactic acid)/poly(vinyl acetate-co-vinyl alcohol) blends as biodegradable food packaging films

International Nuclear Information System (INIS)

Razavi, Seyed Mohammad; Dadbin, Susan; Frounchi, Masoud

2014-01-01

Poly(lactic acid) (PLA)/poly(vinyl acetate-co-vinyl alcohol) [P(VAc-co-VA)] blends as new transparent film packaging materials were prepared at various blend compositions and different vinyl alcohol contents. The blends and pure PLA were irradiated by gamma rays to investigate the extent of changes in the packaging material during gamma ray sterilization process. The miscibility of the blends was dependent on the blend composition and vinyl alcohol content; gamma irradiation had little effect on the extent of miscibility. The glass transition temperature of pure PLA and PLA/P(VAc-co-VA) miscible blends reduced after irradiation. On the other hand in PLA/P(VAc-co-VA) immiscible blends, while the glass transition temperature of the PLA phase decreased; that of the copolymer phase slightly increased. The reduction in the glass transition was about 10 percent for samples irradiated with 50 kGy indicating dominance of chain scission of PLA molecules at high irradiation dose. The latter was verified by drop in mechanical properties of pure PLA after exposing to gamma irradiation at 50 kGy. Blending of PLA with the copolymer P(VAc-co-VA) compensated greatly the adverse effects of irradiation on PLA. The oxygen-barrier property of the blend was superior to the neat PLA and remained almost intact with irradiation. The un-irradiated and irradiated blends had excellent transparency. Gamma ray doses used for sterilization purposes are usually less than 20 kGy. It was shown that gamma irradiation at 20 kGy had no or little adverse effects on PLA/P(VAc-co-VA) blends mechanical and gas barrier properties. - Highlights: • Poly(lactic acid)/poly(vinyl acetate-co-vinyl alcohol) blends were prepared as new packaging film. • The blends are superior to PLA in oxygen gas barrier property. • The blends are suitable for gamma ray sterilization and maintain useful mechanical properties. • The blends are perfectly transparent

Formation of Ketenimines via the Palladium-Catalyzed Decarboxylative π-Allylic Rearrangement of N-Alloc Ynamides.

Science.gov (United States)

Alexander, Juliana R; Cook, Matthew J

2017-11-03

A new approach for the formation of ketenimines via a decarboxylative allylic rearrangement pathway that does not require strong stabilizing or protecting groups has been developed. The products can be readily hydrolyzed into their corresponding secondary amides or reacted with sulfur ylides to perform an additional [2,3]-Wittig process. Mechanistic studies suggest an outer-sphere process in which reductive alkylation is rate-limiting.

In situ polymerization of vinyl monomers in polyester yarns

International Nuclear Information System (INIS)

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

1978-01-01

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

"Aplicação da reação de heck na sintese de compostos heterociclicos"

OpenAIRE

Leonardo Silva Santos

1999-01-01

Resumo: A reação de Heck intramolecular para as lactamas 4a, 4b, 4g e 4f forneceu exclusivamente produtos de ciclização 6-exo-trig em bons rendimentos e foram acompanhadas da migração da dupla ligação exocíclica fornecendo o biciclo 5 a partir da g-Iactama 4a, uma mistura em proporção molar aproximadamente igual a 6:1 dos biciclos 7 e 8 a partir da d- lactama 4b, uma mistura dos isômeros 18 e 19 a partir da lactama 4f na proporção molar aproximadamente igual a 2:1, e apenas o produto exocícli...

Research Needs: Glass Solar Reflectance and Vinyl Siding

Energy Technology Data Exchange (ETDEWEB)

Hart, Robert; Curcija, Charlie; Arasteh, Dariush; Goudey, Howdy; Kohler, Christian; Selkowitz, Stephen

2011-07-07

The subject of glass solar reflectance and its contribution to permanent vinyl siding distortion has not been extensively studied, and some phenomena are not yet well understood. This white paper presents what is known regarding the issue and identifies where more research is needed. Three primary topics are discussed: environmental factors that control the transfer of heat to and from the siding surface; vinyl siding properties that may affect heat build-up and permanent distortion; and factors that determine the properties of reflected solar radiation from glass surfaces, including insulating window glass. Further research is needed to fully characterize the conditions associated with siding distortion, the scope of the problem, physical properties of vinyl siding, insulating window glass reflection characteristics, and possible mitigation or prevention strategies.

Nano-catalysts for upgrading bio-oil: Catalytic decarboxylation and hydrodeoxygenation

Science.gov (United States)

Uemura, Yoshimitsu; Tran, Nga T. T.; Naqvi, Salman Raza; Nishiyama, Norikazu

2017-09-01

Bio-oil is a mixture of oxygenated chemicals produced by fast pyrolysis of lignocellulose, and has attracted much attention recently because the raw material is renewable. Primarily, bio-oil can be used as a replacement of heavy oil. But it is not highly recommended due to bio-oil's inferior properties: high acidity and short shelf life. Upgrading of bio-oil is therefore one of the important technologies nowadays, and is categorized into the two: (A) decrarboxylation/decarbonylation by solid acid catalysts and (B) hydrodeoxygenation (HDO) by metallic catalysts. In our research group, decarboxylation of bio-oil by zeolites and HDO of guaiacol (a model compound of bio-oil) have been investigated. In this paper, recent developments of these upgrading reactions in our research group will be introduced.

Convenient procedures for the α-metallation of vinylic ethers and thioethers

NARCIS (Netherlands)

Verkruijsse, H.D.; Brandsma, L.; Schleyer, P. von R.

1987-01-01

Ethyl vinyl ether H2C=CHOC2H5 and the analogous cyclic vinylic ethers dehydrofuran and 2,3-dihydropyran can be potassiated at −20°C in the α-position with a 1/1/1 molar mixture of BuLi, t-BuOK and TMEDA in hexane. Methyl vinyl sulfide is potassiated very smoothly by a 1/1 molar mixture of BuLi and

Radiation-chemical preparation of poly(vinyl alcohol) hydrogels

International Nuclear Information System (INIS)

Duflot, Anastasia V.; Kitaeva, Natalia K.; Duflot, Vladimir R.

2015-01-01

This work reports the usage of method of radiation-chemical synthesis to prepare cross-linked hydrogels from poly(vinyl alcohol) modified with glycidyl methacrylate. Synthesis kinetics of modified poly(vinyl alcohol) and properties of hydrogels were studied. The gel fraction, swelling, mechanical properties, and water content of the hydrogels were measured. It was found that gel fraction increases with increasing radiation dose, concentration of modified poly(vinyl alcohol), and reaches 60%. It was established by differential scanning calorimetry that a fraction of the “bound” water in hydrogels is 50–70% and independent of gel fraction content. In addition to “bound” and “free” states, water in hydrogels is also present in the intermediate state. - Highlights: • The synthesis and the properties of poly(vinyl alcohol) hydrogels were studied. • PVA was modified by glycidyl methacrylate before gamma cross-linking. • The modification results in decreasing of PVA cross-linking dose by 3 orders lower. • The gel fraction and water content of the hydrogels were measured. • A fraction of the “bound” water in hydrogels is independent of gel fraction content

Mass spectrometric investigation of vinyl-substituted organic boron compounds

International Nuclear Information System (INIS)

Tarielashvili, V.O.; Ordzhonikidze, K.G.; Parulava, L.P.; Vakhaniya, G.V.

1992-01-01

Mass spectrometric investigation of vinyl-substituted organic compounds was conducted. Ionization was performed by electron shock. Possibility of determining boron isotope content is all analyzed organic boron vinyl-substituted compounds by direct method is shown. This simplifies sufficiently and lowers the price of analysis, improves its accuracy and rapidity

Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

Energy Technology Data Exchange (ETDEWEB)

Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

2015-01-01

ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

Thermogravimetric analysis of the polymer acrylate-vinyl ether mixture cured by radiation

International Nuclear Information System (INIS)

Danu, Sugiarto

1998-01-01

An experiment on thermal stability of the polymer acrylate-vinyl ether mixture cured by radiation have been done using thermogravimetric analysis. Three kinds of acrylic oligomers i.e., epoxy acrylate, urethane acrylate, and polypropylene glycol diacrylate, and vinyl ether monomers i.e., triethylene glycol divinyl ether (DVE-3), 1,4-cyclohexane dimethanol divinyl ether (CHVE), and butanediol monovinyl ether (HBVE) were used in the experiment. Reaction was taken via radical and cationic polymerisation. In case of cationic polymerisation, diphenyliodonium hexafluorophosphate fotoinisiator was used in the formulation. Thermogravimetric analysis was conducted in a nitrogen atmosphere at a flow rate of 40 ml/minute with a constant heating rate 10 o C and evaluation range were done from 25 to 500 o C. The results of thermogravimetric analysis showed that acrylate and DVE-3 mixture produced the polymer films with higher thermal stability than the mixture of acrylate with CHVE or HBVE. The composition of acrylate-vinyl ether mixture and degree of unsaturation of vinyl ether monomers influenced the thermal stability of polymer. The mixture of epoxy acrylate-vinyl ether and polypropylene glycol diacrylate-vinyl ether have 1 initial decomposition temperature whereas the urethane acrylate-vinyl ether mixture has 2 initial decomposition temperatures. (authors)

Oil recovery with sulfomethylated poly (lower alkyl vinyl ether/maleic anhydride)

Energy Technology Data Exchange (ETDEWEB)

Norton, C.J.; Falk, D.O.

1973-05-22

Lower alkyl vinyl ether e.g., methyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, hexyl vinyl ether, is copolymerized conventionally with maleic anhydride, the resulting copolymer is treated with ammonia or ammonium hydroxide to form the partial amide-ammonium salt, and this salt is in turn treated with formaldehyde and thereafter or simultaneously with ammonium or alkali metal salt sulfite (including bisulfites, etc.) to form an at least partially sulfomethylated copolymer. Aqueous solutions of the sulfomethylated copolymer are useful in increasing the viscosity of drive fluids used in the supplemented recovery of petroleum from subterranean formations. In general, enhancing the polyionic character of mobility control agents used in supplemented recovery of petroleum provides enhanced recovery. Achieving this enhancement of polyionic character through use of sulfonate groups provides a mobility control agent with good ability to sustain viscosity in the presence of brine and lime, usually present in the connate waters of petroleum-bearing formations. (7 claims)

A general enantioselective route to the chamigrene natural product family

KAUST Repository

White, David E.; Stewart, Ian C.; Seashore-Ludlow, Brinton A.; Grubbs, Robert H.; Stoltz, Brian M.

2010-01-01

Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

A general enantioselective route to the chamigrene natural product family

KAUST Repository

White, David E.

2010-06-01

Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

Surface Properties of a Novel Poly(vinyl alcohol Film Prepared by Heterogeneous Saponification of Poly(vinyl acetate Film

Directory of Open Access Journals (Sweden)

Seong Baek Yang

2017-10-01

Full Text Available Almost general poly(vinyl alcohol (PVA films were prepared by the processing of a PVA solution. For the first time, a novel poly(vinyl alcohol (PVA film was prepared by the saponification of a poly(vinyl acetate (PVAc film in a heterogenous medium. Under the same saponification conditions, the influence of saponification time on the degree of saponification (DS was studied for the preparation of the saponified PVA film, and it was found that the DS varied with time. Optical microscopy was used to confirm the characteristics and surface morphology of the saponified PVA film, revealing unusual black globules in the film structure. The contact angle of the films was measured to study the surface properties, and the results showed that the saponified PVA film had a higher contact angle than the general PVA film. To confirm the transformation of the PVAc film to the PVA film, 1H nuclear magnetic resonance spectroscopy, X-ray diffraction measurements, differential scanning calorimetry, and Fourier-transform infrared spectroscopy were employed.

Tailor-made starch-based conjugates containing well-defined poly(vinyl acetate and its derivative poly(vinyl alcohol

Directory of Open Access Journals (Sweden)

2011-06-01

Full Text Available Reversible addition-fragmentation chain transfer (RAFT polymerization was adopted to synthesize starch-based conjugates that possessed controllable architecture and properties. Starch-based xanthate agent was prepared and applied as chain transfer agent to conduct the living/controlled polymerization (LCP of vinyl acetate, which generated tailor-made conjugates of starch and well-defined poly(vinyl acetate (SVAc. The relevant derivatives, conjugates of starch and chain length-controlled poly(vinyl alcohol (SVA, were obtained subsequently. Various characterizations such as Fourier transform infrared spectra (FTIR, ultraviolet-visible spectroscopy (UV, proton nuclear magnetic resonance (1H NMR, gel permeation chromatography (GPC, X-ray diffraction (XRD, Thermogravimetric analysis (TGA, and dynamic mechanical thermal analysis (DMTA were performed to examine the structure of intermediates and the starch-based conjugates. Static contact angle measurements revealed that the hydrophilic character of starch-based conjugates was tunable. Well-defined SVAc was amphiphilic and it was able to self-assemble into size controllable micelles, which was verified by contact angles, transmission electron microscopy (TEM and dynamic light scattering (DLS tests. SVA exhibited much higher capability to form physically cross-linked hydrogel than starch did. Both the characteristic of SVAc and SVA were chain length-dependent.

Combined experimental and theoretical study of the mechanism and enantioselectivity of palladium-catalyzed intermolecular Heck coupling

DEFF Research Database (Denmark)

Henriksen, Signe Teuber; Norrby, Per-Ola; Kaukoranta, Päivi

2008-01-01

. The steric interactions in this transition state fully account for the enantioselectivity observed with the ligands studied. The calculations also predict relative reactivity and nonlinear mixing effects for the investigated ligands; these predictions are fully validated by experimental testing. Finally......The asymmetric Heck reaction using P,N-ligands has been studied by a combination of theoretical and experimental methods. The reaction follows Halpern-style selectivity; that is, the major isomer is produced from the least favored form of the pre-insertion intermediate. The initially formed Ph......, the low conversion observed with some catalysts was found to be caused by inactivation due to weak binding of the ligand to Pd(0). Adding monodentate PPh3 alleviated the precipitation problem without deteriorating the enantioselectivity and led to one of the most effective catalytic systems to date....

Interpolymer complexses of vinyl ether copolymer with polyacrylic and polymethacrylic acids

Directory of Open Access Journals (Sweden)

E. Shaikhutdinov

2012-03-01

Full Text Available The interactions between macromolecules of copolymers based on vinyl ethers (vinyl ether of monoethanolamine and vinyl buthyl ether and 2-acryloilamido-2-methylpropanesulphonic acid with polyacrylic and polymethacrylic acid and, as well as study the effect of interpolymer interactions in the adsorption of polymers at the aqueous solution-air interface were investigated. The observed synergistic increase in surface activity of macromolecules into polyelectrolyte mixtures explained by the formation of interpolymer complexes polyacid - copolymer.

Case Report of Focal Epithelial Hyperplasia (Heck's Disease) with Polymerase Chain Reaction Detection of Human Papillomavirus 13.

Science.gov (United States)

Brehm, Mary A; Gordon, Katie; Firan, Miahil; Rady, Peter; Agim, Nnenna

2016-05-01

Focal epithelial hyperplasia (FEH), or Heck's disease, is an uncommon benign proliferation of oral mucosa caused by the human papillomavirus (HPV), particularly subtypes 13 and 32. The disease typically presents in young Native American patients and is characterized by multiple asymptomatic papules and nodules on the oral mucosa, lips, tongue, and gingiva. The factors that determine susceptibility to FEH are unknown, but the ethnic and geographic distribution of FEH suggests that genetic predisposition, particularly having the human lymphocytic antigen DR4 type, may be involved in pathogenesis. We report a case of FEH with polymerase chain reaction detection of HPV13 in a healthy 11-year-old Hispanic girl and discuss the current understanding of disease pathogenesis, susceptibility, and treatment. © 2016 Wiley Periodicals, Inc.

Investigating the nature of palladium chain-walking in the enantioselective redox-relay Heck reaction of alkenyl alcohols.

Science.gov (United States)

Hilton, Margaret J; Xu, Li-Ping; Norrby, Per-Ola; Wu, Yun-Dong; Wiest, Olaf; Sigman, Matthew S

2014-12-19

The mechanism of the redox-relay Heck reaction was investigated using deuterium-labeled substrates. Results support a pathway through a low energy palladium-alkyl intermediate that immediately precedes product formation, ruling out a tautomerization mechanism. DFT calculations of the relevant transition structures at the M06/LAN2DZ+f/6-31+G* level of theory show that the former pathway is favored by 5.8 kcal/mol. Palladium chain-walking toward the alcohol, following successive β-hydride eliminations and migratory insertions, is also supported in this study. The stereochemistry of deuterium labels is determined, lending support that the catalyst remains bound to the substrate during the relay process and that both cis- and trans-alkenes form from β-hydride elimination.

46 CFR 154.1750 - Butadiene or vinyl chloride: Refrigeration system.

Science.gov (United States)

2010-10-01

... and Operating Requirements § 154.1750 Butadiene or vinyl chloride: Refrigeration system. A... 46 Shipping 5 2010-10-01 2010-10-01 false Butadiene or vinyl chloride: Refrigeration system. 154.1750 Section 154.1750 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK...

Resonance Raman assignment and evidence for noncoupling of individual 2- and 4-vinyl vibrational modes in a monomeric cyanomethemoglobin

International Nuclear Information System (INIS)

Gersonde, K.; Yu, N.T.; Lin, S.H.; Smith, K.M.; Parish, D.W.

1989-01-01

We have investigated the resonance Raman spectra of monomeric insect cyanomethemoglobins (CTT III and CTT IV) reconstituted with (1) protohemes IX selectively deuterated at the 4-vinyl as well as the 2,4-divinyls, (2) monovinyl-truncated hemes such as pemptoheme (2-hydrogen, 4-vinyl) and isopemptoheme (2-vinyl, 4-hydrogen), (3) symmetric hemes such as protoheme III (with 2- and 3-vinyls) and protoheme XIII (with 1- and 4-vinyls), and (4) hemes without 2- and 4-vinyls such as mesoheme IX, deuteroheme IX, 2,4-dimethyldeuteroheme IX, and 2,4-dibromodeuteroheme IX. Evidence is presented that the highly localized vinyl C = C stretching vibrations at the 2- and 4-positions of the heme in these cyanomet CTT hemoglobins are noncoupled and inequivalent; i.e., the 1631- and 1624-cm-1 lines have been assigned to 2-vinyl and 4-vinyl, respectively. The elimination of the 2-vinyl (in pemptoheme) or the 4-vinyl (in isopemptoheme) does not affect the C = C stretching frequency of the remaining vinyl. Furthermore, two low-frequency vinyl bending modes at 412 and 591 cm-1 exhibit greatly different resonance Raman intensities between 2-vinyl and 4-vinyl. The observed intensity at 412 cm-1 is primarily derived from 4-vinyl, whereas the 591-cm-1 line results exclusively from the 2-vinyl. Again, there is no significant coupling between 2-vinyl and 4-vinyl for these two bending modes

1-O-vinyl glycosides via Tebbe olefination, their use as chiral auxiliaries and monomers.

Science.gov (United States)

Yuan, Jialong; Lindner, Kristof; Frauenrath, Holger

2006-07-21

A series of anomerically pure 1-O-formyl glycosides 1 was prepared and converted into the corresponding 1-O-vinyl glycosides 2 by Tebbe olefination. The unsubstituted vinyl glycosides were obtained as anomerically pure compounds in good yields, and the method of preparation was compatible with the presence of a variety of functional groups. Remarkably, the anomeric formate group was regioselectively converted into the corresponding olefin in the presence of acetate and benzoate protecting groups. With the perspective to use the 1-O-vinyl glycosides as monomers for the preparation of glycosylated poly(vinyl alcohol) derivatives with controlled tacticity, their scope as chiral auxiliaries for a stereodifferentiation in addition reactions to the olefin function was investigated by using the [2+2] cycloaddition to dichloroketene as a model reaction. In particular, vinyl 2,3,4,6-tetra-O-benzoyl-alpha-d-mannopyranoside (2i) exhibited excellent diastereoselectivity. Finally, the 1-O-vinyl glycosides were successfully subjected to radical homopolymerization in bulk or used as electron-rich comonomers in radical copolymerizations with maleic anhydride, yielding alternating, glycosylated poly(vinyl alcohol-alt-maleic anhydride).

Pd-isatin Schiff base complex immobilized onγ-Fe2O3 as a magnetically recyclable catalyst for the Heck and Suzuki cross-coupling reactions

Institute of Scientific and Technical Information of China (English)

Sara Sobhani; Farzaneh Zarifi

2015-01-01

A Pd‐isatin Schiff base complex immobilized onγ‐Fe2O3 (Pd‐isatin Schiff base‐γ‐Fe2O3) was synthe‐sized and characterized by Fourier transform infrared, scanning electron microscopy, high resolu‐tion transmission electron microscopy, X‐ray diffraction, thermogravimetric gravimetric analysis, inductively‐coupled plasma, X‐ray photoelectron spectroscopy, and elemental analysis. It was used as a magnetically reusable Pd catalyst for the Heck and Suzuki cross‐coupling reactions.

Vintage Vinyl Record Design

Science.gov (United States)

Sacco, Michael

2008-01-01

In this article, the author describes a project in which his ninth-grade art students utilized a vinyl record as an unusual medium to create a work that exhibited solid design, great creativity, and strong craftsmanship. Students presented their pieces to the class for critique, explained the process, the media, and their feelings about their…

Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts.

Science.gov (United States)

Le Nôtre, Jérôme; Witte-van Dijk, Susan C M; van Haveren, Jacco; Scott, Elinor L; Sanders, Johan P M

2014-09-01

Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200-250 °C without any external added pressure, conditions significantly milder than those described previously for the same conversion with better yield and selectivity. A comprehensive study of the reaction parameters has been performed, and the isolation of methacrylic acid was achieved in 50% yield. The decarboxylation procedure is also applicable to citric acid, a more widely available bio-based feedstock, and leads to the production of methacrylic acid in one pot in 41% selectivity. Aconitic acid, the intermediate compound in the pathway from citric acid to itaconic acid was also used successfully as a substrate. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Decarboxylation of indole-3-acetic acid and inhibition of growth in Avena sativa seedlings by plant-derived photosensitizers

Energy Technology Data Exchange (ETDEWEB)

Brennan, T.M. [Dickinson Coll., Carlisle, PA (United States). Dept. of Biology

1996-12-01

A number of plant phototoxins, when supplemented with UVA (320-400 nm) radiation, are capable of sensitizing the decomposition of indole-3-acetic acid (IAA), as measured by release of {sup 14}CO{sub 2} from carboxyl-labeled IAA. Alpha-terthienyl ({alpha}T) and harmine caused significant rates of IAA decarboxylation at concentrations as low as 1 nM and were approximately 80% as effective as riboflavin and flavin mononucleotide. Partial inhibition by sodium azide indicates that the {alpha}T-induced decarboxylation of IAA is predominately, but not entirely, a type II reaction mediated by singlet oxygen. Based on changes in UV absorption spectra, it appears that the hormones gibberellic acid, abscisic acid and 6-benzylaminopurine (a cytokinin) are less susceptible to photosensitized decomposition than is IAA. Alpha-terthienyl plus UVA also inhibited elongation growth and reduced endogenous IAA levels in Avena sativa L. coleoptile sections and promoted senescence in intact Avena seedlings. These results confirm the alelopathic potential of plant photosensitizers such as {alpha}T and indicate that the phytohormone IAA may represent an additional target for the action of photosensitizers. (Author).

Tetradentate N2O2 Chelated Palladium(II Complexes: Synthesis, Characterization, and Catalytic Activity towards Mizoroki-Heck Reaction of Aryl Bromides

Directory of Open Access Journals (Sweden)

Siti Kamilah Che Soh

2013-01-01

Full Text Available Four air and moisture-stable palladium(II-Schiff base complexes, N,N′-bis(α-methylsalicylidenepropane-1,3-diamine palladium(II (2a, N,N′-bis(4-methyl-α-methylsalicylidenepropane-1,3-diamine palladium(II (2b, N,N′-bis(3,5-di-tert-butylsalicylidenepropane-1,3-diamine palladium(II (2c, and N,N′-bis(4-methoxy-salicylidenepropane-1,3-diamine palladium(II (2d, have been successfully synthesised and characterised by CHN elemental analyses and conventional spectroscopic methods. These complexes were investigated as catalysts in the phosphine-free Mizoroki-Heck cross-coupling reactions of aryl bromides with methyl acrylate.

High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

KAUST Repository

Stoltz, Brian

2010-06-14

The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

KAUST Repository

Stoltz, Brian; McDougal, Nolan; Virgil, Scott

2010-01-01

The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

Arylation of beta, gamma-unsaturated lactones by a Heck-Matsuda reaction: an unexpected route to aryldiazene butenolides and pyridazinones

Energy Technology Data Exchange (ETDEWEB)

Taylor, Jason G.; Correia, Carlos Roque D., E-mail: roque@iqm.unicamp.b [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

2010-07-01

The palladium catalysed coupling of aryldiazonium salts with {beta}-{gamma}-unsaturated lactones under basic conditions has been investigated. Both (3H)-furanone and {alpha}-angelicalactone were evaluated as substrates in the Heck Matsuda reaction but both failed to afford the desired arylated butenolides. Under basic conditions, {beta}-{gamma}-unsaturated lactones generate highly nucleophilic enolates that preferentially undergo azo coupling reactions with arenediazonium salts to afford aryldiazene butenolides. The electronic and steric effect of the substituents on the aryldiazonium salt in the azo coupling reaction is described. Aryldiazene-lactone derivatives were obtained in good yields from a highly facile and straightforward procedure. An aminoisomaleimide was formed from (3H)-furanone and cyclized to the corresponding pyridazinones in modest yield. (author)

Radicals derived from acetaldehyde and vinyl alcohol.

Science.gov (United States)

Estep, Marissa L; Morgan, W James; Winkles, Alexander T; Abbott, Adam S; Villegas-Escobar, Nery; Mullinax, J Wayne; Turner, Walter E; Wang, Xiao; Turney, Justin M; Schaefer, Henry F

2017-10-18

Vinyl alcohol and acetaldehyde are isoelectronic products of incomplete butanol combustion. Along with the radicals resulting from the removal of atomic hydrogen or the hydroxyl radical, these species are studied here using ab initio methods as complete as coupled cluster theory with single, double, triple, and perturbative quadruple excitations [CCSDT(Q)], with basis sets as large as cc-pV5Z. The relative energies provided herein are further refined by including corrections for relativistic effects, the frozen core approximation, and the Born-Oppenheimer approximation. The effects of anharmonic zero-point vibrational energies are also treated. The syn conformer of vinyl alcohol is predicted to be lower in energy than the anti conformer by 1.1 kcal mol -1 . The alcoholic hydrogen of syn-vinyl alcohol is found to be the easiest to remove, requiring 84.4 kcal mol -1 . Five other radicals are also carefully considered, with four conformers investigated for the 1-hydroxyvinyl radical. Beyond energetics, we have conducted an overhaul of the spectroscopic literature for these species. Our results also provide predictions for fundamental modes yet to be reported experimentally. To our knowledge, the ν 3 (3076 cm -1 ) and ν 4 (2999 cm -1 ) C-H stretches for syn-vinyl alcohol and all but one of the vibrational modes for anti-vinyl alcohol (ν 1 -ν 14 ) are yet to be observed experimentally. For the acetyl radical, ν 6 (1035 cm -1 ), ν 11 (944 cm -1 ), ν 12 (97 cm -1 ), and accounting for our changes to the assignment of the 1419.9 cm -1 experimental mode, ν 10 (1441 cm -1 ), are yet to be observed. We have predicted these unobserved fundamentals and reassigned the experimental 1419.9 cm -1 frequency in the acetyl radical to ν 4 rather than to ν 10 . Our work also strongly supports reassignment of the ν 10 and ν 11 fundamentals of the vinoxy radical. We suggest that the bands assigned to the overtones of these fundamentals were in fact combination bands. Our

Radiation-induced emulsion copolymerization of vinyl chloride with vinyl acetate in an engineering flow system

International Nuclear Information System (INIS)

Tsai, J.T.; Stahel, E.P.; Stannett, V.T.

1979-01-01

A flow reactor system was used to study the radiation-induced emulsion copolymerization of vinyl chloride with vinyl acetate. The emulsion was recirculated from a stirred vessel through transfer lines to a tubular reactor located within a high-intensity Co-60 source. The effects of physical chemical variables such as soap concentration, phase ratio, reaction temperature and residence time distribution on the molecular weight properties were investigated. The rate of copolymerization was found to be proportional to the 0.17 power of the soap concentration. Variation of the monomer-water ratio produced no significant change in rate. The rate increased with an increase in temperature over the range 5 to 50 0 C, while the average molecular weights of the copolymer increased with decreasing polymerization temperature. The molecular weight distribution in this engineering system was found to be essentially similar to those produced in a batch system

Inhibition of mammalian nitric oxide synthases by agmatine, an endogenous polyamine formed by decarboxylation of arginine.

OpenAIRE

Galea, E; Regunathan, S; Eliopoulos, V; Feinstein, D L; Reis, D J

1996-01-01

Agmatine, decarboxylated arginine, is a metabolic product of mammalian cells. Considering the close structural similarity between L-arginine and agmatine, we investigated the interaction of agmatine and nitric oxide synthases (NOSs), which use L-arginine to generate nitric oxide (NO) and citrulline. Brain, macrophages and endothelial cells were respectively used as sources for NOS isoforms I, II and III. Enzyme activity was measured by the production of nitrites or L-citrulline. Agmatine was ...

Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts

NARCIS (Netherlands)

Notre, le J.E.L.; Witte-van Dijk, S.C.M.; Haveren, van J.; Scott, E.L.; Sanders, J.P.M.

2014-01-01

Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200–2508C without any external added pressure, conditions

Generation of a Proton Motive Force by Histidine Decarboxylation and Electrogenic Histidine/Histamine Antiport in Lactobacillus buchneri

OpenAIRE

Molenaar, Douwe; Bosscher, Jaap S.; Brink, Bart ten; Driessen, Arnold J.M.; Konings, Wil N.

1993-01-01

Lactobacillus buchneri ST2A vigorously decarboxylates histidine to the biogenic amine histamine, which is excreted into the medium. Cells grown in the presence of histidine generate both a transmembrane pH gradient, inside alkaline, and an electrical potential (delta psi), inside negative, upon addition of histidine. Studies of the mechanism of histidine uptake and histamine excretion in membrane vesicles and proteoliposomes devoid of cytosolic histidine decarboxylase activity demonstrate tha...

40 CFR 61.65 - Emission standard for ethylene dichloride, vinyl chloride and polyvinyl chloride plants.

Science.gov (United States)

2010-07-01

... dichloride, vinyl chloride and polyvinyl chloride plants. 61.65 Section 61.65 Protection of Environment... AIR POLLUTANTS National Emission Standard for Vinyl Chloride § 61.65 Emission standard for ethylene dichloride, vinyl chloride and polyvinyl chloride plants. An owner or operator of an ethylene dichloride...

Preparation and characterization of film of poly vinyl acetate ethylene copolymer emulsion

International Nuclear Information System (INIS)

Zhang, Yanhua; Gu, Jiyou; Tan, Haiyan; Shi, Junyou; Di, Mingwei; Zuo, Yingfeng; Qiu, Si

2013-01-01

In order to improve the storage modulus and water resistance of poly (vinyl acetate), the vinyl acetate and poly (vinyl alcohol) (PVA) were respectively used as monomers and protective colloid to prepare a new kind of polyvinyl acetate emulsion adhesive by continuous emulsion polymerization. The dynamic mechanics, particle distribution, glass transition temperature, polymer emulsion structure of both polymerized and copolymerized emulsion were analyzed by SEM, DMA and XPS, respectively. The results indicated that the copolymerized emulsion has the appropriate particle size and the uniform particle distribution, the glass transition temperature increased from 50 °C to 70 °C, compared with poly (vinyl acetate). It could be seen from XPS spectra of copolymerized emulsion that key characteristic peak of C=O was still existent. X-ray photoelectron spectra revealed that the addition of EVA did not generate the new bond, whereas the maximum percentage increases in ester was determined in the composite film with the introduction of EVA of 25%, which indicated that the composite film has copolymer structure. The storage modulus and water resistance of poly (vinyl acetate) were improved due to the introduction of the EVA.

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

International Nuclear Information System (INIS)

Gotoda, Masao; Kitada, Yoshinori.

1975-01-01

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

Effect of gamma ray on poly(lactic acid)/poly(vinyl acetate-co-vinyl alcohol) blends as biodegradable food packaging films

Science.gov (United States)

Razavi, Seyed Mohammad; Dadbin, Susan; Frounchi, Masoud

2014-03-01

Poly(lactic acid) (PLA)/poly(vinyl acetate-co-vinyl alcohol) [P(VAc-co-VA)] blends as new transparent film packaging materials were prepared at various blend compositions and different vinyl alcohol contents. The blends and pure PLA were irradiated by gamma rays to investigate the extent of changes in the packaging material during gamma ray sterilization process. The miscibility of the blends was dependent on the blend composition and vinyl alcohol content; gamma irradiation had little effect on the extent of miscibility. The glass transition temperature of pure PLA and PLA/P(VAc-co-VA) miscible blends reduced after irradiation. On the other hand in PLA/P(VAc-co-VA) immiscible blends, while the glass transition temperature of the PLA phase decreased; that of the copolymer phase slightly increased. The reduction in the glass transition was about 10 percent for samples irradiated with 50 kGy indicating dominance of chain scission of PLA molecules at high irradiation dose. The latter was verified by drop in mechanical properties of pure PLA after exposing to gamma irradiation at 50 kGy. Blending of PLA with the copolymer P(VAc-co-VA) compensated greatly the adverse effects of irradiation on PLA. The oxygen-barrier property of the blend was superior to the neat PLA and remained almost intact with irradiation. The un-irradiated and irradiated blends had excellent transparency. Gamma ray doses used for sterilization purposes are usually less than 20 kGy. It was shown that gamma irradiation at 20 kGy had no or little adverse effects on PLA/P(VAc-co-VA) blends mechanical and gas barrier properties.

Synthesis and characterization of para-pyridine linked NHC palladium complexes and their studies for the Heck-Mizoroki coupling reaction.

Science.gov (United States)

Liu, Ya-Ming; Lin, Yi-Chun; Chen, Wen-Ching; Cheng, Jen-Hao; Chen, Yi-Lin; Yap, Glenn P A; Sun, Shih-Sheng; Ong, Tiow-Gan

2012-06-28

This paper describes the synthesis of 1-(pyridine-4-ylmethyl) NHC and their Pd(II) and Ag(I) complexes, which are fully characterized. Interestingly, we have also synthesized a Pd complex 3a-CO(3) using a more direct treatment of K(2)CO(3) with PdCl(2). 3a-CO(3) represents the first reported solid structure of a Pd η(2)-carbonato complex stabilized by an NHC framework. 3a-CO(3) can be easily converted to a PdCl(2) derivative by treating it with chloroform. We have found these palladium complexes mediate the Heck-Mizoroki coupling with a low catalyst loading. Furthermore, we also expand such catalytic manifold toward constructing fused polyaromatic substrates, a highly useful class of compounds in optoelectronic chemistry.

Plastics piping systems for industrial applications : acrylonitrile-butadiene- styrene (ABS), unplasticized poly(vinyl chloride) (PVC-U) and chlorinated poly(vinyl chloride) (PVC-C) : specifications for components and the system : metric series

CERN Document Server

International Organization for Standardization. Geneva

2003-01-01

Plastics piping systems for industrial applications : acrylonitrile-butadiene- styrene (ABS), unplasticized poly(vinyl chloride) (PVC-U) and chlorinated poly(vinyl chloride) (PVC-C) : specifications for components and the system : metric series

Highly filled biocomposites based on ethylene-vinyl acetate copolymer and wood flour

Science.gov (United States)

Shelenkov, P. G.; Pantyukhov, P. V.; Popov, A. A.

2018-05-01

Recently, there is a great interest in the world to biodegradable materials based on synthetic polymers in a composition with natural fillers. Highly filled polymer composite materials based on various grades of synthetic block copolymer of ethylene vinyl acetate with wood flour were under investigation. Five grades of ethylene-vinyl acetate copolymer differing in the content of vinyl acetate groups and a melt flow index were used in this work in order to find the best one for highly filled biocomposites. Wood flour content in biocomposites was 50, 60, 70 weight %. The rheological and physico-mechanical characteristics of the resulting biocomposites were studied.

Effect of Saponification Condition on the Morphology and Diameter of the Electrospun Poly(vinyl acetate) Nanofibers for the Fabrication of Poly(vinyl alcohol) Nanofiber Mats

OpenAIRE

Seong Baek Yang; Jong Won Kim; Jeong Hyun Yeum

2016-01-01

Novel poly(vinyl alcohol) (PVA) nanofiber mats were prepared for the first time through heterogeneous saponification of electrospun poly(vinyl acetate) (PVAc) nanofibers. The effect of varying the saponification conditions, including temperature, time, and concentration of the alkaline solution, on the morphology of the saponified PVA fibers were evaluated by field-emission scanning electron microscopy. At 25 °C, the saponified PVA fibers exhibited a broad diameter distribution. The average f...

Synthesis and structure of aromatic and heterocyclic tellurium compounds 33. Synthesis of [2-(aryltelluro)vinyl]aldehydes and ketones and stereochemistry of nucleophilic substitution under vinyl atom of carbon

International Nuclear Information System (INIS)

Sadekov, I.D.; Rivkin, B.B.; Zakharov, A.V.; Minkin, V.I.

1996-01-01

By means of interaction of (2-vinylchlorida) carbonyl compounds and (2-acylvinyl) triethylammonium chlorides and arenetellurolate-anions certain, [2-(aryltelluro)vinyl]ketones and [2-(aryltelluro)vinyl]aldehydes have been synthesized, while by means of reaction between 2-aroylvinyl chlorides and Li 2 Te some di(2-aroylvinyl)tellurides have been prepared. Interaction of (2-vinylchloride)ketones with arenetellurolate-anions always gives rise to Z-isomers of [2-(aryltelluro)vinyl]ketones as a result of stabilization of intermediate carbanion by intramolecular coordination O→Te. Nucleophilic addition of arenetellurolate-anions to α-acetylene aldehydes and ketones occurs as trans-addition. 36 refs., 2 figs., 1 tab

“Why is it that we can’t let go of the vinyl record?”

OpenAIRE

Julien, Olivier

2015-01-01

If one were to try to summarize Richard Osborne’s Vinyl: A History of the Analogue Record, we might describe it as an endeavour to discover what makes the vinyl disc record such a key medium in the determination of twentieth-century music by sound recording. As the author makes clear from the outset: “Although vinyl lost its status as Britain’s leading albums format as long ago as 1985 and thus looked set for a permanent decline, sales of vinyl LPs rose year on year by 43.7 per cent in 2011....

Graft copolymerization of vinyl monomers onto nylon 6 fibers by γ-ray pre-irradiation in air

International Nuclear Information System (INIS)

Iwasaki, Tatsuo; Ueda, Yoshitsugu

1992-01-01

Vinyl acetate, methyl methacrylate, alkyl acrylates, acrylonitrile, and acrylamide, were grafted onto nylon 6 fibers by the γ-ray pre-irradiation technique, and the effects of grafting on the microstructure and the mechanical properties of the graft copolymers were investigated. According to the analysis by wide-angle X-ray diffraction, the degree of crystallization decreased by increasing the percent graft of poly(vinyl acetate) in the grafted nylon 6 films. The mechanical parameters, such as the Young's modulus and the tensile strength at break, increased with increasing percent graft up to 50%. When percent grafting was smaller than 50%, rather homogeneous amorphous materials were obtained with vinyl acetate, while heterogeneous ones were obtained with other vinyl monomers. A poly(vinyl alcohol) grafted nylon 6 was obtained effectively by saponification of poly(vinyl acetate) grafted nylon 6, the former showing higher mechanical properties than the latter. Similar behavior was observed after saponification of the poly(methyl acrylate) grafted nylon 6. (author)

Preparation of vinyl chloride – vinyl ether copolymers via partial etherification from PVC

Directory of Open Access Journals (Sweden)

2007-08-01

Full Text Available The chemical modifications of poly (vinyl chloride with aliphatic and aromatic alcohols compounds have been investigated at room temperature and atmospheric pressure, catalysed by a new green basic catalyst, the Maghnite-K+. The presence of ether groups in the products is proven by infra red spectroscopy (IR as well as by nuclear magnetic resonance spectroscopy (1H NMR, and characterized by intrinsic viscosity as well as by gel permeation chromatography (GPC.

O-Carboxymethyl Chitosan Supported Heterogeneous Palladium and Ni Catalysts for Heck Reaction

Directory of Open Access Journals (Sweden)

Dongjun Lv

2017-01-01

Full Text Available Two polymer catalysts (Pd-OCMCS and Ni-OCMCS with good reusability were synthesized by coordinating Pd and Ni onto O-carboxymethyl chitosan (OCMCS. The chemical structure and thermal stability of prepared catalysts were determined by Fourier transform infrared (FT-IR spectra, Energy Dispersive Spectrometer (EDSanalysis, X-ray diffraction (XRD, and thermogravimetric analyzer (TG-DTG, and the analysis results showed that the Pd and Ni ions coordinated onto the OCMCS and formed a ligand with the –COOH group, amino groups, and –OH group on the OCMCS, and the EDS and Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES analysis results showed that the loading amounts of Pd and Ni were approximately 8.3% and 8.9%, respectively. In the Heck reaction between aryl halides and n-butyl acrylate catalyzed by the prepared catalyst, the test results showed that the product yield followed the order of aryl iodide > aryl bromide > aryl chloride. Additionally, the product yield for the aryl iodide and aryl bromide could reach up to 99% and 96%, respectively. Moreover, the electron-withdrawing and electron-donating property of the group on the aryl also affected the product yield, and the product yield for aryl halides with electron-withdrawing group p-NO2, p-CH3CO, and p-CHO was higher than that with electron-donating group p-CH3.

29 CFR 1926.1117 - Vinyl chloride.

Science.gov (United States)

2010-07-01

... 29 Labor 8 2010-07-01 2010-07-01 false Vinyl chloride. 1926.1117 Section 1926.1117 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... chloride. Note: The requirements applicable to construction work under this section are identical to those...

Domino-Fluorination-Protodefluorination Enables Decarboxylative Cross-Coupling of α-Oxocarboxylic Acids with Styrene via Photoredox Catalysis.

Science.gov (United States)

Zhang, Muliang; Xi, Junwei; Ruzi, Rehanguli; Li, Nan; Wu, Zhongkai; Li, Weipeng; Zhu, Chengjian

2017-09-15

Domino-fluorination-protodefluorination decarboxylative cross-coupling of α-keto acids with styrene has been developed via photoredox catalysis. The critical part of this strategy is the formation of the carbon-fluorine (C-F) bond by the capture of a carbon-centered radical intermediate, which will overcome side reactions during the styrene radical functionalization process. Experimental studies have provided evidence indicating a domino-fluorination-protodefluorination pathway with α-keto acid initiating the photoredox cycle. The present catalytic protocol also affords a novel approach for the construction of α,β-unsaturated ketones under mild conditions.

Flame retardant cotton fabrics by electron beam-induced polymerization of vinyl phosphonate oligomer

International Nuclear Information System (INIS)

Sawai, Takeshi; Ametani, Kazuo; Enomoto, Ichiro

1988-01-01

Vinyl phosphonate oligomer is presently used commercially as a cellulosic flame retardant in conjugation with N-methylol acrylamide, using a persulfate catalyst and a thermal cure. This combination can also be cured at room temperature with electron beams, as can the vinyl phosphonate alone. For the textile application, fixation of flame retardants by electron beams with low energy is one of the most promising applications. For the purpose of preparing flame resistant cotton fabrics such as bed sheets and pajamas, flame retardant curing of vinyl phosphonate oligomer on cotton fabrics was examined using electron beams from a self-sealed electron beam processor and gamma rays from a 60 Co source. A joint investigation was undertaken by the Tokyo Metropolitan Textile Research Institute and Tokyo Metropolitan Isotope Research Center to determine the feasibility of curing vinyl phosphonate oligomer on the cotton fabrics for textile finishing. (author)

Atmospheric fate of methyl vinyl ketone

DEFF Research Database (Denmark)

Praske, Eric; Crounse, John D; Bates, Kelvin H

2015-01-01

First generation product yields from the OH-initiated oxidation of methyl vinyl ketone (3-buten-2-one, MVK) under both low and high NO conditions are reported. In the low NO chemistry, three distinct reaction channels are identified leading to the formation of (1) OH, glycolaldehyde, and acetyl...

Optical Reading and Playing of Sound Signals from Vinyl Records

OpenAIRE

Hensman, Arnold; Casey, Kevin

2007-01-01

While advanced digital music systems such as compact disk players and MP3 have become the standard in sound reproduction technology, critics claim that conversion to digital often results in a loss of sound quality and richness. For this reason, vinyl records remain the medium of choice for many audiophiles involved in specialist areas. The waveform cut into a vinyl record is an exact replica of the analogue version from the original source. However, while some perceive this media as reproduc...

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

Science.gov (United States)

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

2017-01-01

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

Preparation of poly(vinyl alcohol)-grafted graphene oxide/poly(vinyl alcohol) nanocomposites via in-situ low-temperature emulsion polymerization and their thermal and mechanical characterization

Science.gov (United States)

Zhang, Shengchang; Liu, Pengqing; Zhao, Xiangsen; Xu, Jianjun

2017-02-01

An in-situ polymerization combined with chemical grafting modification method for preparing Poly(vinyl alcohol)-grafted graphene oxide/Poly(vinyl alcohol) (PVA-g-GO/PVA) nanocomposites was reported. Firstly, Poly(vinyl acetate)-grafted graphene oxide/Poly(vinyl acetate) nanocomposites were prepared, and then the PVA-g-GO/PVA nanocomposites could be obtained through alcoholysis reaction. X-ray photoelectron spectrometer and fourier-transform infrared spectrometer confirmed that the PVAc or PVA chains were successfully grafted to GO sheets during in-situ polymerization and alcoholysis. And the results from transmission electron microscopy, scanning electron microscopy and X-ray diffraction showed that the well compatibility and homogenous dispersion of PVA-g-GO in PVA matrix could be achieved. Differential scanning calorimetric, thermogravimetry analysis and tensile test were employed to study the thermal and mechanical properties of the PVA-g-GO/PVA nanocomposites. The results indicated that a 53% improvement of tensile strength and a 36% improvement of Young's modulus were achieved by addition of 0.5 wt% of GO sheets. And the glass transition temperature of PVA-g-GO/PVA nanocomposites was increased, and their thermal stability and crystallization degree were both decreased. Due to well dispersion of fillers and strong interfacial interactions at the filler-matrix interface, in-situ polymerization combined with chemical grafting modification was a good choice to prepare graphene/PVA nanocomposite with excellent mechanical properties.

Structure of chlorinated poly(vinyl chloride). III. Preparation of poly(vinyl chloride)-β,β-d2 as a model for the study of the mechanism of chlorination and of the chlorinated poly(vinyl chloride) structure

International Nuclear Information System (INIS)

Lukas, R.; Kolinsky, M.

1976-01-01

A method for the preparation of poly(vinyl chloride)-β,β-d 2 (PVC-β,β-d 2 ) as a model for the investigation of the mechanism of chlorination and of the CPVC structure has been suggested. The conditions of preparation of deuterated intermediates of a multistage synthesis of vinyl chloride-β,β-d 2 and of suspension-polymerized PVC-β,β-d 2 have been described including the mass balance. Malonic acid was used as the starting compound. Tacticity values of a sample of PVC-β,β-d 2 and its infrared and nuclear magnetic resonance (NMR) spectra are presented and compared with the data already published

(e,2e) momentum spectroscopic study of the C=C π orbitals of the vinyl halides

International Nuclear Information System (INIS)

Gorunganthu, R.R.; Coplan, M.A.; Leung, K.T.; Tossell, J.A.; Moore, J.H.; Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada; Department of Chemistry, University of Maryland, College Park, Maryland 20742)

1989-01-01

The distribution of electron momentum density has been measured for the outermost occupied orbitals of the vinyl halides and ethylene using the (e,2e) technique. In contrast to the ionization potentials for these π orbitals which decrease monotonically from vinyl fluoride to vinyl iodide, the values of the momenta where the distributions are a maximum, p max , increase from the fluoride through the bromide and then shift back to a lower value for the iodide. This observation can be analyzed in terms of B(r), the Fourier transform of the observed momentum distribution, and ΔB(r), the difference between B(r) functions. The shape of ΔB(r) for the fluoride, chloride, and bromide in comparison to ethylene reflects the effect of the carbon--halogen antibonding interaction in these vinyl halides. On the other hand, in vinyl iodide the antibonding interaction is compensated for by the diffuse iodine 5p character of the molecular orbital. The relation of these observations to chemical properties of the vinyl halides is discussed along with differences between experiment and calculations at low momentum

Decontamination efficiency of a sheet of vinyl wall paper as a surface material in radioisotope laboratory

International Nuclear Information System (INIS)

Furukawa, Kazuhiko; Funadera, Kanako

1989-01-01

It has long been desired to prevent surface materials from cracking in a radioisotope laboratory. We applied a sheet of nonflammable wall paper, vinyl cloth, as a surface material to cover concrete wall. It was sufficiently resistant to the reinforced concrete wall cracking. The efficiency of the decontamination of the vinyl cloth was compared with those of stainless steel, iron and painted plates. The contamination and decontamination indices were determined in these surface materials after contamination with [ 32 P]orthophosphate (pH 3, 7 and 11) for 0 to 48 h. Both of the indices of the vinyl cloth were higher than those of the other materials. Further, it was confirmed that the vinyl cloth was resistant to acid and alkaline conditions and radioisotopes could not be permeable. The wipe off efficiency was also investigated in these materials by use of several decontamination detergents. In any reagents tested, the wipe of efficiency of the vinyl cloth was more than 80%. Thus, the vinyl cloth could be used for the surface material and is one of good surface materials in a radioisotope laboratory. (author)

Synthesis of tritium labelled methyl vinyl ketone and its use in copolymer analysis

International Nuclear Information System (INIS)

Burfield, D.R.; Savariar, C.M.

1980-01-01

The synthesis of tritiated methyl vinyl ketone by base catalysed exchange and its use in determining the ketone content of styrene/methyl vinyl ketone copolymers are reported. Methods of assay are described in detail and the general applicability of the method is discussed. (author)

Impact of Industrial Grade Modified PVA to Vinyl Acetate Semi-continuous Emulsion Polymerization and Properties of Final Product

Directory of Open Access Journals (Sweden)

Mindaugas DUBININKAS

2013-03-01

Full Text Available Successful vinyl acetate radical emulsion polymerization in water with different type of industrial grade poly(vinyl alcohol were produced by semi continuous way. The poly(vinyl alcohol type has crucial impact on dispersion rheological as well on films and bonding strength properties. It should be stated that the films containing modified poly (vinyl alcohol has better water resistance and mechanical properties. Poly(vinyl alcohol with higher ethylene moieties content and high hydrolization degree determines extremely low viscosity of final dispersion.DOI: http://dx.doi.org/10.5755/j01.ms.19.1.3823

Radiation chemical grafting of vinyl acetate and styrene on nitrocellulose

International Nuclear Information System (INIS)

Chapiro, A.; Foex, M.; Jendrychowska-Bonamour, A.M.

1977-01-01

Vinyl acetate and styrene were grafted onto nitrocellulose using the direct radiation grafting technique with 500 and 3000 Ci 60 Co γ sources. For vinyl acetate, the reaction proceeds homogeneously. The kinetics are dominated by degradative chain transfer to the nitrocellulose. The polymerization of vinyl acetate was examined in the presence of isoamyl nitrate, a model for nitrocellulose; the transfer constant was determined and the results are treated semi-quantitatively. For styrene, grafting occurs in a swollen film irradiated in the presence of excess monomer. The diffusion of styrene into nitrocellulose is extremely slow; methanol was added to the reaction mixture to favour diffusion which was found to obey Fick's law. The diffusion constant and activation energy of diffusion are evaluated. The grafting kinetics are controlled by monomer diffusion, accounting for the increase of dose-rate exponent with temperature. A spontaneous grafting process occurs in the absence of irradiation. It is initiated by macroradicals arising from thermal decomposition of nitrocellulose. (author)

Scientists Toast the Discovery of Vinyl Alcohol in Interstellar Space

Science.gov (United States)

2001-10-01

Astronomers using the National Science Foundation's 12 Meter Telescope at Kitt Peak, AZ, have discovered the complex organic molecule vinyl alcohol in an interstellar cloud of dust and gas near the center of the Milky Way Galaxy. The discovery of this long-sought compound could reveal tantalizing clues to the mysterious origin of complex organic molecules in space. Vinyl Alcohol and its fellow isomers "The discovery of vinyl alcohol is significant," said Barry Turner, a scientist at the National Radio Astronomy Observatory (NRAO) in Charlottesville, Va., "because it gives us an important tool for understanding the formation of complex organic compounds in interstellar space. It may also help us better understand how life might arise elsewhere in the Cosmos." Vinyl alcohol is an important intermediary in many organic chemistry reactions on Earth, and the last of the three stable members of the C2H4O group of isomers (molecules with the same atoms, but in different arrangements) to be discovered in interstellar space. Turner and his colleague A. J. Apponi of the University of Arizona's Steward Observatory in Tucson detected the vinyl alcohol in Sagittarius B -- a massive molecular cloud located some 26,000 light-years from Earth near the center of our Galaxy. The astronomers were able to detect the specific radio signature of vinyl alcohol during the observational period of May and June of 2001. Their results have been accepted for publication in the Astrophysical Journal Letters. Of the approximately 125 molecules detected in interstellar space, scientists believe that most are formed by gas-phase chemistry, in which smaller molecules (and occasionally atoms) manage to "lock horns" when they collide in space. This process, though efficient at creating simple molecules, cannot explain how vinyl alcohol and other complex chemicals are formed in detectable amounts. For many years now, scientists have been searching for the right mechanism to explain how the building

Adsorption of poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) polymers on zinc, zinc oxide, iron, and iron oxide surfaces.

Science.gov (United States)

Seifert, Susan; Simon, Frank; Baumann, Giesela; Hietschold, Michael; Seifert, Andreas; Spange, Stefan

2011-12-06

The adsorption of poly(vinyl formamide) (PVFA) and the statistic copolymers poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) onto zinc and iron metal particles as well as their oxides was investigated. The adsorbates were characterized by means of XPS, DRIFT spectroscopy, wet chemical analysis, and solvatochromic probes. Dicyano-bis-(1,10-phenanthroline)-iron(II) (1), 3-(4-amino-3-methylphenyl)-7-phenyl-benzo-[1,2-b:4,5-b']difuran-2,6-dione (2), and 4-tert-butyl-2-(dicyano-methylene)-5-[4-(diethylamino)-benzylidene]-Δ(3)-thiazoline (3) as solvatochromic probes were coadsorbed onto zinc oxide to measure various effects of surface polarity. The experimental findings showed that the adsorption mechanism of PVFA and PVFA-co-PVAm strongly depends on the degree of hydrolysis of PVFA and pH values and also on the kind of metal or metal oxide surfaces that were employed as adsorbents. The adsorption mechanism of PVFA/PVFA-co-PVAm onto zinc oxide and iron oxide surfaces is mainly affected by electrostatic interactions. Particularly in the region of pH 5, the adsorption of PVFA/PVFA-co-PVAm onto zinc and iron metal particles is additionally influenced by redox processes, dissolution, and complexation reactions. © 2011 American Chemical Society

Decarboxylation of furfural on Pd(111): Ab initio molecular dynamics simulations

Science.gov (United States)

Xue, Wenhua; Dang, Hongli; Shields, Darwin; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

2013-03-01

Furfural conversion over metal catalysts plays an important role in the studies of biomass-derived feedstocks. We report ab initio molecular dynamics simulations for the decarboxylation process of furfural on the palladium surface at finite temperatures. We observed and analyzed the atomic-scale dynamics of furfural on the Pd(111) surface and the fluctuations of the bondlengths between the atoms in furfural. We found that the dominant bonding structure is the parallel structure in which the furfural plane, while slightly distorted, is parallel to the Pd surface. Analysis of the bondlength fluctuations indicates that the C-H bond is the aldehyde group of a furfural molecule is likely to be broken first, while the C =O bond has a tendency to be isolated as CO. Our results show that the reaction of decarbonylation dominates, consistent with the experimental measurements. Supported by DOE (DE-SC0004600). Simulations and calculations were performed on XSEDE's and NERSC's supercomputers.

Synthesis of hybrid interfacial silica-based nanospheres composite as a support for ultra-small palladium nanoparticle and application of PdNPs/HSN in Mizoroki-Heck reaction

Science.gov (United States)

Rostamnia, Sadegh; Kholdi, Saba

2017-12-01

The silica based hollow nanosphere (silica-HNS) containing polymer of polyaniline was synthesized and chosen as a promising support for PdNPs. Then it was applied as a green catalyst in the reaction of Heck coupling with high yield. TEM and SEM-EDX/mapping images were used to study the structure and morphology. FT-IR spectroscopy, Thermal gravimetry analysis (TGA), and BET were used to characterize and investigate the catalyst. Also, the amounts of Pd loading were characterized by ICP-AES technique. Catalyst recyclability showed 5 successful runs for the reaction.

Separator Membrane from Crosslinked Poly(Vinyl Alcohol and Poly(Methyl Vinyl Ether-alt-Maleic Anhydride

Directory of Open Access Journals (Sweden)

Charu Vashisth Rohatgi

2015-03-01

Full Text Available In this work, we report separator membranes from crosslinking of two polymers, such as poly vinyl alcohol (PVA with an ionic polymer poly(methyl vinyl ether-alt-maleic anhydride (PMVE-MA. Such interpolymer-networked systems were extensively used for biomedical and desalination applications but they were not examined for their potential use as membranes or separators for batteries. Therefore, the chemical interactions between these two polymers and the influence of such crosslinking on physicochemical properties of the membrane are systematically investigated through rheology and by critical gel point study. The hydrogen bonding and the chemical interaction between PMVE-MA and PVA resulted in highly cross-linked membranes. Effect of the molecular weight of PVA on the membrane properties was also examined. The developed membranes were extensively characterized by studying their physicochemical properties (water uptake, swelling ratio, and conductivity, thermal and electrochemical properties using differential scanning calorimetry (DSC, dynamic mechanical analysis (DMA, thermo-gravimetric analysis (TGA and electrochemical impedance spectroscopy (EIS. The DSC study shows the presence of a single Tg in the membranes indicating compatibility of the two polymers in flexible and transparent films. The membranes show good stability and ion conductivity suitable for separator applications.

Separator Membrane from Crosslinked Poly(Vinyl Alcohol) and Poly(Methyl Vinyl Ether-alt-Maleic Anhydride)

Science.gov (United States)

Rohatgi, Charu Vashisth; Dutta, Naba K.; Choudhury, Namita Roy

2015-01-01

In this work, we report separator membranes from crosslinking of two polymers, such as poly vinyl alcohol (PVA) with an ionic polymer poly(methyl vinyl ether-alt-maleic anhydride) (PMVE-MA). Such interpolymer-networked systems were extensively used for biomedical and desalination applications but they were not examined for their potential use as membranes or separators for batteries. Therefore, the chemical interactions between these two polymers and the influence of such crosslinking on physicochemical properties of the membrane are systematically investigated through rheology and by critical gel point study. The hydrogen bonding and the chemical interaction between PMVE-MA and PVA resulted in highly cross-linked membranes. Effect of the molecular weight of PVA on the membrane properties was also examined. The developed membranes were extensively characterized by studying their physicochemical properties (water uptake, swelling ratio, and conductivity), thermal and electrochemical properties using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermo-gravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS). The DSC study shows the presence of a single Tg in the membranes indicating compatibility of the two polymers in flexible and transparent films. The membranes show good stability and ion conductivity suitable for separator applications. PMID:28347019

Proton NMR study of the influence of heme vinyl groups on the formation of the isomeric forms of sulfmyoglobin

International Nuclear Information System (INIS)

Chatfield, M.J.; La Mar, G.N.; Balch, A.L.; Smith, K.M.; Parish, D.W.; LePage, T.J.

1986-01-01

The formation of sulfmyoglobin has been investigated for myoglobin reconstituted with hemins having vinyls replaced by hydrogens to determine the participation of the vinyl groups in the reaction processes. Green complexes are produced in all cases, proving that vinyls are not obligatory for the formation of sulfproteins. In the presence of the 4-vinyl group, the 1 H NMR spectra of the met-cyano derivatives indicate the formation of three green species; however, the most stable of these products is not formed in the absence of this group, confirming reaction of the 4-vinyl in this species. Two new red extractable sulfmyoglobin derivatives are formed in the absence of the 4-vinyl group. (Auth.)

21 CFR 178.3790 - Polymer modifiers in semirigid and rigid vinyl chloride plastics.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Polymer modifiers in semirigid and rigid vinyl...: ADJUVANTS, PRODUCTION AIDS, AND SANITIZERS Certain Adjuvants and Production Aids § 178.3790 Polymer modifiers in semirigid and rigid vinyl chloride plastics. The polymers identified in paragraph (a) of this...

Synthesis and luminescence properties of tris(bipyridine)ruthenium(II)-containing vinyl polymers

International Nuclear Information System (INIS)

Furue, Masaoki; Sumi, Katsuhiro; Nozakura, Shun-ichi

1981-01-01

The luminescence properties of poly[Ru(bpy) 2 (6-vinyl-bpy)-co-6-vinyl-bpy], (I) were compared with those of Ru(bpy) 3 2+ at 77 - 298 K. A larger depletion of luminescence intensity and lifetime was observed in I in fluid solution. The dynamic quenching processes were suggested to be the dominant factor for the energy dissipation in I. (author)

Effect of various solvents on the viscosity-average molecular weight of poly (vinyl acetate)

International Nuclear Information System (INIS)

Rehman, W.U.; But, M.A.; Chughtai, A.; Jamil, T.; Sattar, A.

2006-01-01

Solution polymerization of Vinyl Acetate was carried out in various solvents (benzene, toluene, ethyl acetate, acetonitrile). Dilute solution viscometry was used to determine the viscosity-average molecular weight of the resulting Poly (Vinyl Acetate) (PV Ac) in each case. The viscosity-average molecular weight (M,J of PVAc was found to increase in the order benzene < toluene < ethyl acetate < acetonitrile, It was concluded that under the same reaction conditions (polymerization time, initiator quantity, solvent/monomer ratio, temperature), acetonitrile served as the best solvent for solution. polymerization of Vinyl Acetate monomer. (author)

Plastics piping systems for industrial applications – Acrylonitrile-butadiene-styrene (ABS), unplasticized poly(vinyl chloride) (PVC-U) and chlorinated poly(vinyl chloride) (PVC-C) – Specifications for components and the system – Metric series

CERN Document Server

Deutsches Institut für Normung. Berlin

2003-01-01

Plastics piping systems for industrial applications – Acrylonitrile-butadiene-styrene (ABS), unplasticized poly(vinyl chloride) (PVC-U) and chlorinated poly(vinyl chloride) (PVC-C) – Specifications for components and the system – Metric series

Decarboxylation of Malate in the Crassulacean Acid Metabolism Plant Bryophyllum (Kalanchoe) fedtschenkoi (Role of NAD-Malic Enzyme).

Science.gov (United States)

Cook, R. M.; Lindsay, J. G.; Wilkins, M. B.; Nimmo, H. G.

1995-01-01

The role of NAD-malic enzyme (NAD-ME) in the Crassulacean acid metabolism plant Bryophyllum (Kalanchoe) fedtschenkoi was investigated using preparations of intact and solubilized mitochondria from fully expanded leaves. Intact, coupled mitochondria isolated during the day or night did not differ in their ability to take up [14C]malic acid from the surrounding medium or to respire using malate or succinate as substrate. However, intact mitochondria isolated from plants during the day decarboxylated added malate to pyruvate significantly faster than mitochondria isolated from plants at night. NAD-ME activity in solubilized mitochondrial extracts showed hysteretic kinetics and was stimulated by a number of activators, including acetyl-coenzyme A, fructose-1,6-bisphosphate, and sulfate ions. In the absence of these effectors, reaction progress curves were nonlinear, with a pronounced acceleration phase. The lag period before a steady-state rate was reached in assays of mitochondrial extracts decreased during the photoperiod and increased slowly during the period of darkness. However, these changes in the kinetic properties of the enzyme could not account for the changes in the rate of decarboxylation of malate by intact mitochondria. Gel-filtration experiments showed that mitochondrial extracts contained three forms of NAD-ME with different molecular weights. The relative proportions of the three forms varied somewhat throughout the light/dark cycle, but this did not account for the changes in the kinetics behavior of the enzyme during the diurnal cycle. PMID:12228671

Preparation of vinyl acetate grafted natural rubber by irradiation method

Energy Technology Data Exchange (ETDEWEB)

Porntrairat, A.; Pattamaprom, C. [Center of Excellence on Natural Rubber Technology, Department of Chemical Engineering, Faculty of Engineering, Thammasat University, Pathumthani 12120 (Thailand)

2016-03-09

Improvement in properties of natural rubber could be done by several methods. In this research, gamma radiation technique, which is simple, accurate, easy to control and clean, was applied to enhance the properties of natural rubber (NR) in latex state. The purpose of this research is to study the appropriate condition for preparing grafted natural rubber latex by using irradiation method. Vinyl acetate monomers (VAc) were grafted onto natural rubber latex (NR-g-PVAc) at 0-10 kGys by gamma radiation from Cobalt-60 source at room temperature. Physical properties of grafted natural rubber such as chloroform number, swelling ratio and gel content were measured. The VAc content of NR-g-PVAc was investigated by titration and visualized by FTIR spectroscopy. The FTIR spectra of NR-g-PVAc prepared at 0-10 kGys showed characteristic peaks of the vinyl acetate confirming that VAc could be grafted onto natural rubber molecular chains effectively under appropriate irradiation conditions. From the result, radiation grafting was found to be a useful technique for grafting of vinyl acetate onto natural rubber.

Inactivation of γ-aminobutyric acid aminotransferase by γ-ethynyl- and γ-vinyl GABA

International Nuclear Information System (INIS)

Silverman, R.B.; Burke, J.R.; Nanavati, S.M.

1989-01-01

γ-Ethynyl- and γ-vinyl GABA (vigabatrin) are anticonvulsant agents that have been shown to be mechanism-based inactivators of γ-aminobutyric acid aminotransferase (GABA-T). The inactivation mechanisms of these compounds have been investigated. Inactivation of GABA-T by [ 3 H]γ-ethynyl GABA led to the incorporation of 1.0 equiv of 3 H into the enzyme which is not released by enzyme denaturation. Inactivation by γ-ethynyl GABA of GABA-T reconstituted with [ 3 H]PLP followed by denaturation resulted in release of 3 H as PLP. Eight different possible adducts are consistent with that result. Experiments have been carried out to differentiate these possibilities. Similar studies have been carried out with γ-vinyl GABA. Inactivation by [ 14 C]γ-vinyl GABA resulted in the incorporation of 1.0 equiv of 14 C per active site. Unlike the case with γ-ethynyl GABA, γ-vinyl GABA inactivation of GABA-T reconstituted with [ 3 H]PLP followed by denaturation resulted in release of 3 H as PMP

Rearing of germfree chicks in a vinyl isolator

International Nuclear Information System (INIS)

Ishibashi, Teru; Kametaka, Masao; Ozaki, Akira; Yamamoto, Tetsuzo; Kaneuchi, Choji.

1977-01-01

A method of rearing germfree chicks in a vinyl isolator was developed, Hatchability of eggs was higher than 95% when eggs were sterilized in a 1.5% mercuric chloride solution on the 2nd day before hatching. Sterility was 93% when 5 to 10 chicks were reared in a vinyl isolator for 2 weeks. Depression of body weight gain was observed in chicks fed diet irradiated at higher than 4 Mrad. However, no effects of irradiation on chick growth were observed when fat and the other components were sterilized separately and mixed before feeding. The growth rates of germfree chicks were higher than those of the conventional chicks which were supplied a diluted solution of fresh cecum feces of young hens with a normal intestinal flora pattern at the first feeding. (auth.)

γ-Rays-induced synthesis of hydrogels of vinyl ethers with stimuli-sensitive behavior

International Nuclear Information System (INIS)

Nam, I.K.; Mun, G.A.; Urkimbaeva, P.I.; Nurkeeva, Z.S.

2003-01-01

γ-Radiation method was applied to synthesize novel water-soluble and water-swelling polymers. Vinyl ether of ethylene glycol (VEEG), vinyl butyl (VBE) and vinyl isobutyl (VIBE) ethers were used as monomers. The synthesis of VEEG-VBE and VEEG-VIBE copolymers was carried out in a wide range of feed composition and absorbed dose. It was found that the hydrophobic-hydrophilic balance of the copolymers could be delicately varied by the copolymer composition as well as by the chemical structure of the alkyl substitute in the hydrophobic moiety. The copolymers exhibit thermo-sensitive behavior in water solutions. The value of transition temperature is considerably decreased at a higher concentration of the hydrophobic component in the copolymer composition

A facile one-pot solvothermal method for synthesis of magnetically recoverable Pd-Fe3O4 hybrid nanocatalysts for the Mizoroki-Heck reaction

Science.gov (United States)

Zhen, Fangchen; Ran, Maofei; Chu, Wei; Jiang, Chengfa; Sun, Wenjing

2018-03-01

Pd-Fe3O4 hybrid nanostructures were prepared using a simple one-pot hydrothermal method. The prepared materials were characterized by Fourier transform-infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma, N2 adsorption-desorption, and vibrating sample magnetometry. This self-assembled nanosystem acted as an efficient magnetically recyclable noble metal-based multi-functional nanocatalyst. It showed excellent catalytic activity and stability for the Heck reaction of iodobenzene and styrene under mild conditions. The methods used to prepare the Pd-Fe3O4 catalysts were simple and low-cost, which will be useful for the large-scale development and application of a magnetically recoverable Pd catalyst.

A Kinetic Study of the Emulsion Polymerization of Vinyl Acetate

DEFF Research Database (Denmark)

Friis, N.; Nyhagen, L.

1973-01-01

The emulsion polymerization of vinyl acetate was studied at 50°C. It was found that the rate of polymerization was proportional to the 0.5 power of the initiator concentration and the 0.25 power of the number of particles. The number of particles was proportional to the power 0.5 ± 0.......05 of the emulsifier concentration, but independent of the initiator concentration. The limiting viscosity number of the polymers produced was independent of the initiator concentration and number of polymer particles. It is suggested that the mechanism of vinyl acetate emulsion polymerization is similar...

Oxidative decarboxylation of glycolic and phenylacetic acids with cerium(4) catalyzed by silver ions in the sulfuric acid media

International Nuclear Information System (INIS)

Venkatesvar Rao, G.; Nagardzhun Rao, Ch.; Sajprakash, P.K.

1981-01-01

Oxidative decarboxylation of glycolic and phenylacetic acids by cerium (4) in the presence of Ag + ions is studied. The Ce(4) order equals 1, glycolic acid order in the absence of a catalyst also equals 1 and is fractional (0.5) for a catalytic reaction. The phenylacetic acid order is fractional (0.75). The Ag + ion reaction order is fractional and constitutes 0.32 for glycolic and 0.36 for phenylacetic acids. The reaction mechanism is proposed [ru

Synthesis and characterization of copolymers from hindered amines and vinyl monomers

Directory of Open Access Journals (Sweden)

Marcelo Aparecido Chinelatto

2014-01-01

Full Text Available New copolymers from hindered amines and vinyl monomers were synthesized by radical chain polymerization. To obtain polymeric HALS, acrylamide-(1ATP and acrylate-(4ATP monomers, derivatives from 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethyl-4-piperidinol were synthesized. The radical chain polymerization of 1ATP with styrene (Sty using 1-butanethiol (BTN resulted in a copolymer with 95 units of Sty and 15 units of 1ATP. The radical chain polymerization of 1ATP and vinyl acetate (VAc has produced only 1ATP homopolymer. In the chain polymerization of 4ATP with Sty or VAc, the hydrogen atom bonded to the nitrogen of 4ATP is labile enough to originate another radical at this site. The steric hindrance imposed by methyl groups on this bonding site hampers its reaction with other propagating species and the formation of a copolymer or network structure will be dependent on the size of the pendent group in the vinyl monomer.

The breakdown of vinyl ethers as a two-center synchronous reaction

Science.gov (United States)

Pokidova, T. S.; Shestakov, A. F.

2009-11-01

The experimental data on the molecular decomposition of vinyl ethers of various structures to alkanes and the corresponding aldehydes or ketones in the gas phase were analyzed using the method of intersecting parabolas. The enthalpies and kinetic parameters of decomposition were calculated for 17 reactions. The breakdown of ethers is a two-center concerted reaction characterized by a very high classical potential barrier to the thermally neutral reaction (180-190 kJ/mol). The kinetic parameters (activation energies and rate constants) of back reactions of the formation of vinyl ethers in the addition of aldehydes or ketones to alkanes were calculated using the method of intersecting parabolas. The factors that influenced the activation energy of the decomposition and formation of ethers were discussed. Quantum-chemical calculations of several vinyl ether decomposition reactions were performed. Ether formation reactions were compared with the formation of unsaturated alcohols as competitive reactions, which can occur in the interaction of carbonyl compounds with alkenes.

Nanoscale Characterization of Glass Flake Filled Vinyl Ester Anti-Corrosion Coatings

Directory of Open Access Journals (Sweden)

Salim Barbhuiya

2017-08-01

Full Text Available Vinyl ester is a thermoset matrix resin that is widely used in the coating industry. The presence of glass flakes further enhances the anti-corrosion performance of this coating. This paper reports the nanoscaled characterization of glass flake filled vinyl ester anti-corrosion coatings on mild steel. Bond strength properties of one uncoated and four coated samples with different thicknesses (300, 600, 900 and 1200 μm were studied using nanoscratch technique and ASTM Standard Test. It was found that the bond strength of coating with thickness 900 μm was the highest. The frequency distributions of elastic modulus on coating with 900 μm thickness determined using nanoindentation indicated that only 20–25% of the coating is composed of glass flakes and the balance is vinyl ester matrix. The critical depth at which the material is subject to failure due to external load and abrasion, was found to be around 100 nm.

Terminal Alkene Formation by the Thioesterase of Curacin A Biosynthesis: Structure of a Decarboxylating Thioesterase

Energy Technology Data Exchange (ETDEWEB)

Gehret, Jennifer J.; Gu, Liangcai; Gerwick, William H.; Wipf, Peter; Sherman, David H.; Smith, Janet L. (Pitt); (Michigan); (UCSD)

2011-11-07

Curacin A is a polyketide synthase (PKS)-non-ribosomal peptide synthetase-derived natural product with potent anticancer properties generated by the marine cyanobacterium Lyngbya majuscula. Type I modular PKS assembly lines typically employ a thioesterase (TE) domain to off-load carboxylic acid or macrolactone products from an adjacent acyl carrier protein (ACP) domain. In a striking departure from this scheme the curacin A PKS employs tandem sulfotransferase and TE domains to form a terminal alkene moiety. Sulfotransferase sulfonation of {beta}-hydroxy-acyl-ACP is followed by TE hydrolysis, decarboxylation, and sulfate elimination (Gu, L., Wang, B., Kulkarni, A., Gehret, J. J., Lloyd, K. R., Gerwick, L., Gerwick, W. H., Wipf, P., Hakansson, K., Smith, J. L., and Sherman, D. H. (2009) J. Am. Chem. Soc. 131, 16033-16035). With low sequence identity to other PKS TEs (<15%), the curacin TE represents a new thioesterase subfamily. The 1.7-{angstrom} curacin TE crystal structure reveals how the familiar {alpha}/{beta}-hydrolase architecture is adapted to specificity for {beta}-sulfated substrates. A Ser-His-Glu catalytic triad is centered in an open active site cleft between the core domain and a lid subdomain. Unlike TEs from other PKSs, the lid is fixed in an open conformation on one side by dimer contacts of a protruding helix and on the other side by an arginine anchor from the lid into the core. Adjacent to the catalytic triad, another arginine residue is positioned to recognize the substrate {beta}-sulfate group. The essential features of the curacin TE are conserved in sequences of five other putative bacterial ACP-ST-TE tridomains. Formation of a sulfate leaving group as a biosynthetic strategy to facilitate acyl chain decarboxylation is of potential value as a route to hydrocarbon biofuels.

Emission and Mechanical Evaluations of Vinyl-Ester Resin Systems

National Research Council Canada - National Science Library

Sands, James

2003-01-01

Vinyl-ester resins (VE) are frequently used in liquid molding of composite materials for several applications including naval and army structures, commercial boat manufacturing, and building construction...

Laser induced augmentation of silver nanospheres to nanowires in ethanol fostered by Poly Vinyl Pyrrolidone

Energy Technology Data Exchange (ETDEWEB)

Sebastian, Suneetha, E-mail: sunikutty@gmail.com; Linslal, C.L.; Vallabhan, C.P.G.; Nampoori, V.P.N.; Radhakrishnan, P.; Kailasnath, M.

2014-11-30

Highlights: • Silver nanospheres are synthesised in ethanol containing Poly Vinyl Pyrrolidone which acts as a polymeric capping agent to nanoparticles thus improving its stability. • Laser irradiation onto the colloidal solution of silver nanoparticles produced well defined nanowires through ripening mechanism promoted by Poly Vinyl Pyrrolidone. • Nanowires so formed are having an average length of 8.7 μm and width of 160 nm. - Abstract: Stable uniform silver nanospheres having an average diameter of 45 nm are synthesised in ethanol containing Poly Vinyl Pyrrolidone using Laser Ablation in Liquid technique. Further irradiation of the nanocolloidal solution by focussed laser beam produced stable well defined silver nanowires through ripening mechanism fostered by the presence of Poly Vinyl Pyrrolidone. Confirmation of the mechanism is obtained from Transmission Electron Microscopic images of the nanocolloidal solution irradiated for different time durations.

Electrodialytic Transport Properties of Anion-Exchange Membranes Prepared from Poly(vinyl alcohol) and Poly(vinyl alcohol-co-methacryloyl aminopropyl trimethyl ammonium chloride).

Science.gov (United States)

Jikihara, Atsushi; Ohashi, Reina; Kakihana, Yuriko; Higa, Mitsuru; Kobayashi, Kenichi

2013-01-02

Random-type anion-exchange membranes (AEMs) have been prepared by blending poly(vinyl alcohol) (PVA) and the random copolymer-type polycation, poly(vinyl alcohol-co-methacryloyl aminopropyl trimethyl ammonium chloride) at various molar percentages of anion-exchange groups to vinyl alcohol groups, Cpc, and by cross-linking the PVA chains with glutaraldehyde (GA) solution at various GA concentrations, CGA. The characteristics of the random-type AEMs were compared with blend-type AEMs prepared in our previous study. At equal molar percentages of the anion exchange groups, the water content of the random-type AEMs was lower than that of the blend-type AEMs. The effective charge density of the random-type AEMs increased with increasing Cpc and reached a maximum value. Further, the maximum value of the effective charge density increased with increasing CGA. The maximum value of the effective charge density, 0.42 mol/dm3, was obtained for the random-type AEM with Cpc = 4.2 mol % and CGA = 0.15 vol %. A comparison of the random-type and blend-type AEMs with almost the same Cpc showed that the random-type AEMs had lower membrane resistance than the blend-type ones. The membrane resistance and dynamic transport number of the random-type AEM with Cpc = 6.0 mol % and CGA = 0.15 vol % were 4.8 Ω cm2 and 0.83, respectively.

Vinyl flooring in the home is associated with children's airborne butylbenzyl phthalate and urinary metabolite concentrations.

Science.gov (United States)

Just, Allan C; Miller, Rachel L; Perzanowski, Matthew S; Rundle, Andrew G; Chen, Qixuan; Jung, Kyung Hwa; Hoepner, Lori; Camann, David E; Calafat, Antonia M; Perera, Frederica P; Whyatt, Robin M

2015-01-01

Prior studies have shown that vinyl flooring as well as the vinyl-softening plasticizers butylbenzyl phthalate (BBzP) and di(2-ethylhexyl) phthalate (DEHP) are associated with asthma and airway inflammation. Although DEHP exposure is primarily dietary, whether home vinyl flooring contributes to indoor air and urinary metabolite concentrations for these two phthalates is unclear. Exposures to BBzP and DEHP were examined in a prospective birth cohort of New York City children (n=239) using: (i) visual observation of potential phthalate containing flooring, (ii) a 2-week home indoor air sample, and (iii) concurrent urinary metabolites in a subset (n=193). The category "vinyl or linoleum" flooring was observed in 135 (56%) of monitored rooms; these rooms had statistically significantly higher indoor air geometric mean concentrations of BBzP (23.9 ng/m(3)) than rooms with wood or carpet flooring (10.6 ng/m(3)). Children from homes with "vinyl or linoleum" flooring also had significantly higher urinary BBzP metabolite concentrations than other children. Indoor air BBzP and urinary metabolite concentrations were correlated positively (Spearman's rho 0.40). By contrast, indoor air DEHP was not associated with flooring type nor with its urinary metabolite concentrations. Vinyl flooring in the home may be an important source of children's exposure to BBzP via indoor air.

Crystallisation of hydroxyapatite in phosphorylated poly(vinyl alcohol) as a synthetic route to tough mechanical hybrid materials

International Nuclear Information System (INIS)

Kusakabe, Akane; Hirota, Ken; Mizutani, Tadashi

2017-01-01

Partially phosphorylated poly(vinyl alcohol) was prepared by treating poly(vinyl alcohol) with 100% phosphoric acid, and 5, 10 and 20% of the hydroxyl groups were converted to phosphoric acid ester. Addition of Ca 2+ to an aqueous solution of phosphorylated poly(vinyl alcohol) gave a transparent gel. Five cycles of alternate soaking of the gel in aqueous CaCl 2 and aqueous (NH 4 ) 2 HPO 4 were carried out to crystallise hydroxyapatite (HAP) in the phosphorylated poly(vinyl alcohol) matrix. The X-ray diffraction peaks of HAP formed in 5% phosphorylated PVA were sharp, while those of HAP formed in 20% phosphorylated PVA were broad. The contents of inorganic phase in the hybrid powder were increased from 58 to 76 wt% as the fraction of phosphate groups in the gel was decreased from 20% to 5%. The hybrid powder was first subjected to uniaxial pressing, followed by cold isostatic pressing (CIP) and warm isostatic pressing (WIP) at 120 °C at pressures of 300–980 MPa, to obtain the specimens for three-point bending test. These hybrid specimens showed bending strengths of 15–53 MPa. The hybrid compacts prepared from 10% phosphorylated poly(vinyl alcohol) showed the smallest Young's modulus, the largest displacement at break, and the largest fracture energy, showing that it has the highest toughness among the hybrid materials prepared from poly(vinyl alcohol) with varying degrees of phosphorylation. - Graphical abstract: Densification of hydroxyapatite crystallised in 10% phosphorylated poly(vinyl alcohol) gave the toughest compact. - Highlights: • Hydroxyapatite was crystallised in phosphorylated poly(vinyl alcohol) gels. • Crystallite size of hydroxyapatite decreased as phosphate density was increased. • The hybrid specimens prepared in 10% phosphorylated gel was the toughest. • Phosphate density in organic matrix regulated the mechanical properties of the hybrid.

Crystallisation of hydroxyapatite in phosphorylated poly(vinyl alcohol) as a synthetic route to tough mechanical hybrid materials

Energy Technology Data Exchange (ETDEWEB)

Kusakabe, Akane; Hirota, Ken; Mizutani, Tadashi, E-mail: tmizutan@mail.doshisha.ac.jp

2017-01-01

Partially phosphorylated poly(vinyl alcohol) was prepared by treating poly(vinyl alcohol) with 100% phosphoric acid, and 5, 10 and 20% of the hydroxyl groups were converted to phosphoric acid ester. Addition of Ca{sup 2+} to an aqueous solution of phosphorylated poly(vinyl alcohol) gave a transparent gel. Five cycles of alternate soaking of the gel in aqueous CaCl{sub 2} and aqueous (NH{sub 4}){sub 2}HPO{sub 4} were carried out to crystallise hydroxyapatite (HAP) in the phosphorylated poly(vinyl alcohol) matrix. The X-ray diffraction peaks of HAP formed in 5% phosphorylated PVA were sharp, while those of HAP formed in 20% phosphorylated PVA were broad. The contents of inorganic phase in the hybrid powder were increased from 58 to 76 wt% as the fraction of phosphate groups in the gel was decreased from 20% to 5%. The hybrid powder was first subjected to uniaxial pressing, followed by cold isostatic pressing (CIP) and warm isostatic pressing (WIP) at 120 °C at pressures of 300–980 MPa, to obtain the specimens for three-point bending test. These hybrid specimens showed bending strengths of 15–53 MPa. The hybrid compacts prepared from 10% phosphorylated poly(vinyl alcohol) showed the smallest Young's modulus, the largest displacement at break, and the largest fracture energy, showing that it has the highest toughness among the hybrid materials prepared from poly(vinyl alcohol) with varying degrees of phosphorylation. - Graphical abstract: Densification of hydroxyapatite crystallised in 10% phosphorylated poly(vinyl alcohol) gave the toughest compact. - Highlights: • Hydroxyapatite was crystallised in phosphorylated poly(vinyl alcohol) gels. • Crystallite size of hydroxyapatite decreased as phosphate density was increased. • The hybrid specimens prepared in 10% phosphorylated gel was the toughest. • Phosphate density in organic matrix regulated the mechanical properties of the hybrid.

Radiation polymerization of 2-hydroxyethyl methacrylate-vinyl pyrrolidone-water system

International Nuclear Information System (INIS)

Kumakura, M.; Kaetsu, I.

1988-01-01

Polymerization was studied using mixtures of 2-hydroxyethyl methacrylate(HEMA)-water, vinyl pyrrolidone(NVP)-water and 2-hydroxyethyl methacrylate-vinyl pyrrolidone-water. The mixtures were irradiated with gamma radiation from a 60 Co source. Irradiation was carried out at temperatures of 0, -24, -45, -63, -78, and -196 degC. The dependence was studied of the polymerization rate on temperature during irradiation for the individual mixtures, as were the effect of monomer composition on the polymerization of the HEMA-NVP-water system at 0 degC, the effect of water on NVP polymerization and the relationship between water absorption and the composition of the monomer. (E.S.). 4 figs., 6 refs

An Evaluation of Fracture Toughness of Vinyl Ester Composites Cured under Microwave Conditions

Science.gov (United States)

Ku, H.; Chan, W. L.; Trada, M.; Baddeley, D.

2007-12-01

The shrinkage of vinyl ester particulate composites has been reduced by curing the resins under microwave conditions. The reduction in the shrinkage of the resins by microwaves will enable the manufacture of large vinyl ester composite items possible (H.S. Ku, G. Van Erp, J.A.R. Ball, and S. Ayers, Shrinkage Reduction of Thermoset Fibre Composites during Hardening using Microwaves Irradiation for Curing, Proceedings, Second World Engineering Congress, Kuching, Malaysia, 2002a, 22-25 July, p 177-182; H.S. Ku, Risks Involved in Curing Vinyl Ester Resins Using Microwaves Irradiation. J. Mater. Synth. Proces. 2002b, 10(2), p 97-106; S.H. Ku, Curing Vinyl Ester Particle Reinforced Composites Using Microwaves. J. Comp. Mater., (2003a), 37(22), p 2027-2042; S.H. Ku and E. Siores, Shrinkage Reduction of Thermoset Matrix Particle Reinforced Composites During Hardening Using Microwaves Irradiation, Trans. Hong Kong Inst. Eng., 2004, 11(3), p 29-34). In tensile tests, the yield strengths of samples cured under microwave conditions obtained are within 5% of those obtained by ambient curing; it is also found that with 180 W microwave power, the tensile strengths obtained for all duration of exposure to microwaves are also within the 5% of those obtained by ambient curing. While, with 360 W microwave power, the tensile strengths obtained for all duration of exposure to microwaves are 5% higher than those obtained by ambient curing. Whereas, with 540 W microwave power, the tensile strengths obtained for most samples are 5% below those obtained by ambient curing (H. Ku, V.C. Puttgunta, and M. Trada, Young’s Modulus of Vinyl Ester Composites Cured by Microwave Irradiation: Preliminary Results, J. Electromagnet. Waves Appl., 2007, 20(14), p. 1911-1924). This project, using 33% by weight fly ash reinforced vinyl ester composite [VE/FLYSH (33%)], is to further investigate the difference in fracture toughness between microwave cured vinyl ester particulate composites and those cured

Rheological properties of poly-vinyl-chloride solutions in varioussolvents

International Nuclear Information System (INIS)

Kurbanaliev, M.K.; Narzullaev, B.N.; Dustov, I.K.; Marupov, R.M.

1976-01-01

The present article is the result of studying of curves process ofpoly-vinyl-chloride solutions in wide interval of tension and velocities ofshear in thermodynamically good and bad solvents at various temperatures

Multiplicative Structure and Hecke Rings of Generator Matrices for Codes over Quotient Rings of Euclidean Domains

Directory of Open Access Journals (Sweden)

Hajime Matsui

2017-12-01

Full Text Available In this study, we consider codes over Euclidean domains modulo their ideals. In the first half of the study, we deal with arbitrary Euclidean domains. We show that the product of generator matrices of codes over the rings mod a and mod b produces generator matrices of all codes over the ring mod a b , i.e., this correspondence is onto. Moreover, we show that if a and b are coprime, then this correspondence is one-to-one, i.e., there exist unique codes over the rings mod a and mod b that produce any given code over the ring mod a b through the product of their generator matrices. In the second half of the study, we focus on the typical Euclidean domains such as the rational integer ring, one-variable polynomial rings, rings of Gaussian and Eisenstein integers, p-adic integer rings and rings of one-variable formal power series. We define the reduced generator matrices of codes over Euclidean domains modulo their ideals and show their uniqueness. Finally, we apply our theory of reduced generator matrices to the Hecke rings of matrices over these Euclidean domains.

APPLICATION OF TRITON X-100 COATED POLY VINYL ...

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and Zn(II) ions based on the uptake of their complexes with ... The presence of heavy metals in ... Poly vinyl chloride high molecular weight was purchased .... 7.0 and then the charge intensity of the functional groups of solid materials played a ...

Immobilized Palladium Nanoparticles on Zirconium Carboxy-Aminophosphonates Nanosheets as an Efficient Recoverable Heterogeneous Catalyst for Suzuki–Miyaura and Heck Coupling

Directory of Open Access Journals (Sweden)

Vadym Kozell

2017-06-01

Full Text Available Zirconium phosphate glycine diphosphonate nanosheets (ZPGly have been used as support for the preparation of solid palladium nanoparticles, namely Pd@ZPGly. Thanks to the presence of carboxy-aminophosponate groups on the layer surface, ZPGly-based materials were able to stabilize a high amount of palladium (up to 22 wt % also minimizing the amount of metal leached in the final products of representative important cross-coupling processes selected for proving the catalysts’ efficiency. The catalytic systems have been fully characterized and used in low amounts (0.1 mol % in the Suzuki–Miyaura and Heck cross-couplings. Moreover, the protocols were optimized for the use of recoverable azeotropic mixtures (aq. EtOH 96% or aq. CH3CN 84%, respectively and in the flow procedure allowing one to isolate the final pure products, without any purification step, with very low residual palladium content and with a very low waste production.

Antioxidant Microemulsion-based Ethylene Vinyl Acetate Film Containing Mangiferin and Surfactants

Directory of Open Access Journals (Sweden)

Boonnattakorn Rungkan

2016-01-01

Full Text Available Mangiferin, a natural antioxidant additive, was incorporated into an ethylene vinyl acetate copolymer (EVA containing 18% vinyl acetate (VA using the emulsion solvent evaporation technique. Sorbitan ester (Span®20 and polymeric surfactant (Pluronic®P−123 were compared. Mangiferin was finely dispersed in the suspension with the addition of surfactants studied. Span®20 was chosen as the surfactant for film preparation in the next step due to the dispersing and film forming properties. Effects of vinyl acetate (VA contents on the film properties were investigated. The EVA films with 12% VA had the highest tensile strength and oxygen barrier, followed by 18, 25 and 40% VA, respectively. Addition of Span®20 had only a slight effect on mechanical and barrier properties of the films, but markedly increased the release of mangiferin from the EVA matrices except in the 40% VA films. The maximum concentrations of mangiferin released from the 40, 25, 18 and 12% VA films into 95% ethanol were 83.30, 66.84, 51.77 and 34.57 μg·mL−11, respectively. The release concentrations from the 40 and 25% VA films was 2.4 and 1.9 folds of that from the 12% VA film, respectively. The antioxidant activity of the EVA films containing mangiferin and Span®20 was 80% radical-scavenging capacity (RSC for the 40 and 25% VA and 60% RSC for the 18 and 12% VA. The release of mangiferin from the EVA matrices may be controlled by appropriate selection of the surfactants and vinyl acetate contents.

Investigations on mechanical and two-body abrasive wear behaviour of glass/carbon fabric reinforced vinyl ester composites

International Nuclear Information System (INIS)

Suresha, B.; Kumar, Kunigal N. Shiva

2009-01-01

The aim of the research article is to study the mechanical and two-body abrasive wear behaviour of glass/carbon fabric reinforced vinyl ester composites. The measured wear volume loss increases with increase in abrading distance/abrasive particle size. However, the specific wear rate decreases with increase in abrading distance and decrease in abrasive particle size. The results showed that the highest specific wear rate is for glass fabric reinforced vinyl ester composite with a value of 10.89 x 10 -11 m 3 /Nm and the lowest wear rate is for carbon fabric reinforced vinyl ester composite with a value of 4.02 x 10 -11 m 3 /Nm. Mechanical properties were evaluated and obtained values are compared with the wear behaviour. The worn surface features have been examined using scanning electron microscope (SEM). Photomicrographs of the worn surfaces revealed higher percentage of broken glass fiber as compared to carbon fiber. Also better interfacial adhesion between carbon and vinyl ester in carbon reinforced vinyl ester composite was observed.

Vinyl ester resin and process for curing same with ionizing radiation in the presence of amines

International Nuclear Information System (INIS)

Mani, I.

1975-01-01

The addition of about 2 to 5 weight percent of certain amines to a thermosettable mixture of certain vinyl monomers and a polymerizable vinyl ester resin reduces the dosage level of ionizing radiation required to cure the mixture. (U.S.)

Vinyl flooring in the home is associated with children’s airborne butylbenzyl phthalate and urinary metabolite concentrations

Science.gov (United States)

Just, Allan C.; Miller, Rachel L.; Perzanowski, Matthew S.; Rundle, Andrew G.; Chen, Qixuan; Jung, Kyung Hwa; Hoepner, Lori; Camann, David E.; Calafat, Antonia M.; Perera, Frederica P.; Whyatt, Robin M.

2015-01-01

Prior studies have shown that vinyl flooring, as well as the vinyl-softening plasticizers butylbenzyl phthalate (BBzP) and di(2-ethylhexyl) phthalate (DEHP), are associated with asthma and airway inflammation. While DEHP exposure is primarily dietary, whether home vinyl flooring contributes to indoor air and urinary metabolite concentrations for these two phthalates is unclear. Exposures to BBzP and DEHP were examined in a prospective birth cohort of New York City children (n=239) using: (1) visual observation of potential phthalate containing flooring, (2) a two-week home indoor air sample, and (3) concurrent urinary metabolites in a subset (n=193). The category “vinyl or linoleum” flooring was observed in 135 (56%) of monitored rooms; these rooms had statistically significantly higher indoor air geometric mean concentrations of BBzP (23.9 ng/m3) than rooms with wood or carpet flooring (10.6 ng/m3). Children from homes with “vinyl or linoleum” flooring also had significantly higher urinary BBzP metabolite concentrations than other children. Indoor air BBzP and urinary metabolite concentrations were correlated positively (Spearman’s rho 0.40). By contrast, indoor air DEHP was not associated with flooring type nor with its urinary metabolite concentrations. Vinyl flooring in the home may be an important source of children’s exposure to BBzP via indoor air. PMID:25690585

Rubber-like poly(vinyl alcohol) gel

Energy Technology Data Exchange (ETDEWEB)

Nambu, Masao (Nippon Oil Co. Ltd., Yokohama (Japan). Central Technical Research Lab.)

1990-09-01

Anomalous poly (vinyl alcohol) gel has been found in our laboratory since 1980. The gel is prepared by repeated freezing (or freeze-dehydration) of aqueous poly (vinyl alcohol). Experiments establish the fact that anomalous gel is never produced in the course of freezing, but during sustained thawing the gelation does occur. Moreover, it was found that the softening point of the gel increases at 37degC. It is assumed that crystal nuclei are generated on freezing, then on thawing, some of them grow to very fine crystals which act as polymer network-knots (cross-linking). Additional freezing provide other seeds, which grow similarly, and these are accumulated until rubber-like gel is produced. The gel was always water-resistant at 37degC, and the potassium permanganate consumption of the extracted water layer remained far below the official restricted value for medical materials. The gel can be sterilized with gamma-rays or chlorhexidine. Moreover, it satisfies the official standards of acute toxicity, pyrogen, intracutaneous reaction, hemolyzation, and intracorporeal implantation, respectively. Applications to adhesion-preventing membrane (for joint or pericardium), tamponade (for jaw defects), electrode (for electroretinogram or artificial inner ear), artificial denture base and phantoms for magnetic resonance imaging were examined. (author) 54 refs.

Water-dispersable hybrid Au-Pd nanoparticles as catalysts in ethanol oxidation, aqueous phase Suzuki-Miyaura and Heck reactions

KAUST Repository

Song, Hyon Min

2012-01-01

The catalytic activities of water-dispersable Au@Pd core-shell nanoparticles (NPs) and Au-Pd alloy NPs were examined. There is growing interest in Au-Pd hybridized NPs in a supported matrix or non-supported forms as catalysts in various reactions that are not limited to conventional Pd-related reactions. Four different Au@Pd core-shell NPs in this study were prepared at room temperature with help from the emulsion phase surrounding the Au core NPs. Au-Pd alloy NPs were prepared over 90 °C, and underwent phase transfer to aqueous medium for their catalytic use. Au@Pd core-shell NPs show catalytic activity in ethanol oxidation reactions as electrocatalysts, and both core-shell and alloy NPs are good to excellent catalysts in various Suzuki-Miyaura and Heck reactions as heterogeneous catalysts. Specifically, Au@Pd core-shell NPs with sharp branched arms show the highest yield in the reactions tested in this study. A relatively small amount (0.25 mol%) was used throughout the catalytic reactions. © 2012 The Royal Society of Chemistry.

A Model Approach for Finding Cleaning Solutions for Plasticized Poly(Vinyl Chloride) Surfaces of Collections Objects

DEFF Research Database (Denmark)

Sanz Landaluze, Jon; Egsgaard, Helge; Morales Munoz, Clara

2014-01-01

This study focused on developing a surface cleaning treatment for one type of commercially available plasticized poly(vinyl chloride). The effects of cleaning solutions on samples of plasticized poly(vinyl chloride) were examined by several methods. The sample surface, prior to and after artifici...

21 CFR 177.1980 - Vinyl chloride-propylene copolymers.

Science.gov (United States)

2010-04-01

... used as components of articles intended for contact with food, subject to the provisions of this... chlorine content is in the range of 53 to 56 percent as determined by any suitable analytical procedure of... section. (d) Analytical methods: The analytical methods for determining whether vinyl chloride-propylene...

'Vinyl never say die': The re-incarnation, adoption and diffusion of retro-technologies

OpenAIRE

Sarpong, D.; Dong, S.; Appiah, G.

2016-01-01

New technologies continue to shape the way music is produced, distributed and consumed. The new turn to digital streaming services like iTunes, Spotify and Pandora, in particular, means that very recent music format technologies such as cassettes and CD's have almost lost their value. Surprisingly, one 'obsolete' music format technology, Vinyl record, is making a rapid comeback. Vinyl sales around the world, in recent times, have increased year on year, and the number of music enthusiast reac...

Methyltriphenylphosphonium Methylcarbonate, an All-In-One Wittig Vinylation Reagent.

Science.gov (United States)

Cattelan, Lisa; Noè, Marco; Selva, Maurizio; Demitri, Nicola; Perosa, Alvise

2015-12-07

The methyltriphenylphosphonium methylcarbonate salt [Ph3 PCH3 ][CH3 OCO2 ], obtained directly by quaternarization of triphenylphosphine with dimethylcarbonate, is a latent ylide that promotes Wittig vinylation of aldehydes and ketones. Alkenes are obtained simply by mixing [Ph3 PCH3 ][CH3 OCO2 ] and the carbonyl and heating in a solvent (no base, no halides, and no inorganic byproducts). Deuterium exchange experiments and the particularly short anion-cation distance measured by XRD in [Ph3 PCH3 ][CH3 OCO2 ] allowed to explain the nature and reactivity of this species. Green chemistry metrics (atom economy, mass index, environmental factor) indicate that this vinylation procedure is more efficient than comparable ones. Deuterated [Ph3 PCD3 ][CH3 OCO2 ] promoted the synthesis of deuterated olefins. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation on the thermal properties of new thermo-reversible networks based on poly(vinyl furfural and multifunctional maleimide compounds

Directory of Open Access Journals (Sweden)

C. Gaina

2012-02-01

Full Text Available New thermo-reversible networks were obtained from poly(vinyl furfural and multifunctional maleimide monomers by Diels-Alder (DA and retro-DA reactions. The poly(vinyl furfural having acetalization degree of 15 and 25% were obtained by the acid-catalyzed homogenous acetalization of poly(vinyl alcohol with 2-furfural in a nonaqueous media. The thermal and viscoelastic behaviour of the cross-linked materials have been studied via differential scanning calorimetry, dynamic mechanical analysis and thermogravimetric analysis. The networks exhibit considerable swelling in those organic solvents that dissolve both poly(vinyl furfural and bismaleimides; by heating in aprotic dipolar solvents at 150°C, they become soluble.

75 FR 5578 - Submission for OMB Review; Comment Request-Flammability Standards for Clothing Textiles and Vinyl...

Science.gov (United States)

2010-02-03

... Standards for Clothing Textiles and Vinyl Plastic Film AGENCY: Consumer Product Safety Commission. ACTION: Notice. SUMMARY: Pursuant to the Paperwork Reduction Act of 1995 (44 U.S.C. Chapter 35), the Consumer... Commission's flammability standards for clothing textiles and vinyl plastic film. DATES: Written comments on...

Effect of organoelemental compounds of group 3 elements on radical polymerization of vinyl monomers

International Nuclear Information System (INIS)

Grishin, D.F.; Mojkin, A.A.

1996-01-01

When alkyl, alkyl alkoxy, and alkyl halide derivatives of boron and aluminium are introduced into the system in amounts that are comparable to the concentration of initiator, they coordinate to the growing macroradicals, thus changing their reactivity, and exert regulating effect on the rate of polymerization of vinyl monomers and the molecular mass of the resulting polymers. The said organoelemental compounds accelerate the polymerization of butyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate, and vinylidene chloride, reduce the molecular mass of acrylic polymers, and virtually do not affect the polymerization of styrene. The specific features of vinyl polymerization are associated with participation of organoelemental additives at the stages of chain growth and chain termination and can be explained within the framework of the mechanism of radical-coordination polymerization. 32 refs., 3 tabs

N-heterocycle carbene (NHC)-ligated cyclopalladated N,N-dimethylbenzylamine: a highly active, practical and versatile catalyst for the Heck-Mizoroki reaction.

Science.gov (United States)

Peh, Guang-Rong; Kantchev, Eric Assen B; Zhang, Chi; Ying, Jackie Y

2009-05-21

The wide dissemination of catalytic protocols in academic and industrial laboratories is facilitated by the development of catalysts that are not only highly active but also user-friendly, stable to moisture, air and long term storage and easy to prepare on a large scale. Herein we describe a protocol for the Heck-Mizoroki reaction mediated by cyclopalladated N,N-dimethylbenzylamine (dmba) ligated with a N-heterocyclic carbene, 1,3-bis(mesityl)imidazol-2-ylidene (IMes), that fulfils these criteria. The precatalyst can be synthesized on approximately 100 g scale by a tri-component, sequential, one-pot reaction of N,N-dimethylbenzylamine, PdCl2 and IMes.HCl in refluxing acetonitrile in air in the presence of K2CO3. This single component catalyst is stable to air, moisture and long term storage and can be conveniently dispensed as a stock solution in NMP. It mediates the Heck-Mizoroki reaction of a range of aryl- and heteroaryl bromides in reagent grade NMP at the 0.1-2 mol% range without the need for rigorous anhydrous techniques or a glovebox, and is active even in air. The catalyst is capable of achieving very high levels of catalytic activity (TON of up to 5.22 x 10(5)) for the coupling of a deactivated arylbromide, p-bromoanisole, with tBu acrylate as a benchmark substrate pair. A wide range of aryl bromides, iodides and, for the first time with a NHC-Pd catalyst, a triflate was coupled with diverse acrylate derivatives (nitrile, tert-butyl ester and amides) and styrene derivatives. The use of excess (>2 equiv.) of the aryl bromide and tert-butyl acrylate leads to mixture of tert-butyl beta,beta-diarylacrylate and tert-butyl cinnamate derivatives depending on the substitution pattern of the aryl bromide. Electron rich m- and p-substituted arylbromides give the diarylated products exclusively, whereas electron-poor aryl bromides give predominantly mono-arylated products. For o-substituted aryl bromides, no doubly arylated products could be obtained under any

Chemical modification of poly(vinyl alcohol): evaluation of hydrophilic/lipophilic balance

International Nuclear Information System (INIS)

Aranha, Isabele B.; Lucas, Elizabete F.

2001-01-01

Poly(vinyl alcohol) terpolymers have been obtained by reaction of partially hydrolized poly(vinyl alcohol) with different acid chlorides. The objective is the preparation of polymers with slight differences in their hydrophilic/lipophilic balance and in the interfacial activities of their solutions. The chemical modifications were characterized by means of 1 H NMR and the polymer properties were evaluated in terms of changes in solubility and surface tension. By chemical modification, polymers with low percentage of hydrophobic group were obtained. The water-soluble polymers obtained did not have the surface tension of their solutions altered. The solubility of the modified polymers decreased markedly, even with low contents of hydrophobic groups. (author)

Simple and fast polydimethylsiloxane (PDMS) patterning using a cutting plotter and vinyl adhesives to achieve etching results.

Science.gov (United States)

Hyun Kim; Sun-Young Yoo; Ji Sung Kim; Zihuan Wang; Woon Hee Lee; Kyo-In Koo; Jong-Mo Seo; Dong-Il Cho

2017-07-01

Inhibition of polydimethylsiloxane (PDMS) polymerization could be observed when spin-coated over vinyl substrates. The degree of polymerization, partially curing or fully curing, depended on the PDMS thickness coated over the vinyl substrate. This characteristic was exploited to achieve simple and fast PDMS patterning method using a vinyl adhesive layer patterned through a cutting plotter. The proposed patterning method showed results resembling PDMS etching. Therefore, patterning PDMS over PDMS, glass, silicon, and gold substrates were tested to compare the results with conventional etching methods. Vinyl stencils with widths ranging from 200μm to 1500μm were used for the procedure. To evaluate the accuracy of the cutting plotter, stencil designed on the AutoCAD software and the actual stencil widths were compared. Furthermore, this method's accuracy was also evaluated by comparing the widths of the actual stencils and etched PDMS results.

Biocatalytic Asymmetric Synthesis of (1R, 2S)-N-Boc-vinyl-ACCA Ethyl Ester with a Newly Isolated Sphingomonas aquatilis.

Science.gov (United States)

Zhu, Shaozhou; Shi, Ying; Zhang, Xinyu; Zheng, Guojun

2018-02-01

1-amino cyclopropane-1-carboxylic acid (ACCA) and its derivatives are essential pharmacophoric unit that widely used in drug research and development. Specifically, (1R, 2S)-N-Boc-vinyl-ACCA ethyl ester (vinyl-ACCA) is a key chiral intermediate in the synthesis of highly potent hepatitis C virus (HCV) NS3/4A protease inhibitors such as asunaprevir and simeprevir. Developing strategies for the asymmetric synthesis of vinyl-ACCA is thus extremely high demand. In this study, 378 bacterial strains were isolated from soil samples using N-Boc-vinyl-ACCA ethyl ester as the sole carbon source and were screened for esterase activity. Fourteen of which worked effectively for the asymmetric synthesis of (1R, 2S)-N-Boc-1-vinyl ACCA ethyl ester. The strain CY-2, identified as Sphingomonas aquatilis, which showed the highest stability and enantioselectivity was selected as whole cell biocatalyst for further study. A systematic study of all factors influencing the enzymatic hydrolysis was performed. Under optimized conditions, resolution of rac-vinyl-ACCA to (1R, 2S)-N-Boc-1-vinyl ACCA ethyl ester with 88.2% ee and 62.4% conversion (E = 9) was achieved. Besides, S. aquatilis was also used to transform other 10 different substrates. Notably, it was found that 7 of them could be stereoselectively hydrolyzed, especially for (1R,2S)-1-amino-vinyl-ACCA ethyl ester hydrochloride (99.6% ee, E>200). Our investigations provide a new efficient whole cell biocatalyst for resolution of ACCA and might be developed for industry application.

Radiation effect of ethylene/vinyl alcohol copolymer

International Nuclear Information System (INIS)

Liu Meihua; Jilin Univ., Changchun; Deng Pengyang; Sun Jiazhen; Dong Lisong; Sun Guoen; Zhang Wanxi

2006-01-01

The radiation effect of ethylene-vinyl alcohol copolymer (EVOH), EVOH/glycerin blend was studied by solvent extraction, gel permeation chromatography (GPC) and Fourier transform infrared spectrum (FTIR) methods. Samples were irradiated up to 1800 kGy at room temperature under N 2 . The results show that degradation is the main reaction in pure EVOH. Trace gel content could be found in E151 irradiated to at least 800 kGy, and only 5.9% gel content was found in the sample irradiated to 1200 kGy. While trace gel content could be found in F101 irradiated to at least 1800 kGy, the different gelation doses of E151 and F101 are due to different contents of vinyl alcohol units. Unsaturation structure can be found in the irradiated EVOH. The content increased at first, and then decreased, with the dose. The existence of double bond enhances the radiation efficiency of EVOH. For EVOH/glycerin blend, the gel content was higher than that of pure EVOH when the absorbed dose exceeds 800 kGy, and the gel content increased with the absorbed dose. But it cannot enhance radiation efficiency of EVOH as water. (authors)

Synthesis of vinyl phosphites

International Nuclear Information System (INIS)

Kabachnik, M.M.; Novikova, Z.S.; Neganova, E.G.; Lutsenko, I.F.

1986-01-01

The authors investigated the reactions of phosphoriodidites and phosphinous iodides with a number of aldehydes and ketones in presence of tertiary amines (triethylamine, pyridine, N,N-diethylaniline), and they have shown that as a result of the reactions the corresponding vinyl esters of phosphorus acids are formed. The reactions of phosphoriodidites (and phosphorodiamidous iodides) with aliphatic aldehydes (acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde) go at a molar reactant ratio of 1:1 in either at room temperature and are practically complete in 5-6 h. The yields of the alkenyl phosphites (phosphorodiamidites) were 45-70%. The compositions and structures of the compounds obtained were confirmed by elemental analysis and the IR and 1 H and 31 P NMR spectra

Investigating the activity of quinine analogues versus chloroquine resistant Plasmodium falciparum.

Science.gov (United States)

Dinio, Theresa; Gorka, Alexander P; McGinniss, Andrew; Roepe, Paul D; Morgan, Jeremy B

2012-05-15

Plasmodium falciparum, the deadliest malarial parasite species, has developed resistance against nearly all man-made antimalarial drugs within the past century. However, quinine (QN), the first antimalarial drug, remains efficacious worldwide. Some chloroquine resistant (CQR) P. falciparum strains or isolates show mild cross resistance to QN, but many do not. Further optimization of QN may provide a well-tolerated therapy with improved activity versus CQR malaria. Thus, using the Heck reaction, we have pursued a structure-activity relationship study, including vinyl group modifications of QN. Certain derivatives show good antiplasmodial activity in QN-resistant and QN-sensitive strains, with lower IC(50) values relative to QN. Copyright © 2012 Elsevier Ltd. All rights reserved.

How the Internet Facilitates the Activity within a Consumer Culture : - A Study of the Online Vinyl Record Network

OpenAIRE

Söderlindh, Stefan; Broman, David

2009-01-01

The purpose of this thesis is to describe and analyze how the online vinyl record network functions from both a consumer and retailer perspective, in order to gain an understanding of how the Internet facilitates the activity within a consumer culture. The vinyl record industry is experiencing a revival, with an upswing in sales and media attention and a significant increase in the amount of online trading. This inductive study contains data from qualitative interviews with ten vinyl record c...

Influence of substituents in vinyl groups on reactivity of parylene during polymerization process

International Nuclear Information System (INIS)

Freza, Sylwia; Skurski, Piotr; Bobrowski, Maciej

2010-01-01

The MCSCF calculations indicate that both triplet and singlet state of biradical di-para-xylylene can exist during polymerization of parylene in gas phase and both can potentially react with vinyl molecules. The singlet-state open-shell dimer turned out to exhibit multiconfigurational character. In the case of triplet state of the dimer two mechanisms of the reactions with various species containing vinyl groups have been examined at the B3LYP/6-31G level. The kinetic and thermodynamical barriers have been estimated for the reaction path involving the π-bond cleavage as well as for the route describing the hydrogen atom transfer. It was found that the overall reactions are thermodynamically favorable, whereas appropriate kinetic barriers for certain derivatives are very small (close to 0 kcal/mol) which in turn makes allowances for easy reactivity under accessible conditions. The calculated mechanisms indicate the influence of substituents in vinyl groups for reactivity of parylene during LPCVD process.

Strain Rate Dependent Ductile-to-Brittle Transition of Graphite Platelet Reinforced Vinyl Ester Nanocomposites

Directory of Open Access Journals (Sweden)

Brahmananda Pramanik

2014-01-01

Full Text Available In previous research, the fractal dimensions of fractured surfaces of vinyl ester based nanocomposites were estimated applying classical method on 3D digital microscopic images. The fracture energy and fracture toughness were obtained from fractal dimensions. A noteworthy observation, the strain rate dependent ductile-to-brittle transition of vinyl ester based nanocomposites, is reinvestigated in the current study. The candidate materials of xGnP (exfoliated graphite nanoplatelets reinforced and with additional CTBN (Carboxyl Terminated Butadiene Nitrile toughened vinyl ester based nanocomposites that are subjected to both quasi-static and high strain rate indirect tensile load using the traditional Brazilian test method. High-strain rate indirect tensile testing is performed with a modified Split-Hopkinson Pressure Bar (SHPB. Pristine vinyl ester shows ductile deformation under quasi-static loading and brittle failure when subjected to high-strain rate loading. This observation reconfirms the previous research findings on strain rate dependent ductile-to-brittle transition of this material system. Investigation of both quasi-static and dynamic indirect tensile test responses show the strain rate effect on the tensile strength and energy absorbing capacity of the candidate materials. Contribution of nanoreinforcement to the tensile properties is reported in this paper.

Poly(vinyl alcohol)-heparin hydrogels as sensor catheter membranes

NARCIS (Netherlands)

Brinkman, E.; van der Does, L.; Bantjes, A.

1991-01-01

Poly(vinyl alcohol)-heparin hydrogels with varying water content were synthesized for use as sensor catheter membranes. Films were cast from aqueous mixtures of poly(viny) alcohol) (PVA), a photosensitive cross-linker p-diazonium diphenyl amine polymer (PA), glutaraldehyde (GA) and heparin. After

Fluorescent vinyl and styryl coumarins: A comprehensive DFT study ...

Indian Academy of Sciences (India)

Kiran Avhad

2017-11-14

Nov 14, 2017 ... Nonlinear optical properties of 3-styryl and 3-vinyl coumarin dyes have been investigated with ..... Figure 4. Dipole moment (μ in Debye) graph in the ground state (S0) and excited state (S1) in .... It gives information on shape,.

Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

KAUST Repository

Behenna, Douglas C.

2011-12-18

The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

KAUST Repository

Vidal, Fernando

2016-07-07

The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

KAUST Repository

Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.-X.

2016-01-01

The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

[3 + 2]-Cycloadditions of nitrile ylides after photoactivation of vinyl azides under flow conditions

Directory of Open Access Journals (Sweden)

Stephan Cludius-Brandt

2013-08-01

Full Text Available The photodenitrogenation of vinyl azides to 2H-azirines by using a photoflow reactor is reported and compared with thermal formation of 2H-azirines. Photochemically, the ring of the 2H-azirines was opened to yield the nitrile ylides, which underwent a [3 + 2]-cycloaddition with 1,3-dipolarophiles. When diisopropyl azodicarboxylate serves as the dipolarophile, 1,3,4-triazoles become directly accessible starting from the corresponding vinyl azide.

Effects of solvents on the radiation grafting reaction of vinyl compounds on poly (3-hydroxybutyrate)

International Nuclear Information System (INIS)

Torres, Maykel González; Talavera, José Rogelio Rodríguez; Muñoz, Susana Vargas; Pérez, Manuel González; Castro, Ma. Pilar. Carreón.; Cortes, Jorge Cerna

2015-01-01

Vinyl Acetate was grafted onto poly (3-hydroxybutyrate) by the simultaneous gamma irradiation method using different types of solvents and in bulk (solvent free), at 10 kGy and 1.62 kGy/h dose and dose rate respectively. Subsequent complete hydrolysis allowed the conversion of grafted chains from poly (vinyl acetate) to poly (vinyl alcohol). The aim of this study is to determine the effect of solvent through the estimation of the dependence of the degree of grafting with the choice of solvent, the calculation of the degree of crystallinity, and to study the biodegradation of the products. The results showed a greater degree of grafting in bulk, while the more suitable solvent was hexane. Characterization of the grafted copolymer indicated that crystallinity percentage decreased by an increase in grafting, while the biodegradability was promoted by the increment in poly (vinyl alcohol) grafted. - Highlights: • PHB was indirectly grafted with PVA, by complete hydrolysis of grafted PVAc. • The effect of solvents on the grafting, crystallinity and biodegradation was studied. • The characterizations of the products were obtained by SEM, TGA, and DSC

Preparation of poly(vinyl alcohol)/kaolinite nanocomposites via in situ polymerization

International Nuclear Information System (INIS)

Jia Xin; Li Yanfeng; Zhang Bo; Cheng Qiong; Zhang Shujiang

2008-01-01

Poly(vinyl alcohol)/kaolinite intercalated nanocomposites (Kao-PVA) were prepared via in situ intercalation radical polymerization. Vinyl acetate (VAc) was intercalated into kaolinite by a displacement method using dimethyl sulfoxide/kaolinite (Kao-DMSO) as the intermediate. Then, PVAc/kaolinite (Kao-PVAc) was obtained via radical polymerization with benzoyl peroxide (BPO) as initiator. Last, PVAc/kaolinite was saponified via direct-hydrolysis with NaOH solution in order to obtain PVA/kaolinite nanocomposites, which was characterized by Fourier-Transformation spectroscopy (FTIR), wide X-ray diffraction (WXRD) and transmission electron microscopy (TEM). Their differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) results of the obtained PVA/kaolinite suggested that the thermal properties had an obvious improvement

Colloidal titration of aqueous zirconium solutions with poly(vinyl sulfate) by potentiometric endpoint detection using a toluidine blue selective electrode.

Science.gov (United States)

Sakurada, Osamu; Kato, Yasutake; Kito, Noriyoshi; Kameyama, Keiichi; Hattori, Toshiaki; Hashiba, Minoru

2004-02-01

Zirconium oxy-salts were hydrolyzed to form positively charged polymer or cluster species in acidic solutions. The zirconium hydrolyzed polymer was found to react with a negatively charged polyelectrolyte, such as poly(vinyl sulfate), and to form a stoichiometric polyion complex. Thus, colloidal titration with poly(vinyl sulfate) was applied to measure the zirconium concentration in an acidic solution by using a Toluidine Blue selective plasticized poly(vinyl chloride) membrane electrode as a potentiometric end-point detecting device. The determination could be performed with 1% of the relative standard deviation. The colloidal titration stoichiometry at pH < or = 2 was one mol of zirconium per equivalent mol of poly(vinyl sulfate).

Preparation of poly(vinyl alcohol)-grafted graphene oxide/poly(vinyl alcohol) nanocomposites via in-situ low-temperature emulsion polymerization and their thermal and mechanical characterization

Energy Technology Data Exchange (ETDEWEB)

Zhang, Shengchang; Liu, Pengqing, E-mail: liupq@scu.edu.cn; Zhao, Xiangsen; Xu, Jianjun, E-mail: xujj@scu.edu.cn

2017-02-28

Highlights: • In-situ emulsion polymerization and alcoholysis reaction is a good method to prepare GO/PVA nanocomposites. • Surface chemical grafting modification of GO with PVA chains was also carried out during the in-situ emulsion polymerization and alcoholysis reaction. • The surface chemical grafting modification of GO by in-situ polymerization and alcoholysis reaction could not only improve the dispersion of fillers in matrix, but also the interfacial interactions between fillers and matrix. • The thermal and mechanical properties of PVA-g-GO/PVA nanocompistes were also studied. - Abstract: An in-situ polymerization combined with chemical grafting modification method for preparing Poly(vinyl alcohol)-grafted graphene oxide/Poly(vinyl alcohol) (PVA-g-GO/PVA) nanocomposites was reported. Firstly, Poly(vinyl acetate)-grafted graphene oxide/Poly(vinyl acetate) nanocomposites were prepared, and then the PVA-g-GO/PVA nanocomposites could be obtained through alcoholysis reaction. X-ray photoelectron spectrometer and fourier-transform infrared spectrometer confirmed that the PVAc or PVA chains were successfully grafted to GO sheets during in-situ polymerization and alcoholysis. And the results from transmission electron microscopy, scanning electron microscopy and X-ray diffraction showed that the well compatibility and homogenous dispersion of PVA-g-GO in PVA matrix could be achieved. Differential scanning calorimetric, thermogravimetry analysis and tensile test were employed to study the thermal and mechanical properties of the PVA-g-GO/PVA nanocomposites. The results indicated that a 53% improvement of tensile strength and a 36% improvement of Young’s modulus were achieved by addition of 0.5 wt% of GO sheets. And the glass transition temperature of PVA-g-GO/PVA nanocomposites was increased, and their thermal stability and crystallization degree were both decreased. Due to well dispersion of fillers and strong interfacial interactions at the filler

Preparation of poly(vinyl alcohol)-grafted graphene oxide/poly(vinyl alcohol) nanocomposites via in-situ low-temperature emulsion polymerization and their thermal and mechanical characterization

International Nuclear Information System (INIS)

Zhang, Shengchang; Liu, Pengqing; Zhao, Xiangsen; Xu, Jianjun

2017-01-01

Highlights: • In-situ emulsion polymerization and alcoholysis reaction is a good method to prepare GO/PVA nanocomposites. • Surface chemical grafting modification of GO with PVA chains was also carried out during the in-situ emulsion polymerization and alcoholysis reaction. • The surface chemical grafting modification of GO by in-situ polymerization and alcoholysis reaction could not only improve the dispersion of fillers in matrix, but also the interfacial interactions between fillers and matrix. • The thermal and mechanical properties of PVA-g-GO/PVA nanocompistes were also studied. - Abstract: An in-situ polymerization combined with chemical grafting modification method for preparing Poly(vinyl alcohol)-grafted graphene oxide/Poly(vinyl alcohol) (PVA-g-GO/PVA) nanocomposites was reported. Firstly, Poly(vinyl acetate)-grafted graphene oxide/Poly(vinyl acetate) nanocomposites were prepared, and then the PVA-g-GO/PVA nanocomposites could be obtained through alcoholysis reaction. X-ray photoelectron spectrometer and fourier-transform infrared spectrometer confirmed that the PVAc or PVA chains were successfully grafted to GO sheets during in-situ polymerization and alcoholysis. And the results from transmission electron microscopy, scanning electron microscopy and X-ray diffraction showed that the well compatibility and homogenous dispersion of PVA-g-GO in PVA matrix could be achieved. Differential scanning calorimetric, thermogravimetry analysis and tensile test were employed to study the thermal and mechanical properties of the PVA-g-GO/PVA nanocomposites. The results indicated that a 53% improvement of tensile strength and a 36% improvement of Young’s modulus were achieved by addition of 0.5 wt% of GO sheets. And the glass transition temperature of PVA-g-GO/PVA nanocomposites was increased, and their thermal stability and crystallization degree were both decreased. Due to well dispersion of fillers and strong interfacial interactions at the filler

Poly(vinyl alcohol) gels as photoacoustic breast phantoms revisited

NARCIS (Netherlands)

Xia, Wenfeng; Piras, Daniele; Heijblom, Michelle; Steenbergen, Wiendelt; van Leeuwen, Ton G.; Manohar, Srirang

2011-01-01

A popular phantom in photoacoustic imaging is poly(vinyl alcohol) (PVA) hydrogel fabricated by freezing and thawing (F-T) aqueous solutions of PVA. The material possesses acoustic and optical properties similar to those of tissue. Earlier work characterized PVA gels in small test specimens where

Poly(vinyl alcohol) gels as photoacoustic breast phantoms revisited

NARCIS (Netherlands)

Xia, W.; Piras, D.; Heijblom, M.; Steenbergen, Wiendelt; van Leeuwen, Ton; Manohar, Srirang

2011-01-01

A popular phantom in photoacoustic imaging is poly(vinyl alcohol) (PVA) hydrogel fabricated by freezing and thawing (F–T) aqueous solutions of PVA. The material possesses acoustic and optical properties similar to those of tissue. Earlier work characterized PVA gels in small test specimens where

Investigation Into Accessible Surface Vinyl Concentrations of Nonstoichiometric PDMS Microspheres from Hydrosilylation Reactions and Their Further Crosslinking Reactions

DEFF Research Database (Denmark)

Ma, Baoguang; Hansen, Jens Henrik; Hvilsted, Søren

2015-01-01

The introduction of surface vinyl groups to PDMS microspheres broadens the latter's applicability range since the microspheres can be further functionalized or crosslinked into elastomers. Quantification of the surface vinyl concentration of PDMS microspheres is therefore essential. Here, a novel...

Rhodium(III)-Catalyzed ortho-Alkylation of Phenoxy Substrates with Diazo Compounds via C-H Activation: A Case of Decarboxylative Pyrimidine/Pyridine Migratory Cyclization Rather than Removal of Pyrimidine/Pyridine Directing Group.

Science.gov (United States)

Ravi, Manjula; Allu, Srinivasarao; Swamy, K C Kumara

2017-03-03

An efficient Rh(III)-catalyzed ortho-alkylation of phenoxy substrates with diazo compounds has been achieved for the first time using pyrimidine or pyridine as the directing group. Furthermore, bis-alkylation has also been achieved using para-substituted phenoxypyrimidine and 3 mol equiv of the diazo ester. The ortho-alkylated derivatives of phenoxy products possessing the ester functionality undergo decarboxylative pyrimidine/pyridine migratory cyclization (rather than deprotection of pyrimidine/pyridine group) using 20% NaOEt in EtOH affording a novel class of 3-(pyrimidin-2(1H)-ylidene)benzofuran-2(3H)-ones and 6-methyl-3-(pyridin-2(1H)-ylidene)benzofuran-2(3H)-one. The ortho-alkylated phenoxypyridine possessing ester functionality also undergoes decarboxylative pyridine migratory cyclization using MeOTf/NaOMe in toluene providing 6-methyl-3-(1-methylpyridin-2(1H)-ylidene)benzofuran-2(3H)-one.

Pd nanoparticles immobilized on carbon nanotubes with a polyaniline coaxial coating for the Heck reaction: coating thickness as the key factor influencing the efficiency and stability of the catalyst

KAUST Repository

Yu, Rui

2018-02-12

Pd nanoparticles (NPs) supported on polyaniline (PANI)-coated carbon nanotubes (CNTs) were synthesized using a low-cost and simple method for application in the Heck reaction. The effects of the PANI/CNT coating weight ratio on the catalytic stability and recyclability of the composite were determined by using a combination of experimental and computational methods. The results show that through coordination of the N-species in PANI with the Pd NPs, the nitrogen-rich PANI@CNT provides a strong support for the Pd NPs. The thickness of the PANI layer is the key in determining the stability of the catalyst. PANI becomes protonated in the presence of CNTs, as electron transfer from the former to the latter creates strong interactions between the two. Thus, PANI becomes more stable in nanocomposites with a higher CNT content, e.g., PANI/CNT = 0.5 : 1. The catalyst with a PANI/CNT ratio of 0.5 : 1 exhibited the best recycling performance, and only a small loss of activity was observed after 10 cycles. However, upon increasing the PANI content (e.g., PANI/CNT = 4 : 1), the PANI units tend to form bulk structures that are less stable than those that wrap around the CNTs. Such a structure is unstable; therefore, the PANI layers can easily deform or break away from the CNT backbones. Hence, these catalysts deactivate during recycling. Thus, our study demonstrates that the assembly of noble-metal NPs on CNTs bearing a thin coaxial PANI coating is a powerful technique to prepare reusable catalysts for the Heck reaction. Coating thickness is also a key factor affecting the efficiency and stability of the catalyst.

Pd nanoparticles immobilized on carbon nanotubes with a polyaniline coaxial coating for the Heck reaction: coating thickness as the key factor influencing the efficiency and stability of the catalyst

KAUST Repository

Yu, Rui; Liu, Rui; Deng, Jie; Ran, Maofei; Wang, Ning; Chu, Wei; He, Zhiwei; Du, Zheng; Jiang, Chengfa; Sun, Wenjing

2018-01-01

Pd nanoparticles (NPs) supported on polyaniline (PANI)-coated carbon nanotubes (CNTs) were synthesized using a low-cost and simple method for application in the Heck reaction. The effects of the PANI/CNT coating weight ratio on the catalytic stability and recyclability of the composite were determined by using a combination of experimental and computational methods. The results show that through coordination of the N-species in PANI with the Pd NPs, the nitrogen-rich PANI@CNT provides a strong support for the Pd NPs. The thickness of the PANI layer is the key in determining the stability of the catalyst. PANI becomes protonated in the presence of CNTs, as electron transfer from the former to the latter creates strong interactions between the two. Thus, PANI becomes more stable in nanocomposites with a higher CNT content, e.g., PANI/CNT = 0.5 : 1. The catalyst with a PANI/CNT ratio of 0.5 : 1 exhibited the best recycling performance, and only a small loss of activity was observed after 10 cycles. However, upon increasing the PANI content (e.g., PANI/CNT = 4 : 1), the PANI units tend to form bulk structures that are less stable than those that wrap around the CNTs. Such a structure is unstable; therefore, the PANI layers can easily deform or break away from the CNT backbones. Hence, these catalysts deactivate during recycling. Thus, our study demonstrates that the assembly of noble-metal NPs on CNTs bearing a thin coaxial PANI coating is a powerful technique to prepare reusable catalysts for the Heck reaction. Coating thickness is also a key factor affecting the efficiency and stability of the catalyst.

An Investigation of Chitosan-Grafted-Poly(vinyl alcohol) as an Electrolyte Membrane

OpenAIRE

Panu Danwanichakul; Pongchayont Sirikhajornnam

2013-01-01

The membrane of chitosan-grafted-poly(vinyl alcohol)/poly(vinyl alcohol) (CS-g-PVA/PVA) was investigated along with chitosan (CS), PVA, CS/PVA, and Nafion 117 membranes for transport properties of water and methanol, mechanical properties, and ionic conductivity. The ionic conductivity, σ, of the crosslinked CS-g-PVA/PVA membrane was about 4.37 mS cm−1 and the methanol permeability, PS, was 1.8×10−7 cm2s−1. These gave the selectivity, σ/PS, of 23.95 mS·s·cm−3 compared with 16.35 mS·s·cm−3 of ...

The radiation-induced copolymerization of vinyl acetate with dibutyl maleate

International Nuclear Information System (INIS)

Du Plessis, T.A.; Lustig, A.

1975-01-01

The radiation-induced copolymerization of vinyl acetate with dibutyl maleate was investigated in the temperature range from -50 0 to 90 0 . A copolymer of the unsaturated ester with vinyl acetate was obtained in which the comonomers alternate with regularity along the polymer chain over the entire range of comonomer compositions and temperature range investigated. Both the rate of copolymerization and the molecular weight of the resulting copolymer were found to depend strongly on the comonomer composition. The monomer reactivity ratios were found to be practically zero. The apparent activation energy was found to change at 5 0 with an increase in temperature from a value of 1,6 kcal/mole to a value of 4,4kcal/mole. Scavenger studies indicate that a free radical mechanism prevails over the entire temperature range investigated. (Author) [af

Radiation grafting from binary monomer mixtures. II. Vinyl ether of monoethanolamine and N-vinylpyrrolidone

International Nuclear Information System (INIS)

Nurkeeva, Zauresh S.; Abdel Aal, A.-S.; Kupchishin, Anatoliy I.; Khutoryanskiy, Vitaliy V.; Mun, Grigoriy A.; Beksyrgaeva, Aida G.

2003-01-01

Radiation grafting from binary monomer mixtures of vinyl ether of monoethanolamine and N-vinylpyrrolidone onto polyethylene films has been studied. The structure of the grafted films was characterized by FTIR spectroscopy. Water uptake and contact angle measurements confirmed that the grafting leads to a considerable hydrophilization of the films surface. The presence of the more active N-vinylpyrrolidone enhances the grafting of the less active vinyl ether of monoethanolamine. Sorption properties of grafted films with respect to copper (II) ions have been studied

Radiation grafting from binary mixtures of vinyl ether of mono ethanol amine with N-vinylpyrrolidone and vinyl ether of ethylene glycol onto polyolefins films and metallization of obtained films

International Nuclear Information System (INIS)

Al'-Saed Abdel' Aal'; Nurkeeva, Z.; Khutoryanskij, V.; Mun, G.; Sangajlo, M.

2003-01-01

Radiation grafting from binary mixtures of vinyl ether of mono ethanol amine with N-vinylpyrrolidone and vinyl ether of ethylene glycol onto polyolefins films using γ-radiation and accelerated electrons has been studied. IR-spectroscopy is used to confirm the structure of grafted films. A combination of and metallization of obtained films. A combination of gravimetric and potentiometric techniques is applied to determine the fraction of each monomer in graft copolymer. Water uptake and contact angle measurements confirmed that the grafting process improve the hydrophilic properties of obtained films. The obtained materials are metallized by electroless copper plating. The metallized films have good electro conductive properties. (author)

Spectroscopic detection and mapping of vinyl cyanide on Titan

Science.gov (United States)

Cordiner, Martin; Yukiko Palmer, Maureen; Lai, James; Nixon, Conor A.; Teanby, Nicholas; Charnley, Steven B.; Vuitton, Veronique; Kisiel, Zbigniew; Irwin, Patrick; Molter, Ned; Mumma, Michael J.

2017-10-01

The first spectroscopic detection of vinyl cyanide (otherwise known as acrylonitrile; C2H3CN) on Titan was obtained by Palmer et al. (2017), based on three rotational emission lines observed with ALMA at millimeter wavelengths (in receiver band 6). The astrobiological significance of this detection was highlighted due to the theorized ability of C2H3CN molecules to combine into cell membrane-like structures under the cold conditions found in Titan's hydrocarbon lakes. Here we report the detection of three additional C2H3CN transitions at higher frequencies (from ALMA band 7 flux calibration data). We present the first emission maps for this gas on Titan, and compare the molecular distribution with that of other nitriles observed with ALMA including HC3N, CH3CN, C2H5CN and HNC. The molecular abundance patterns are interpreted based on our understanding of Titan's high-altitude photochemistry and time-variable global circulation. Similar to the short-lived HC3N molecule, vinyl cyanide is found to be most abundant in the vicinity of the southern (winter) pole, whereas the longer-lived CH3CN is more concentrated in the north. The vertical abundance profile of C2H3CN (from radiative transfer modeling), as well as its latitudinal distribution, are consistent with a short photochemical lifetime for this species. Complementary results from our more recent (2017) nitrile mapping studies at higher spatial resolution will also be discussed.REFERENCES:Palmer, M. Y., Cordiner, M. A., Nixon, C. A. et al. "ALMA detection and astrobiological potential of vinyl cyanide on Titan", Sci. Adv. 2017, 3, e1700022

New examples of the vinylation of NH-heterocycles with acetylene at atmospheric pressure in the KOH-DMSO system

Energy Technology Data Exchange (ETDEWEB)

Trofimov, B.A.; Nesterenko, R.N.; Mikhaleva, A.I.; Shapiro, A.B.; Aliev, I.A.; Yakovleva, I.V.; Kalabin, G.A.

1986-10-01

Vinylation of 2-hetarylpyrroles, 4,5-dihydrobenzo(g)indole, and 1,2,3,4-tetrahydro-..gamma..-carbinols at atmospheric pressure in the superbasic system KOH-DMSO at 100-120/sup 0/C has given the corresponding N-vinyl derivatives in yields of 92-99%.

Phytoscreening for vinyl chloride in groundwater discharging to a stream

DEFF Research Database (Denmark)

Ottosen, Cecilie Bang; Rønde, Vinni Kampman; Trapp, Stefan

2018-01-01

and hence different uptake/loss scenarios. Vinyl chloride (VC) as well as cis-dichloroethylene (cis-DCE), trichloroethylene (TCE), and tetrachloroethylene (PCE) were detected in the trees, documenting that phytoscreening is a viable method to locate chlorinated ethene plumes, including VC, discharging...

40 CFR 61.63 - Emission standard for vinyl chloride plants.

Science.gov (United States)

2010-07-01

... plants. 61.63 Section 61.63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS National Emission Standard... formation and purification: The concentration of vinyl chloride in each exhaust gas stream from any...

Using the Maturity Method in Predicting the Compressive Strength of Vinyl Ester Polymer Concrete at an Early Age

Directory of Open Access Journals (Sweden)

Nan Ji Jin

2017-01-01

Full Text Available The compressive strength of vinyl ester polymer concrete is predicted using the maturity method. The compressive strength rapidly increased until the curing age of 24 hrs and thereafter slowly increased until the curing age of 72 hrs. As the MMA content increased, the compressive strength decreased. Furthermore, as the curing temperature decreased, compressive strength decreased. For vinyl ester polymer concrete, datum temperature, ranging from −22.5 to −24.6°C, decreased as the MMA content increased. The maturity index equation for cement concrete cannot be applied to polymer concrete and the maturity of vinyl ester polymer concrete can only be estimated through control of the time interval Δt. Thus, this study introduced a suitable scaled-down factor (n for the determination of polymer concrete’s maturity, and a factor of 0.3 was the most suitable. Also, the DR-HILL compressive strength prediction model was determined as applicable to vinyl ester polymer concrete among the dose-response models. For the parameters of the prediction model, applying the parameters by combining all data obtained from the three different amounts of MMA content was deemed acceptable. The study results could be useful for the quality control of vinyl ester polymer concrete and nondestructive prediction of early age strength.

Synthesis of alkynes from vinyl triflates using tetrabutylammonium fluoride.

Science.gov (United States)

Okutani, Masaru; Mori, Yuji

2015-01-01

A convenient method for the preparation of alkynes and alkynyl esters from ketones and β-keto esters is described which involves the formation of vinyl triflates, followed by elimination with tetrabutylammonium fluoride trihydrate, to give alkynes. Unlike established elimination methods, the method requires neither a strong base nor anhydrous conditions.

Reactive compatibilization of ethylene-co-vinyl acetate/starch blends

NARCIS (Netherlands)

Ma, P.; Hristova - Bogaerds, D.G.; Schmit, P.; Goossens, J.G.P.; Lemstra, P.J.

2012-01-01

The dispersion of starch as a filler in hydrophobic ethylene-co-vinyl acetate (EVA) rubber is an issue. To obtain a fine dispersion of starch in EVA rubber, EVA/starch blends were prepared by reactive extrusion in the pres- ence of maleic anhydride (MA), benzoyl peroxide (BPO), and glycerol. MA,

Comparison of slime-producing coagulase-negative Staphylococcus colonization rates on vinyl and ceramic tile flooring materials.

Science.gov (United States)

Yazgi, H; Uyanik, M H; Ayyildiz, A

2009-01-01

This study investigated the colonization of slime-producing coagulase-negative Staphylococcus (CoNS) in 80 patient wards in Turkey (40 vinyl and 40 ceramic tile floors). A total of 480 samples that included 557 CoNS isolates were obtained. Slime production was investigated with the Christensen method and methicillin-susceptibility was tested by the disk-diffusion method. There was a significant difference in the percentage of slime-producing CoNS isolates on vinyl (12.4%) versus ceramic tile flooring (4.4%). From vinyl flooring, the percentage of slime producing methicillin-resistant CoNS (MRCoNS) (8.9%) was significantly higher than for methicillin-sensitive CoNS (MSCoNS) (3.6%), whereas there was no difference from ceramic tile flooring (2.5% MRCoNS versus 1.8% MSCoNS). The most commonly isolated slime-producing CoNS species was S. epidermidis on both types of flooring. It is concluded that vinyl flooring seems to be a more suitable colonization surface for slime-producing CoNS than ceramic tile floors. Further studies are needed to investigate bacterial strains colonized on flooring materials, which are potential pathogens for nosocomial infections.

Sequential aminodiene Diels-Alder approach to the ergoline skeleton.

Science.gov (United States)

Padwa, Albert; Bur, Scott K; Zhang, Hongjun

2005-08-19

Through a novel sequence of aminodiene Diels-Alder reactions, several substituted amidofurans were readily converted to tricyclic ketones in good yield. The formation of the tricyclic ketone system is the result of a ring opening and dehydration of a transient oxabicyclic adduct formed by an intramolecular Diels-Alder cycloaddition of an amidofuran with a cyclohexenone moiety tethered such that it participates in the cycloaddition as the 2pi component. A convenient way to construct the cyclohexenone is to make use of some aminodiene chemistry developed by Rawal. An angular carbomethoxy group is required in order to activate the olefin toward cycloaddition with Rawal's diene. The presence of this activating group not only prevents the isomerization of the advanced ergoline intermediate to a naphthalene but can also be leveraged for an oxidation to provide Uhle's ketone (13). The easily formed Kornfeld ketone analogue 25 was readily transformed into the corresponding triflate 41 by the action of triflic anhydride and a base. Oxidative addition of vinyl triflate 41 to Pd(0) and the ability of the resulting vinyl palladium species to undergo cross-coupling with terminal alkynes prompted us to devise an expeditious route to lysergic acid. Unfortunately, our inability to carry out a regioselective Heck reaction using vinyl triflate 41 and the methylene amino acrylate ester 48 thwarted the completion of the synthesis of lysergic acid.

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

Science.gov (United States)

Chemical and Engineering News, 1980

1980-01-01

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

Far-infrared Spectroscopic Characterization of Anti-vinyl Alcohol

Science.gov (United States)

Bunn, Hayley; Soliday, Rebekah M.; Sumner, Isaiah; Raston, Paul L.

2017-09-01

We report a detailed analysis of the high-resolution far-infrared spectrum of anti-vinyl alcohol, which has been previously identified toward Sagittarius B2(N). The ν 15 OH torsional fundamental investigated here is more than 200 cm-1 removed from the next nearest vibration, making it practically unperturbed and ideal to help refine the ground state rotational constants that were previously determined from 25 microwave lines. We assigned 1335 lines within the ν 15 fundamental centered at 261.5512 cm-1, with J and K a ranges of 1-59 and 0-16, respectively. The microwave and far-infrared line positions were fit with Watson-type A- and S-reduced Hamiltonians, with the inclusion of quartic and select sextic distortion terms. This resulted in a significant refinement of the ground state constants, in addition to the determination of the {ν }15=1 state constants for the first time. The spectroscopic parameters are in good agreement with the results from anharmonic coupled-cluster calculations, and should be useful in searches for rotationally and/or vibrationally warm anti-vinyl alcohol in interstellar molecular clouds.

Reduction of CT beam hardening artefacts of ethylene vinyl alcohol copolymer by variation of the tantalum content: evaluation in a standardized aortic endoleak phantom

International Nuclear Information System (INIS)

Treitl, Karla M.; Scherr, Michael; Foerth, Monika; Braun, Franziska; Maxien, Daniel; Treitl, Marcus

2015-01-01

Our aim was to develop an aortic stent graft phantom to simulate endoleak treatment and to find a tantalum content (TC) of ethylene-vinyl-alcohol-copolymer that causes fewer computed tomography (CT) beam hardening artefacts, but still allows for fluoroscopic visualization. Ethylene-vinyl-alcohol-copolymer specimens of different TC (10-50 %, and 100 %) were injected in an aortic phantom bearing a stent graft and endoleak cavities with simulated re-perfusion. Fluoroscopic visibility of the ethylene-vinyl-alcohol-copolymer specimens was analyzed. In addition, six radiologists analyzed endoleak visibility, and artefact intensity of ethylene-vinyl-alcohol-copolymer in CT. Reduction of TC significantly decreased CT artefact intensity of ethylene-vinyl-alcohol-copolymer and increased visibility of endoleak re-perfusion (p < 0.000). It also significantly decreased fluoroscopic visibility of ethylene-vinyl-alcohol-copolymer (R = 0.883, p ≤ 0.01), and increased the active embolic volumes prior to visualization (Δ ≥ 40 μl). Ethylene-vinyl-alcohol-copolymer specimens with a TC of 45-50 % exhibited reasonable visibility, a low active embolic volume and a tolerable CT artefact intensity. The developed aortic stent graft phantom allows for a reproducible simulation of embolization of endoleaks. The data suggest a reduction of the TC of ethylene-vinyl-alcohol-copolymer to 45 -50 % of the original, to interfere less with diagnostic imaging in follow-up CT examinations, while still allowing for fluoroscopic visualization. (orig.)

Zinc(II) catalyzed conversion of alkynes to vinyl triflates in the presence of silyl triflates.

Science.gov (United States)

Al-huniti, Mohammed H; Lepore, Salvatore D

2014-08-15

The conversion of alkynes to their corresponding vinyl triflates in the presence of stoichiometric TMS-triflate was greatly facilitated by the triflate salt of several transition metal catalysts most especially Zn(OTf)2. Products are formed in high regioselectivity under mild conditions. Internal alkynes bearing an aryl substituent afford vinyl triflates with a modest preference for the Z-isomer especially with larger substituents. A mechanism is put forward to explain the unique role of silicon in this system.

Synthesis of Ethylene or Propylene/1,3-Butadiene Copolymers Possessing Pendant Vinyl Groups with Virtually No Internal Olefins

Directory of Open Access Journals (Sweden)

Kenji Michiue

2015-11-01

Full Text Available In general, ethylene/1,3-butadiene copolymerizations provides copolymers possessing both pendant vinyls and vinylenes as olefinic moieties. We, at MCI, studied the substituent effects of C2-symmetric zirconocene complexes, rac-[Me2Si(Indenyl’2]ZrCl2 (Indenyl’ = generic substituted indenyl, after activation on the ratio of the pendant vinyls and vinylenes of the resultant copolymers. Complexes examined in this study were rac-dimethylsilylbis (1-indenylzirconium dichloride (1, rac-dimethylsilyl-bis[1-(2-methyl-4,5-benzoindenyl] zirconium dichloride (2, rac-dimethylsilyl-bis[l-(2-methyl -4-phenylindenyl]zirconium dichloride (3, rac-dimethy1si1y1- bis(2-ethyl-4-phenylindenyl zirconium dichloride (4, rac-dimethylsilyl-bis[l-(2-n-propyl -4-(1-naphthylindenyl]zirconium dichloride (5, rac-dimethylsilyl-[1-(2-ethyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta [a]naphthalenylindenyl][1-(2-n-propyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta[a] naphthalenylindenyl]zirconium dichloride (6, rac-dimethylsilyl-bis[1-(2-ethyl-4-(9-phenanthrylindenyl]zirconium dichloride (7, and rac-dimethylsilyl-bis[l-(2-n-propyl-4-(9-phenanthrylindenyl]zirconium dichloride (8. We found that the ratio of the pendant vinyls and vinylenes is strongly affected by the bulkiness of the substituent on the complexes examined. The vinyl content increased linearly in the following order, 8 > 7 > 6 > 5 > 4 > 3 > 2 > 1. Notably, complex 8/DMAO formed ethylene/1,3-butadiene copolymers possessing predominant vinyl groups, which can be crucial precursors for functionalized polyolefins. Likewise, complex 8/DMAO afforded propylene/1,3-butadiene copolymers with predominant vinyl groups.

Fracture inspection by BHTV logging through a vinyl chloride tube; Enbi pipe ga sonyusareta kosei deno BHTV ni yoru kiretsu chosa

Energy Technology Data Exchange (ETDEWEB)

Horikawa, H.; Okabe, T.; Takasugi, S. [GERD Geothermal Energy Research and Development Co. Ltd., Tokyo (Japan); Yamauchi, Y.; Imanishi, H. [Osaka Soil Test, Osaka (Japan)

1997-05-27

A borehole televiewer (BHTV) logging was conducted to investigate cracks in bored wells. The logging process shoots ultrasonic waves onto bore walls and utilizes reflection waves from the bore walls. If the bores are filled with muddy water, or the ultrasonic waves can pass through even if vinyl chloride tubes have been inserted after excavation, the state of the bore walls can be investigated in principle. Conventional optical scanners are, however, incapable of making this investigation. The BHTV logging can be used for identifying lithofacies from reflection intensities from bore walls (it depends on sound impedance of rocks), not to speak of finding cracks. As a result of making logging upon setting time windows from 105 to 145 {mu} sec in a bored well inserted with a vinyl chloride tube, cracks in the bore wall were identified clearly through the vinyl chloride tube. If the distance between the bore wall and the vinyl chloride tube becomes smaller, setting the time window becomes difficult, making reflection data acquisition more difficult. Impacts of decentering in the vinyl chloride tube on the data and the crack analysis result are small. The reflection intensity has decreased by about half as a result of having the circular vinyl chloride tube inserted. 5 refs., 9 figs., 1 tab.

Characterization of nanocellulose reinforced semi-interpenetrating polymer network of poly(vinyl alcohol) & polyacrylamide composite films.

Science.gov (United States)

Mandal, Arup; Chakrabarty, Debabrata

2015-12-10

Semi-interpenetrating polymer network (semi-IPN) of poly(vinyl alcohol)/polyacrylamide was reinforced with various doses of nanocellulose. The different composite films thus prepared were characterized with respect to their mechanical, thermal, morphological and barrier properties. The composite film containing 5 wt.% of nanocellulose showed the highest tensile strength. The semi-interpenetrating polymer network of poly(vinyl alcohol)/polyacrylamide; and its various composites with nanocellulose were almost identical in their thermal stability. Each of the composites however exhibited much superior stability with respect to the linear poly(vinyl alcohol) and crosslinked polyacrylamide. The scanning electron microscopy (SEM) and atomic force microscopy (AFM) studies exhibited phase separated morphology where agglomerates of nanocellulose were found to be dispersed in the matrix of the semi-IPN. The moisture vapor transmission rate (MVTR) was the lowest for the film containing 5 wt.% of nanocellulose. Copyright © 2015 Elsevier Ltd. All rights reserved.

Poly(aniline-co-m-aminobenzoic acid) deposited on poly(vinyl ...

Indian Academy of Sciences (India)

Abstract. In this work, we have deposited poly(aniline-co-m-aminobenzoic acid) on poly(vinyl alcohol) (PVA) by in situ ... along the polyaniline (PANI) chain results in self dop- ing of PANI and ..... The value of electrical conductivity is found to be ...

Cross-Coupling of Sodium Sulfinates with Aryl, Heteroaryl and Vinyl Halides by Nickel/photoredox dual catalysis

KAUST Repository

Yue, Huifeng

2017-12-06

An efficient photoredox/nickel dual catalyzed sulfonylation reaction of aryl, heteroaryl, and vinyl halides has been achieved for the first time. This newly developed sulfonylation protocol provides a versatile method for the synthesis of diverse aromatic sulfones at room temperature and shows excellent functional group tolerance. The electrophilic coupling partners are not limited to aryl, heteroaryl and vinyl bromides but also less reactive aryl chlorides are suitable substrates for this transformation.

Cross-Coupling of Sodium Sulfinates with Aryl, Heteroaryl and Vinyl Halides by Nickel/photoredox dual catalysis

KAUST Repository

Yue, Huifeng; Zhu, Chen; Rueping, Magnus

2017-01-01

An efficient photoredox/nickel dual catalyzed sulfonylation reaction of aryl, heteroaryl, and vinyl halides has been achieved for the first time. This newly developed sulfonylation protocol provides a versatile method for the synthesis of diverse aromatic sulfones at room temperature and shows excellent functional group tolerance. The electrophilic coupling partners are not limited to aryl, heteroaryl and vinyl bromides but also less reactive aryl chlorides are suitable substrates for this transformation.

Vinyl Chloride Emulsion Polymerization Reaction: Effect of Various Formulations

Directory of Open Access Journals (Sweden)

Seyed Mehrdad Jalilian

2013-01-01

Full Text Available A mixture  of  sodium  lauryl  sulfate  (SLS  as  ionic  emulsifer  and  stearyl alcohol as non-ionic emulsifer was employed in a vinyl chloride emulsion polymerization  reaction  to  study  the  infuence  of  various  interactive parameters involved in the reaction system. It was found that the particle size was dependent on the amount and type of emulsifer. The average particle size of polyvinyl chloride was dropped by higher amount of emulsifying agents.  At the gel point, more heat was generated by higher amount of vinyl chloride fed into the reaction system. The molecular weight of the polymer was decreased by increases in reaction temperature while,  it  increased by augmenting  the amount of emulsifer. According to the 13C NMR and FTIR spectroscopic data no defect was detected in the chain structure of synthetic polyvinylchloride product. An optimization of polymerization reaction condition was reached based on ultimate particle size desired for its favorable distribution in plastisols.

Pyrolysis-gas chromatography-mass spectrometry for studying N-vinyl-2-pyrrolidone-co-vinyl acetate copolymers and their dissolution behaviour.

Science.gov (United States)

Chojnacka, Aleksandra; Ghaffar, Abdul; Feilden, Andrew; Treacher, Kevin; Janssen, Hans-Gerd; Schoenmakers, Peter

2011-11-14

Knowledge on the solubility behaviour and dissolution rate of speciality and commodity polymers is very important for the use of such materials in high-tech applications. We have developed methods for the quantification and characterization of dissolved copolymers of N-vinyl-2-pyrrolidone (VP) and vinyl acetate (VA) during dissolution in water. The methods are based on pyrolysis (Py) performed in a programmed-temperature vaporization injector with subsequent identification and quantification of the components in the pyrolysate using capillary gas chromatography-mass spectrometry (GC-MS). By injecting large volumes and applying cryo-focussing at the top of the column, low detection limits could be achieved. The monomer ratio was found to have the greatest effect on the dissolution rate of the PVP-co-VA copolymers. The material with the highest amount of VA (50%) dissolves significantly slower than the other grades. Size-exclusion chromatography (SEC) and Py-GC-MS were used to measure molecular weights and average chemical compositions, respectively. Combined off-line SEC//Py-GC-MS was used to determine the copolymer composition (VP/VA ratio), as a function of the molecular weight for the pure polymers. In the dissolution experiments, a constant VP/VA ratio across the dissolution curve was observed for all copolymers analysed. This suggests a random distribution of the two monomers over the molecules. Copyright © 2011 Elsevier B.V. All rights reserved.

Preparation of CuS nanoparticles embedded in poly(vinyl alcohol ...

Indian Academy of Sciences (India)

WINTEC

ray diffraction (XRD) analyses and electron diffraction pattern also revealed the forming of CuS crystal structure in the PVA fibres. Keywords. CuS nanoparticles; electrospinning; poly(vinyl alcohol). 1. Introduction. In the past decade, the preparation of low-dimensional semiconductor nanostructures has become a hotspot of.

Complex-radical copolymerization of vinyl monomers on organoelemental initiators

International Nuclear Information System (INIS)

Grishin, D.F.

1993-01-01

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

Effect of Compatibilization on Poly-ε-Caprolactone Grafting onto Poly(ethylene-co-vinyl alcohol

Directory of Open Access Journals (Sweden)

Mohamed Taha

2011-10-01

Full Text Available The non-miscibility of the reactants during solvent free poly-ε-caprolactone grafting onto poly(ethylene-co-vinyl alcohol (EVOH dramatically affects reaction kinetics. Different solutions were proposed to accelerate the exchange reactions between poly(ethylene-co-vinyl alcohol and poly-ε-caprolactone. Reactions were conducted in a batch reactor or a mini twin-screw extruder. The addition of a poly(ethylene-co-vinyl alcohol-g-poly-ε-caprolactone copolymer increased the compatibility of the reactants and led to a higher reaction rate. This copolymer was either prepared separately and added at the reaction beginning or prepared in situ grafting caprolactone from EVOH. The reactive system evolution was analyzed using molar mass evolution, microstructure characterization, thermal properties and the reactive blend morphology. The compatibilization effect combined with optimized reaction conditions, such as concentration and nature of catalyst and temperature, resulted in an important increase in reaction rates. Among the tested catalysts, 1,5,7-Triazabicyclo [4.4.0]dec-5-ene was a more efficient catalyst for grafting reactions than Tin (II 2-ethylhexanoate.

ANALYSIS OF ADIPATE ESTER CONTENTS IN POLY(VINYL CHLORIDE) PLASTICS

DEFF Research Database (Denmark)

Berg, Rolf W.; Otero, Amalia Dopazo

2006-01-01

Fourier transform (FT-) Raman spectroscopy excited with a 1064 nm laser can be used to determine the content of plasticizers in commercial flexible poly vinyl chloride (PVC) products. Our previous study [T. Nørbygaard, R.W. Berg, Analysis of phthalate ester content in PVC plastics by means of FT......-Raman Spectroscopy, Appl. Spectrosc. 58 (4) (2004) 410–413]—on detection of the presence of phthalate esters in PVC by FT-Raman spectroscopy — is here extended to the similar case of adipate esters (AEs) in samples of soft poly vinyl chloride plastics. Spectra of a range of adipate ester plasticizers (11 AEs......) in pure form are reported. We studied if qualitative and quantitative determination of the adipate ester content would be possible based on the use of proper reference samples. It was found that AEs as a group cannot be definitively identified by their characteristic Raman bands because other aliphatic...

Oil recovery with vinyl sulfonic acid-acrylamide copolymers

Energy Technology Data Exchange (ETDEWEB)

Norton, C.J.; Falk, D.O.

1973-12-18

An aqueous polymer flood containing sulfomethylated alkali metal vinyl sulfonate-acrylamide copolymers was proposed for use in secondary or tertiary enhanced oil recovery. The sulfonate groups on the copolymers sustain the viscosity of the flood in the presence of brine and lime. Injection of the copolymer solution into a waterflooded Berea core, produced 30.5 percent of the residual oil. It is preferred that the copolymers are partially hydrolyzed.

Properties of poly(vinyl alcohol)–borax gel doped with neodymium ...

Indian Academy of Sciences (India)

visible region then leads to luminescent emission in the near infra-red region. The spectral qualities of the ... molecular hydrogen bonding between the hydroxyl groups on poly(vinyl ..... mately results in near IR emissions. The maximum of the.

Radiation cross-linking of ethylene vinyl alcohol copolymer functionalized with m-isopropenyl-α,α-dimethyl benzyl isocyanate

International Nuclear Information System (INIS)

Ekman, K.B.; Naesman, J.H.

1993-01-01

An ethylene vinyl alcohol copolymer was functionalized with m-isopropenyl-α,α-dimethyl benzyl isocyanate using reactive processing in a mixer. The functionalization introduces pendant unsaturation to the polymer, which allows radiation cross-linked to gel contents >70% at radiation doses below 100 kGy. Unfunctionalized ethylene vinyl alcohol copolymer, on the other hand, forms no gel upon irradiation. The functionalization was completed within a few minutes of reactive mixing, which was confirmed with both FTIR and 13 C-NMR measurements. The oxygen permeability of ethylene vinyl alcohol copolymer increased with increasing degree of functionalization, and irradiation of the samples formed trapped radicals, which act as oxygen scavengers. Consequently no oxygen permeability was detected. However, radical activity was inhibited by annealing the samples at 110 C resulting in a 24% higher oxygen permeability value for the irradiated unfunctionalized copolymer. The oxygen permeability values of the irradiated functionalized samples were approximately 13% lower. Laminates of m-isopropenyl-α,α-dimethyl benzyl isocyanate functionalized ethylene vinyl alcohol copolymer and m-isopropenyl-α,α-dimethyl benzyl isocyanate functionalized ethylene hydroxyethyl methacrylate copolymer acquired improved adhesive strength both at dry and wet conditions as well as at elevated temperature upon exposure to radiation

Biotransformation of ferulic acid to 4-vinyl guaiacol by Lactobacillus ...

African Journals Online (AJOL)

Continuously growing demand for natural flavors has led to a tremendous increase in biotransformation process employing microorganisms of different genera using ferulic acid (FA) as the precursor. In this study, potential of Lactobacillus farciminis (ATCC 29644) for biotransformation of FA to 4-vinyl guaiacol (4VG) was ...

Preparation of CuS nanoparticles embedded in poly(vinyl alcohol)

Indian Academy of Sciences (India)

Poly(vinyl alcohol) (PVA)/CuS composite nanofibres were successfully prepared by electrospinning technique and gas–solid reaction. Scanning electron microscopic (SEM) images showed that the average diameter of PVA/CuS fibres was about 150–200 nm. Transmission electron microscopy (TEM) proved that a majority ...

Delocalization does not always stabilize : a quantum chemical analysis of -substituent effects on 54 alkyl and vinyl cations

NARCIS (Netherlands)

Alem, van K.; Lodder, G.; Zuilhof, H.

2002-01-01

The effects of -substituents on alkyl and vinyl cations are studied using high-level ab initio calculations. The geometries, stabilities, and electronic properties of 27 alkyl cations and 27 vinyl cations with -substituents are computed at the B3LYP/6-311 G(d,p), MP2/6-311 G(d,p), and CBS-Q levels.

Spectral and Mechanistic Investigation of Oxidative Decarboxylation of Phenylsulfinylacetic Acid by Cr(VI)

International Nuclear Information System (INIS)

Subramaniam, Perumal; Selvi, Natesan Thamil; Devi, Soundarapandian Sugirtha

2014-01-01

The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile . 80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [H + ] and ionic strength. The reaction is acid catalysed, the order with respect to [H + ] is unity and the active oxidizing species is found to be HCrO 3 + . The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of HCrO 3 + forming a sulfonium ion intermediate. The intermediate then undergoes α,β-cleavage leading to the liberation of CO 2 . The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log k 2 and Hammett σ constants with a negative value of reaction constant. The ρ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs

Solid polymer electrolytes based on alternating copolymers of vinyl ethers with methoxy oligo(ethyleneoxy)ethyl groups and vinylene carbonate

International Nuclear Information System (INIS)

Itoh, Takahito; Fujita, Katsuhito; Inoue, Kentaro; Iwama, Hiroki; Kondoh, Kensaku; Uno, Takahiro; Kubo, Masataka

2013-01-01

Graphical abstract: - Highlights: • Synthesis of alternating copolymers of vinyl ethers and vinylene carbonate. • Preparation of polymer electrolytes based on the alternating copolymers with LiTFSI. • Structure-property relationship for alternating copolymers-based electrolytes. • Interfacial stability between polymer electrolytes with lithium metal electrode. - Abstract: Alternating copolymers (poly(1a-g-alt-VC)) of vinyl ethers with various methoxy oligo(ethyleneoxy)ethyl groups and vinylene carbonate (VC) were prepared, and the thermal and electrochemical properties of their polymer electrolytes with LiTFSI and interfacial stability between the polymer electrolyte and Li metal electrode were investigated. T g 's increased linearly with salt contents, and decreased with an increase in the chain length of methoxy oligo(ethyleneoxy)ethyl groups in the vinyl ethers at constant salt concentration. The slopes of T g vs. [Li]/[O] were identical, independent of the polymer structure. The ionic conductivities of the polymer electrolytes increased with increasing the side-chain ethyleneoxy (EO) unit length of the vinyl ether unit in the alternating copolymers, and also their temperature dependences became relatively smaller in the polymer electrolytes having longer EO units in the vinyl ethers. The highest ionic conductivity, 1.2 × 10 −4 S/cm at 30 °C, was obtained in the alternating copolymer with a side-chain EO unit length of 23.5 in the vinyl ether unit. Ion transport coupled with the segmental motion of the polymer is dominant in these polymer electrolytes. Interfacial resistance increased gradually with contact time, indicative of the formation of passivation films on the Li metal electrode. These polymer electrolytes are thermally stable and have large electrochemical windows of use

Terpyridine modified poly(vinyl chloride) : possibilities for supramolecular grafting and crosslinking

NARCIS (Netherlands)

Meier, M.A.R.; Schubert, U.S.

2003-01-01

Commercially available poly(vinyl chloride) (PVC) was covalently modified with terpyridine supramolecular binding units in a two-step reaction. First, PVC was modified with aromatic thiols to introduce OH functionalities into the polymer backbone, which were subsequently reacted with an

Inhibiting the deterioration of plasticised poly (vinyl chloride) in museum collections

DEFF Research Database (Denmark)

Shashoua, Yvonne

2003-01-01

Plasticized poly (vinyl chloride) (PVC) is found in museum collections as three dimensional objects and as packaging materials. Many PVC materials deteriorate within 25 years of acquisition. Migration and chemical breakdown of plasticizer, accompanied by dehydrochlorination of the polymer are the...

Photochemical generation of highly destabilized vinyl cations: the effects of alpha- and beta-trifluoromethyl versus alpha- and beta-methyl substituents

NARCIS (Netherlands)

Alem, van K.; Belder, G.; Lodder, G.; Zuilhof, H.

2005-01-01

The photochemical reactions in methanol of the vinylic halides 1-4, halostyrenes with a methyl or a trifluoromethyl substituent at the - or -position, have been investigated quantitatively. Next to E/Z isomerization, the reactions are formation of vinyl radicals, leading to reductive dehalogenation

Solution-Processed Organic Solar Cells with Power Conversion Efficiencies of 2.5% using Benzothiadiazole/Imide-Based Acceptors

KAUST Repository

Bloking, Jason T.

2011-12-27

A new series of electron-deficient molecules based on a central benzothiadiazole moiety flanked with vinylimides has been synthesized via Heck chemistry and used in solution-processed organic photovoltaics (OPV). Two new compounds, 4,7-bis(4-(N-hexyl-phthalimide)vinyl)benzo[c]1,2,5-thiadiazole (PI-BT) and 4,7-bis(4-(N-hexyl-naphthalimide)vinyl)benzo[c]1,2,5-thiadiazole (NI-BT), show significantly different behaviors in bulk heterojunction (BHJ) solar cells using poly(3-hexylthiophene) (P3HT) as the electron donor. Two-dimensional grazing incidence X-ray scattering (2D GIXS) experiments demonstrate that PI-BT shows significant crystallization in spin-coated thin films, whereas NI-BT does not. Density functional theory (DFT) calculations predict that while PI-BT maintains a planar structure in the ground state, steric interactions cause a twist in the NI-BT molecule, likely preventing significant crystallization. In BHJ solar cells with P3HT as donor, PI-BT devices achieved a large open-circuit voltage of 0.96 V and a maximum device power-conversion efficiency of 2.54%, whereas NI-BT containing devices only achieved 0.1% power-conversion efficiency. © 2011 American Chemical Society.

Thermal and dynamic mechanical properties of grafted kenaf filled poly (vinyl chloride)/ethylene vinyl acetate composites

International Nuclear Information System (INIS)

Bakar, Nurfatimah Abu; Chee, Ching Yern; Abdullah, Luqman Chuah; Ratnam, Chantara Thevy; Ibrahim, Nor Azowa

2015-01-01

Highlights: • Study on thermal and dynamic mechanical properties of PVC/EVA/PMMA grafted kenaf fiber. • PMMA grafted kenaf fiber showed good interaction with PVC/EVA blends. • Thermal stability of the composites increase upon PMMA grafting on kenaf fiber. • The crystallinity of the composites decrease upon PMMA grafting on kenaf fiber. • PMMA grafted fiber provides more reinforcement on PVC/EVA/grafted PMMA composite. - Abstract: The effects of kenaf and poly (methyl methacrylate grafted kenaf on the thermal and dynamic mechanical properties of poly (vinyl chloride), PVC and ethylene vinyl acetate, EVA blends were investigated. The PVC/EVA/kenaf composites were prepared by mixing the grafted and ungrafted kenaf fiber and PVC/EVA blend using HAAKE Rheomixer at a temperature of 150 °C and the rotor speed at 50 rpm for 20 min. The composites were subjected to Differential Scanning Calorimetric (DSC), Thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), Fourier transform infrared (FTIR) and Scanning Electron Microscopy (SEM) studies. The DSC data revealed that the crystallinity of the EVA decreased with the addition of 30% grafted and ungrafted kenaf fibers. TGA and derivative thermogravimetric (DTG) curves displayed an increase in the thermal stability of the composites upon grafting of the fiber. Studies on DMA indicate that the T g of the PVC and EVA in the PVC/EVA/kenaf composites has been shifted to higher temperature with the addition of the kenaf fiber. The presence of PMMA on the surface of grafted kenaf fiber was further confirmed by the analytical results from FTIR. The morphology of fractured surfaces of the composites, which was examined by a scanning electron microscope, showed the adhesion between the kenaf fiber and the PVC/EVA matrix was improved upon grafting of the kenaf fiber

Contrasting growth properties of Nocardioides JS614 on threedifferent vinyl halides.

Science.gov (United States)

Taylor, Anne E; Bottomley, Peter J; Semprini, Lewis

2018-02-01

Ethene (ETH)-grown inocula of Nocardioides JS614 grow on vinyl chloride (VC), vinyl fluoride (VF), or vinyl bromide (VB) as the sole carbon and energy source, with faster growth rates and higher cell yields on VC and VF than on VB. However, whereas acetate-grown inocula of JS614 grow on VC and VF after a lag period, growth on VB did not occur unless supplemental ethene oxide (EtO) was present in the medium. Despite inferior growth on VB, the maximum rate of VB consumption by ETH-grown cells was ~ 50% greater than the rates of VC and VF consumption, but Br - release during VB consumption was non-stoichiometric with VB consumption (~ 66%) compared to 100% release of Cl - and F - during VC and VF consumption. Evidence was obtained for VB turnover-dependent toxicity of cell metabolism in JS614 with both acetate-dependent respiration and growth being significantly reduced by VB turnover, but no VC or VF turnover-dependent toxicity of growth was detected. Reduced growth rate and cell yield of JS614 on VB probably resulted from a combination of inefficient metabolic processing of the highly unstable VB epoxide (t 0.5  = 45 s), accompanied by growth inhibitory effects of VB metabolites on acetate-dependent metabolism. The exact role(s) of EtO in promoting growth of alkene repressed JS614 on VB remains unresolved, with evidence of EtO inducing epoxide consuming activity prior to an increase in alkene oxidizing activity and supplementing reductant supply when VB is the growth substrate.

Enhanced PL and EL properties of Alq3/nano-TiO2 with the modification of 8-vinyl POSS

Science.gov (United States)

Li, Jie; Xie, Bing; Xia, Kai; Zhao, Chunmao; Li, Yingchun; Hu, Shengliang

2018-04-01

In this study, tris (8-hydroxyquinoline) aluminum/nano-titanium dioxide (Alq3/nano-TiO2) composites were synthesized using a simply in-situ process with 8-vinyl polyhedral oligomeric silsesquioxane (POSS) as a modifier. The as-prepared Alq3/nano-TiO2 composites were characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and ultraviolet visible (UV-vis) absorption spectra. The effect of modification on luminescence properties for the samples was studied by photoluminescence (PL) spectra, electroluminescence (EL) spectra and time-resolved luminescence decay curves. Organic light emitting diodes (OLEDs) with the corresponded emitting layer structure were investigated. The results show that the amphiphilicity of the 8-vinyl POSS leads to well-dispersion state of the nano-TiO2 in the Alq3. Adding a proper weight percentage of 8-vinyl POSS is beneficial for the PL and EL properties enhancement of the composites. OLED using the Alq3/nano-TiO2 with 1 wt% 8-vinyl POSS emitting layer has the low turn-on voltage (4.7 V at 1 cd/m2), high maximum luminance (7463 cd/m2 at 8.75 V), and high luminous efficiency (1.13 cd/A at 100 mA/cm2). Adding 1 wt% 8-vinyl POSS in Alq3/nano-TiO2 can increase the EL intensity by a factor of 37.1 at 8 V. These values are better than those for OLEDs using the Alq3 emitting layer. The increase in luminance and current efficiency stability can be attributed to the energy transfer process between the Alq3 and the nano-TiO2, and the suppression of the self-quenching by caged 8-vinyl POSS molecules.

Structure of pyridine and quinoline vinyl ethers according to data from 1H and 13C NMR spectra and quantum-chemical calculations

International Nuclear Information System (INIS)

Afonin, A.V.; Voronov, V.K.; Andriankov, M.A.; Danovich, D.K.

1987-01-01

A systematic investigation of the structure of the vinyl ethers of heterocyclic compounds has not been undertaken. The present work was devoted to investigation of the stereochemical and electronic structure of the vinyl ethers of pyridine and quinoline. The PMR spectra of the samples were recorded for 5% solutions in deuterochloroform on a Tesla BS-497 spectrometer at 100 MHz. The 13 C NMR spectra were recorded on a Tesla BS-567A spectrometer at 25.1 MHz in deuterochloroform with the samples at concentrations of 30%. The internal standard was HMDS. The vinyl ethers of pyridine and quinoline exist preferentially in the nonplanar S-trans conformation. In the vinyl esters of pyridine and quinoline the p-π conjugation is concurrent in nature and depends on the position of the vinyloxy group in the heterocycle

Interaction between poly(vinyl pyridine) and poly(2,6-dimethyl-1,4-phenylene oxide) : A copolymer blend miscibility study

NARCIS (Netherlands)

de Wit, Joost; van Ekenstein, Gert Alberda; ten Brinke, Gerrit

2007-01-01

The phase behavior of blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) with random copolymers of styrene and 2-vinyl pyridine, Poly(S-co-2VP), as well as with random copolymers of styrene and 4-vinyl pyridine, Poly(S-co-4VP), has been investigated in order to estimate the values of the

(He 1) photoelectron spectra of vinyl- and (1-dimethylaminovinyl)pyridines

International Nuclear Information System (INIS)

Baidin, V.N.; Koikov, L.N.; Terent'ev, P.B.; Gloriozov, I.P.

1985-01-01

The (He 1) photoelectron spectra of α=, β-, γ-vinyl, α-, β-, and γ-(1-dimethylvinyl)-pyridines, 1-dimethyl- and 1-diethylaminostyrenes were obtained and interpreted within the framework of the molecular orbital perturbation theory. In both pyridine derivative series, there is a regular increase in the ionization energy of the 1α 2 , π/sub C=C/ and n/sub en/ orbitals and decrease in the ionization energy of the 2b 1 orbitals in the order α 2 and 2b 1 is found for γ-vinylpyridine). The splitting of the energy levels of the heterocycle in dimethylaminovinylpyridines is less than in the corresponding vinyl derivatives, which indicates a weakening of the interaction between the aromatic (or heteroaromatic) ring and the enamine fragment extruding from the ring plane. The ionization energy of the unshared electron pair of the nitrogen atom of the pyridine ring for all the compounds except for α- (1-dimethylaminovinyl)pyridine (which displays an ortho effect) is close to that for pyridine. The photoelectron spectral data are compared with the MO energies calculated by the MINDO/3 method

Biomaterial properties evaluation of poly(vinyl acetate- alt-maleic anhydride)/chitosan nanocapsules

Science.gov (United States)

Raţă, Delia Mihaela; Popa, Marcel; Chailan, Jean-François; Zamfir, Carmen Lăcrămioara; Peptu, Cătălina Anişoara

2014-08-01

Nanocapsules with diameter around 100 nm based on a natural polymer (chitosan) and a synthetic polymer poly(vinyl acetate- alt-maleic anhydride) [poly(MAVA)] by interfacial condensation method were prepared. The present study proposes a new type of biocompatible nanocapsules based on poly(vinyl acetate- alt-maleic anhydride-chitosan) (MCS) able to become a reliable support for inclusion and release of drugs. The spherical shape of the nanocapsules was evidenced by scanning electron microscopy. Nanocapsules presented a good Norfloxacin loading and release capacity. Haemocompatibility tests have demonstrated that the nanocapsules present a low toxicity and a good compatibility with sanguine medium. The biocompatibility properties of the nanocapsules after their intraperitoneal administration in rats were evidenced by histopathological examination of different organs (brain, liver, kidney, and lung). The results are encouraging and the nanocapsules can be used as controlled drug delivery systems.

Synthesis and characterization of foldable and magnetic field-sensitive, freestanding poly(vinyl acetate)/poly(vinyl chloride)/polyfuran composite and nanocomposite films

Energy Technology Data Exchange (ETDEWEB)

Sarıtaş, Sevilay; Eşsiz, Serpil; Sarı, Bekir, E-mail: bsari@gazi.edu.tr

2017-07-01

Highlights: • In this study, ternary composite/nanocomposite films were synthesized. • Magnetic field-sensitive folding films were prepared without any elastomer. • Morphological studies show that all composite films have a smooth surface. • The ternary composites/nanocomposite show improved thermal stability compared to the pure PF. - Abstract: In this study, polyfuran and poly(vinyl acetate)/poly(vinyl chloride)/polyfuran ternary composites were synthesized via the chemical polymerization method. The temperature and magnetic field–sensitive novel composites and the nanocomposite were obtained in the form of powders and films. It was observed that the prepared novel conductive films have superior properties at a certain temperature range (25–50 °C) such as bending and folding. The structural properties, thermal behavior, surface morphology, internal structure, and surface roughness of the prepared samples were investigated by various characterization techniques. The conductivities of the samples were measured at room temperature and different temperatures by the four-point technique. X-ray Diffraction analysis results demonstrated that the PF and composites have an amorphous structure, whereas the nanocomposite is in crystalline form. The saturation magnetization (Ms) values of the magnetite and nanocomposite were found to be 58.9 and 5.3 emu g{sup −1}, respectively. It was found that magnetite-doped nanocomposite has superparamagnetic properties at room temperature.

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

Science.gov (United States)

Pichavant, Loic; Guillermain, Céline; Coqueret, Xavier

2010-09-13

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

Catalysis in the Service of Green Chemistry: Nobel Prize-Winning Palladium-Catalysed Cross-Couplings, Run in Water at Room Temperature: Heck, Suzuki-Miyaura and Negishi reactions carried out in the absence of organic solvents, enabled by micellar catalysis.

Science.gov (United States)

Lipshutz, Bruce H; Taft, Benjamin R; Abela, Alexander R; Ghorai, Subir; Krasovskiy, Arkady; Duplais, Christophe

2012-04-01

Palladium-catalysed cross-couplings, in particular Heck, Suzuki-Miyaura and Negishi reactions developed over three decades ago, are routinely carried out in organic solvents. However, alternative media are currently of considerable interest given an increasing emphasis on making organic processes 'greener'; for example, by minimising organic waste in the form of organic solvents. Water is the obvious leading candidate in this regard. Hence, this review focuses on the application of micellar catalysis, in which a 'designer' surfactant enables these award-winning coupling reactions to be run in water at room temperature.

High performances unsaturated polyester based nanocomposites: Effect of vinyl modified nanosilica on mechanical properties

Directory of Open Access Journals (Sweden)

J. D. Rusmirovic

2016-02-01

Full Text Available Influences of the vinyl modified nanosilica Aerosil® 380, i.e./i>, vinyl and methacryloyl silane coupling agent and linseed oil fatty acids (BD reactive residues, on the mechanical properties of the unsaturated polyester resins (UPes based nanocomposites, was studied. The polycondensation of maleic anhydride and products of poly(ethylene terephthalate (PET depolymerization with propylene glycol, with and without separation of ethylene glycol, yields UPe1 and UPe2 resin, respectively. The hydroxyl terminated PET depolymerization products (glycolyzates and UPes were characterized by acid and hydroxyl values, Fourier Transform Infrared (FTIR and nuclear magneti resonance (NMR spectroscopies. Transmission electron microscopy (TEM confirmed that silica nanoparticles formed domains of aggregates in the polymer matrix. An increase from 195 to 247% of stress at break (σb, and from 109 to 131% of impact strength (σi of UPes based nanocomposites was obtained for 1 wt% addition of vinyl modified silica. Flexural strength (σf increase from 106 to 156% for both UPes based nanocomposites with 1 wt% addition of BD modified silica. Cross-linking density (ν, storage modulus (G', tanδ and Tg of the nanocomposite were determined from the dynamic mechanical testing and discussed in relation to the structure of silica modification.

Nanocomposite photoactuators based on an ethylene vinyl acetate copolymer filled with carbon nanotubes

Czech Academy of Sciences Publication Activity Database

Czaniková, K.; Torras, N.; Esteve, J.; Krupa, I.; Kasák, P.; Pavlova, Ewa; Račko, D.; Chodák, I.; Omastová, M.

2013-01-01

Roč. 186, September (2013), s. 701-710 ISSN 0925-4005 Institutional support: RVO:61389013 Keywords : actuator * carbon nanotubes * ethylene vinyl acetate copolymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.840, year: 2013

Synthesis of Ethylene or Propylene/1,3-Butadiene Copolymers Possessing Pendant Vinyl Groups with Virtually No Internal Olefins

OpenAIRE

Kenji Michiue; Makoto Mitani; Terunori Fujita

2015-01-01

In general, ethylene/1,3-butadiene copolymerizations provides copolymers possessing both pendant vinyls and vinylenes as olefinic moieties. We, at MCI, studied the substituent effects of C2-symmetric zirconocene complexes, rac-[Me2Si(Indenyl’)2]ZrCl2 (Indenyl’ = generic substituted indenyl), after activation on the ratio of the pendant vinyls and vinylenes of the resultant copolymers. Complexes examined in this study were rac-dimethylsilylbis (1-indenyl)zirconium dichloride (1), rac-dimethyls...

The γ-radiation induced grafting of unsaturated segmented polyurethanes with N-vinyl pyrrolidone

International Nuclear Information System (INIS)

Egboh, S.H.; George, M.H.; Barrie, J.A.

1984-01-01

Linear unsaturated segmented polyurethanes have been modified by hydrophilic grafting at 40 deg C with N-vinyl pyrrolidone, in N,N-dimethylformamide as solvent, using 60 Cobalt γ-irradiation. Graft copolymers were isolated from homopolymers by selective solvent extraction using a Soxhlet apparatus. The effects of reaction time, total dose, temperature and monomer concentration, on the graft yields have been examined. Relatively high irradiation doses were avoided during the grafting experiments to prevent possible degradation of the segmented polyurethanes and gelation of the homopolymer, poly(N-vinyl pyrrolidone). The ungrafted and grafted copolymers were characterized, and the graft copolymers were shown to be more thermally stable than the original polyurethanes, by thermogravimetric analysis. An explanation for the observed variation of the graft yields with some of the experimental variables is suggested. (author)

Wax inhibitor based on ethylene vinyl acetate with methyl methacrylate and diethanolamine for crude oil pipeline

Science.gov (United States)

Anisuzzaman, S. M.; Abang, S.; Bono, A.; Krishnaiah, D.; Karali, R.; Safuan, M. K.

2017-06-01

Wax precipitation and deposition is one of the most significant flow assurance challenges in the production system of the crude oil. Wax inhibitors are developed as a preventive strategy to avoid an absolute wax deposition. Wax inhibitors are polymers which can be known as pour point depressants as they impede the wax crystals formation, growth, and deposition. In this study three formulations of wax inhibitors were prepared, ethylene vinyl acetate, ethylene vinyl acetate co-methyl methacrylate (EVA co-MMA) and ethylene vinyl acetate co-diethanolamine (EVA co-DEA) and the comparison of their efficiencies in terms of cloud point¸ pour point, performance inhibition efficiency (%PIE) and viscosity were evaluated. The cloud point and pour point for both EVA and EVA co-MMA were similar, 15°C and 10-5°C, respectively. Whereas, the cloud point and pour point for EVA co-DEA were better, 10°C and 10-5°C respectively. In conclusion, EVA co-DEA had shown the best % PIE (28.42%) which indicates highest percentage reduction of wax deposit as compared to the other two inhibitors.

Positron scattering from vinyl acetate

International Nuclear Information System (INIS)

Chiari, L; Brunger, M J; Zecca, A; Blanco, F; García, G

2014-01-01

Using a Beer–Lambert attenuation approach, we report measured total cross sections (TCSs) for positron scattering from vinyl acetate (C 4 H 6 O 2 ) in the incident positron energy range 0.15–50 eV. In addition, we also report an independent atom model with screening corrected additivity rule computation results for the TCSs, differential and integral elastic cross sections, the positronium formation cross section and inelastic integral cross sections. The energy range of these calculations is 1–1000 eV. While there is a reasonable qualitative correspondence between measurement and calculation for the TCSs, in terms of the energy dependence of those cross sections, the theory was found to be a factor of ∼2 larger in magnitude at the lower energies, even after the measured data were corrected for the forward angle scattering effect. (paper)

Cel vinyls: materials and methods.

Science.gov (United States)

Harrison, S J

1983-12-01

Many commercial uses of media are applicable to medical/scientific media production and illustration, not the least of which are techniques pioneered in the commercial cartooning field. Whether or not the illustrative effort culminates in a "cartoon," the production techniques of the cartooning industry cannot be overlooked by the illustrator faced with providing projection graphics, whether animated or still, for slides, motion pictures, television or even print media. When Walt Disney introduced Mickey Mouse as "Steamboat Willie" in 1928, his technology opened the door for exploration of cartooning media by all artists. Only in comparatively recent years have these tools been used by the scientific illustrator. In this article cel vinyl acrylics or cartoon colors will be discussed: the rationale for the use of this medium, materials and methods, and considerations related to the photography of this art form.

Occurrence, characterization and analysis of vinyl chloride as a degradation product of chloro ethenes from waste sites. Vorkommen, Beurteilung und Analytik von Vinylchlorid als Abbauprodukt chlorierter Ethene in Altlasten

Energy Technology Data Exchange (ETDEWEB)

Koester, M. (Harress Geotechnik GmbH, Harburg (Germany, F.R.))

1989-12-01

Reductive dehalogenation reactions occuring within the central part of contaminated areas may result in the formation of vinyl chloride as a product of chlorinated hydrocarbon degradation. This degradation takes place in an anaerobic environment, and proceeds from tetrachloroethene through trichloroethene and dichloroethene (cis, trans) to vinyl chloride. The analysis of vinyl chloride from gas and water samples is performed by means of capillary gas chromatography, using a flame ionization detector (FID). It could be shown from the analysis of some 200 samples from various tetrachloroethene and trichloroethene waste sites, that high dichloroethene concentrations were correlated with elevated vinyl chloride concentrations. The ratio between dichloroethene and vinyl chloride although depending on the chemical and physical properties of the subsoil, is roughly 10:1. Since vinyl chloride is known to be carcinogenic, action levels and clean-up standards are accordingly low, resulting in new requirement for remedial activities. (orig.).

Preparation of Macroporous Poly (vinyl alcohol-co-triallyl isocyanurate) Beads Bearing Aminocarboxylic Acid as Functional Groups by Suspension Polymerization

Institute of Scientific and Technical Information of China (English)

无

2003-01-01

Macroporous poly (vinyl acetate-co-triallyl isocyanurate) beads were prepared with suspension polymerization method. The copolymer beads were then transformed into poly (vinyl alcohol-co-triallyl isocyanurate) by ester exchange reaction. Aminocarboxylic acids were immobilized on the copolymer beads by the esterification of hydroxyl groups with diethyl-lenetriaminepentaacetic bisanhydride. The weak acid exchange capacities, specific surface areas and mean pore diameters of the resultant resin beads were measured.

Fabrication of 3D interconnected porous TiO{sub 2} nanotubes templated by poly(vinyl chloride-g-4-vinyl pyridine) for dye-sensitized solar cells

Energy Technology Data Exchange (ETDEWEB)

Koh, Joo Hwan; Koh, Jong Kwan; Seo, Jin Ah; Kim, Jong Hak [Department of Chemical and Biomolecular Engineering, Yonsei University, 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Shin, Jong-Shik, E-mail: jonghak@yonsei.ac.kr [Department of Biotechnology, Yonsei University, 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea, Republic of)

2011-09-07

Porous TiO{sub 2} nanotube arrays with three-dimensional (3D) interconnectivity were prepared using a sol-gel process assisted by poly(vinyl chloride-graft-4-vinyl pyridine), PVC-g-P4VP graft copolymer and a ZnO nanorod template. A 7 {mu}m long ZnO nanorod array was grown from the fluorine-doped tin oxide (FTO) glass via a liquid phase deposition method. The TiO{sub 2} sol-gel solution templated by the PVC-g-P4VP graft copolymer produced a random 3D interconnection between the adjacent ZnO nanorods during spin coating. Upon etching of ZnO, TiO{sub 2} nanotubes consisting of 10-15 nm nanoparticles were generated, as confirmed by wide-angle x-ray scattering (WAXS), energy-filtering transmission electron microscopy (EF-TEM) and field-emission scanning electron microscopy (FE-SEM). The ordered and interconnected nanotube architecture showed an enhanced light scattering effect and increased penetration of polymer electrolytes in dye-sensitized solar cells (DSSC). The energy conversion efficiency reached 1.82% for liquid electrolyte, and 1.46% for low molecular weight (M{sub w}) and 0.74% for high M{sub w} polymer electrolytes.

Effect of side chain length and degree of polymerization on the decomposition and crystallization behaviour of chlorinated poly(vinyl ester) oligomers

International Nuclear Information System (INIS)

Heinze, D.; Mang, Th.; Popescu, C.; Weichold, O.

2016-01-01

Highlights: • Thermal behaviour of telomerized polyvinyl esters is investigated. • Thermal stability relies mainly on the contribution of side chains. • At equal molecular weights thermal stability is dictated by length of side chain. • Increasing the length of side chains improves also the packing degree of polymer. - Abstract: Four members of a homologous series of chlorinated poly(vinyl ester) oligomers CCl_3–(CH_2CH (OCO(CH_2)_mCH_3))_n–Cl with degrees of polymerization of 10 and 20 were prepared by telomerisation using carbon tetrachloride. The number of side chain carbon atoms ranges from 2 (poly(vinyl acetate) to 18 (poly(vinyl stearate)). The effect of the n-alkyl side chain length and of the degree of polymerization on the thermal stability and crystallization behaviour of the synthesized compounds was investigated. All oligomers degrade in two major steps by first losing HCl and side chains with subsequent breakdown of the backbone. The members with short side chains, up to poly(vinyl octanoate), are amorphous and show internal plasticization, whereas those with high number of side chain carbon atoms are semi-crystalline due to side-chain crystallization. A better packing for poly(vinyl stearate) is also noticeable. The glass transition and melting temperatures as well as the onset temperature of decomposition are influenced to a larger extent by the side chain length than by the degree of polymerization. Thermal stability is improved if both the size and number of side chains increase, but only a long side chain causes a significant increase of the resistance to degradation. This results in a stabilization of PVAc so that oligomers from poly(vinyl octanoate) on are stable under atmospheric conditions. Thus, the way to design stable, chlorinated PVEs oligomers is to use a long n-alkyl side chain.

Effect of side chain length and degree of polymerization on the decomposition and crystallization behaviour of chlorinated poly(vinyl ester) oligomers

Energy Technology Data Exchange (ETDEWEB)

Heinze, D.; Mang, Th. [Aachen University of Applied Sciences, Heinrich-Mussmann-Str. 1, 52428 Jülich (Germany); Popescu, C., E-mail: crisan.popescu@kao.com [KAO Germany GmbH, Pfungstädterstr. 98-100, 64297 Darmstadt (Germany); Weichold, O., E-mail: weichold@ibac.rwth-aachen.de [Institute of Building Materials Research, Schinkelstr. 3, 52062 Aachen (Germany)

2016-08-10

Highlights: • Thermal behaviour of telomerized polyvinyl esters is investigated. • Thermal stability relies mainly on the contribution of side chains. • At equal molecular weights thermal stability is dictated by length of side chain. • Increasing the length of side chains improves also the packing degree of polymer. - Abstract: Four members of a homologous series of chlorinated poly(vinyl ester) oligomers CCl{sub 3}–(CH{sub 2}CH (OCO(CH{sub 2}){sub m}CH{sub 3})){sub n}–Cl with degrees of polymerization of 10 and 20 were prepared by telomerisation using carbon tetrachloride. The number of side chain carbon atoms ranges from 2 (poly(vinyl acetate) to 18 (poly(vinyl stearate)). The effect of the n-alkyl side chain length and of the degree of polymerization on the thermal stability and crystallization behaviour of the synthesized compounds was investigated. All oligomers degrade in two major steps by first losing HCl and side chains with subsequent breakdown of the backbone. The members with short side chains, up to poly(vinyl octanoate), are amorphous and show internal plasticization, whereas those with high number of side chain carbon atoms are semi-crystalline due to side-chain crystallization. A better packing for poly(vinyl stearate) is also noticeable. The glass transition and melting temperatures as well as the onset temperature of decomposition are influenced to a larger extent by the side chain length than by the degree of polymerization. Thermal stability is improved if both the size and number of side chains increase, but only a long side chain causes a significant increase of the resistance to degradation. This results in a stabilization of PVAc so that oligomers from poly(vinyl octanoate) on are stable under atmospheric conditions. Thus, the way to design stable, chlorinated PVEs oligomers is to use a long n-alkyl side chain.

Composite poly(vinyl alcohol/poly(vinyl acetate electrospun nanofibrous mats as a novel wound dressing matrix for controlled release of drugs

Directory of Open Access Journals (Sweden)

Jannesari M

2011-05-01

Full Text Available Marziyeh Jannesari1, Jaleh Varshosaz2, Mohammad Morshed1, Maedeh Zamani11Department of Textile Engineering, Isfahan University of Technology, Isfahan, Iran; 2Department of Pharmaceutics, School of Pharmacy and Pharmaceutical Sciences Research Center, Isfahan University of Medical Sciences, Isfahan, IranAbstract: The aim of this study was to develop novel biomedicated nanofiber electrospun mats for controlled drug release, especially drug release directly to an injury site to accelerate wound healing. Nanofibers of poly(vinyl alcohol (PVA, poly(vinyl acetate (PVAc, and a 50:50 composite blend, loaded with ciprofloxacin HCl (CipHCl, were successfully prepared by an electrospinning technique for the first time. The morphology and average diameter of the electrospun nanofibers were investigated by scanning electron microscopy. X-ray diffraction studies indicated an amorphous distribution of the drug inside the nanofiber blend. Introducing the drug into polymeric solutions significantly decreased solution viscosities as well as nanofiber diameter. In vitro drug release evaluations showed that both the kind of polymer and the amount of drug loaded greatly affected the degree of swelling, weight loss, and initial burst and rate of drug release. Blending PVA and PVAc exhibited a useful and convenient method for electrospinning in order to control the rate and period of drug release in wound healing applications. Also, the thickness of the blend nanofiber mats strongly influenced the initial release and rate of drug release.Keywords: biodegradable polymers, drug delivery, controlled release, electrospun nanofibers, wound dressing

Influence of acrylonitrile butadiene rubber on recyclability of blends prepared from poly(vinyl chloride) and poly(methyl methacrylate).

Science.gov (United States)

Suresh, Sunil S; Mohanty, Smita; Nayak, Sanjay K

2018-06-01

The current investigation deals with the recycling possibilities of poly(vinyl chloride) and poly(methyl methacrylate) in the presence of acrylonitrile butadiene rubber. Recycled blends of poly(vinyl chloride)/poly(methyl methacrylate) are successfully formed from the plastic constituents, those are recovered from waste computer products. However, lower impact performance of the blend and lower stability of the poly(vinyl chloride) phase in the recycled blend restricts its further usage in industrial purposes. Therefore, effective utilisation acrylonitrile butadiene rubber in a recycled blend was considered for improving mechanical and thermal performance. Incorporation of acrylonitrile butadiene rubber resulted in the improvement in impact performance as well as elongation-at-break of the recycled blend. The optimum impact performance was found in the blend with 9 wt% acrylonitrile butadiene rubber, which shows 363% of enhancement as compared with its parent blend. Moreover, incorporated acrylonitrile butadiene rubber also stabilises the poly(vinyl chloride) phase present in the recycled blend, similarly Fourier transform infrared spectroscopy studies indicate the interactions of various functionalities present in the recycled blend and acrylonitrile butadiene rubber. In addition to this, thermogravimetric analysis indicates the improvement in the thermal stability of the recycled blend after the addition of acrylonitrile butadiene rubber into it. The existence of partial miscibility in the recycled blend was identified using differential scanning calorimetry and scanning electron microscopy.

Poly(vinyl alcohol) cryogel phantoms for use in ultrasound and MR imaging

International Nuclear Information System (INIS)

Surry, K J M; Austin, H J B; Fenster, A; Peters, T M

2004-01-01

Poly(vinyl alcohol) cryogel, PVA-C, is presented as a tissue-mimicking material, suitable for application in magnetic resonance (MR) imaging and ultrasound imaging. A 10% by weight poly(vinyl alcohol) in water solution was used to form PVA-C, which is solidified through a freeze-thaw process. The number of freeze-thaw cycles affects the properties of the material. The ultrasound and MR imaging characteristics were investigated using cylindrical samples of PVA-C. The speed of sound was found to range from 1520 to 1540 m s -1 , and the attenuation coefficients were in the range of 0.075-0.28 dB (cm MHz) -1 . T1 and T2 relaxation values were found to be 718-1034 ms and 108-175 ms, respectively. We also present applications of this material in an anthropomorphic brain phantom, a multi-volume stenosed vessel phantom and breast biopsy phantoms. Some suggestions are made for how best to handle this material in the phantom design and development process

Aging Characteristics and Effect of Gamma Radiation on Ethylene Vinyl Acetate Copolymer

International Nuclear Information System (INIS)

Alya, S.S.; Hegazy, E.A.; Senb, M.; El-Oker, M.M.

2008-01-01

Artificial aging of Ethylene vinyl acetate copolymer (EVA-13% vinyl acetate content) exposed to thermal aging at 80 degree C, to UV irradiation with wavelength close to 259 nm and to gamma radiation up to 377 kGy, in the presence of air, has been studied. FTIR measurements were performed to follow the chemical changes, which may occur in the samples during aging. The IR study indicated that, some chemical changes took place during thermal, UV aging and gamma irradiation. The formation of Ketone and Lactone groups at 1715 and 1780 cm-1, respectively, were observed for all samples. DSC thermo grams of thermally aged samples revealed a shift to higher temperature of the melting point and the crystallinity increased with increasing aging time for all the thermally treated and cooled samples at different conditions. For gamma-irradiated samples, a slight decrease in the melting point was observed and the degree of crystallinity increased almost linearly up to 200 kGy

Fixation of some chemically modified reactive dye during gamma irradiation of cotton fabrics in presence of vinyl and acrylic monomers

International Nuclear Information System (INIS)

Zohdy, M.H.; El-Naggar, A.M.; Abdallah, W.A.

1999-01-01

The radiation grafting of vinyl sulfone dye having an activated double bond in presence of styrene monomer or its mixtures with ethyl acrylate onto cotton fabric has been investigated. The chemical reaction of the vinyl sulfone form with peroxy radicals on cotton fabric through covalent bonding is tested by extracting the dyed samples in 50% aqueous DMF solution. It was found that the presence of styene monomer in the dyeing solution is essential for the reaction or grafting of the vinyl sulfone dye. However, when a constant styrene concentration of 5% was used in the dye bath, the color strength expressed as K/S was found to increase by increasing the dye concentration. The results showed that the color strength obtained in case of using 10% ethyl acrylate is much lower than in the case of using the same concentration of styrene monomer. A solvent composition of equal ratios of methanol and water has been proven to be suitable to produce the highest improvement in the color strength. The irradiation dose was found to play an important role in initiating the reaction of the vinyl sulfone dye

Changes in chemical permeation of disposable latex, nitrile, and vinyl gloves exposed to simulated movement.

Science.gov (United States)

Phalen, Robert N; Le, Thi; Wong, Weng Kee

2014-01-01

Glove movement can affect chemical permeation of organic compounds through polymer glove products. However, conflicting reports make it difficult to compare the effects of movement on chemical permeation through commonly available glove types. The aim of this study was to evaluate the effect of movement on chemical permeation of an organic solvent through disposable latex, nitrile, and vinyl gloves. Simulated whole-glove permeation testing was conducted using ethyl alcohol and a previously designed permeation test system. With exposure to movement, a significant decrease (p ≤ 0.001) in breakthrough time (BT) was observed for the latex (-23%) and nitrile gloves (-31%). With exposure to movement, only the nitrile glove exhibited a significant increase (p ≤ 0.001) in steady-state permeation rate (+47%) and cumulative permeation at 30 min (+111%). Even though the nitrile glove provided optimum chemical resistance against ethyl alcohol, it was most affected by movement. With exposure to movement, the latex glove was an equivalent option for overall worker protection, because it was less affected by movement and the permeation rate was lower than that of the nitrile glove. In contrast, the vinyl glove was the least affected by movement, but did not provide adequate chemical resistance to ethyl alcohol in comparison with the nitrile and latex gloves. Glove selection should take movement and polymer type into account. Some glove polymer types are less affected by movement, most notably the latex glove in this test. With nitrile gloves, at least a factor of three should be used when attempting to assign a protection factor when repetitive hand motions are anticipated. Ultimately, the latex gloves outperformed nitrile and vinyl in these tests, which evaluated the effect of movement on chemical permeation. Future research should aim to resolve some of the observed discrepancies in test results with latex and vinyl gloves.

/sup 13/C-/sup 13/C spin-spin coupling constants in structural investigations. II. Conformational structure of vinyl ethers

Energy Technology Data Exchange (ETDEWEB)

Krivdin, L.B.; Shcherbakov, V.V.; Bzhezovskii, V.M.; Kalabin, G.A.

1986-10-10

The /sup 13/C-/sup 13/C spin-spin coupling constants between the carbon nuclei of the vinyl group were measured for a series of vinyl ethers. It was established that the unshared electron pairs of the oxygen atom can make a substantial stereospecific contribution to the direct /sup 13/C-/sup 13/C constants of the adjacent nuclei. The observed effect was used to establish the conformational structure of the compounds.

Microstructure and molecular interaction in glycerol plasticized chitosan/poly(vinyl alcohol) blending films

Science.gov (United States)

Poly (vinyl alcohol) (PVA)/chitosan (CS) blended films plasticized by glycerol were investigated using mechanical testing, atomic force microscopy (AFM), differential scanning calorimetry (DSC) and FTIR spectroscopy, with primary emphasis on the effects of the glycerol content and the molecular weig...

Study of the influence of the molecular structure of vinyl compounds on their ability to form polymer films by electro-polymerization under cathodic polarisation

International Nuclear Information System (INIS)

Deniau, Guy

1990-01-01

This research thesis addresses the study of new vinyl compounds, and aims at improving knowledge on the interaction between metal and a vinyl molecule under an intense electric field (the field of the double electrochemical layer), and more particularly at studying the influence of the molecular structure of the vinyl compound as well as the occurring reactions. After a first part presenting physical-chemical principles and knowledge which govern the whole set of reactions which are occurring within an electrolysis reactor, and a brief historical overview, this research thesis proposes a presentation of molecules which have been chosen for this study (vinyl compounds) and a justification of this choice. The author also presents the experimental device and describes the process implementation. Then, he presents and analyses experimental results. It appears that only some studied molecules result in the formation of polymer film [fr

Elution behavior of poly(ethylene glycol) through poly(vinyl alcohol) gel column using several solvents as eluents

International Nuclear Information System (INIS)

Hirayama, Chuichi; Motozato, Yoshiaki; Matsumoto, Kazuaki.

1983-01-01

γ-Irradiated poly(vinyl alcohol) beads, which were sufficiently allowed to swell in water, were washed with methanol, and then were packed into column. Gel chromatography was performed using methanol, benzene, esters and ketones as eluents and poly(ethylene glycol) as a sample. When the elution was carried out using methanol and benzene as eluents, elution behavior of samples was ordinary. When ethyl formate, methyl acetate and ethyl propionate were used as eluents, samples were slightly adsorbed and the elution was delayed. In the case the elution was carried out using ethyl acetate, propyl acetate, butyl acetate and ethyl methyl ketone as eluents, samples were adsorbed strongly on the bed material, and the adsorption curve was analogous to the calibration curve using methanol as an eluent. Dried poly(vinyl alcohol) gel as a packing material, showed ordinary elution behaviors for the samples. The adsorption of poly(ethylene glycol) on the present bed material was attributed to the existence of hydrated water on poly(vinyl alcohol) gel matrix. (author)

The Inhibition of Aluminum Corrosion in Sulfuric Acid by Poly(1-vinyl-3-alkyl-imidazolium Hexafluorophosphate).

Science.gov (United States)

Arellanes-Lozada, Paulina; Olivares-Xometl, Octavio; Guzmán-Lucero, Diego; Likhanova, Natalya V; Domínguez-Aguilar, Marco A; Lijanova, Irina V; Arce-Estrada, Elsa

2014-08-07

Compounds of poly(ionic liquid)s (PILs), derived from imidazole with different alkylic chain lengths located in the third position of the imidazolium ring (poly(1-vinyl-3-dodecyl-imidazolium) (PImC 12 ), poly(1-vinyl-3-octylimidazolium) (PImC₈) and poly(1-vinyl-3-butylimidazolium) (PImC₄) hexafluorophosphate) were synthesized. These compounds were tested as corrosion inhibitors on aluminum alloy AA6061 in diluted sulfuric acid (0.1-1 M H₂SO₄) by weight loss tests, polarization resistance measurements and inductively coupled plasma optical emission spectroscopy. Langmuir's isotherms suggested film formation on bare alloy while standard free energy indicated inhibition by a physisorption process. However, compound efficiencies as inhibitors ranked low (PImC 12 > PImC₈ > PImC₄) to reach 61% for PImC 12 in highly diluted acidic solution. Apparently, the high mobility of sulfates favored their adsorption in comparison to PILs. The surface film displayed general corrosion, and pitting occurred as a consequence of PILs' partial inhibition along with a continuous dissolution of defective patchy film on formation. A slight improvement in efficiency was displayed by compounds having high molecular weight and a long alkyl chain, as a consequence of steric hindrance and PIL interactions.

Synthesis, Chemosensory Properties, and Self-Assembly of Terpyridine-Containing Conjugated Polycarbazole through RAFT Polymerization and Heck Coupling Reaction

Directory of Open Access Journals (Sweden)

Po-Chih Yang

2017-09-01

Full Text Available We report the responsive fluorescence chemosensory phenomena of a carbazole-functionalized crosslinked polymer (PCaT with pendent terpyridine (tpy groups as receptors of metal ions. The polymer was synthesized using Heck polymerization between 3,6-dibromide groups in a carbazole-based polymer (PC2Br and divinyl tpy monomer. The effects of the polymeric structure on the optical and chemosensory properties of the PCaT were compared with those of a carbazole-tpy alternating conjugated polymer (PCT. Photoluminescence titrations demonstrated that the PCaT and PCT had the high sensing ability toward Fe3+ ions, with Stern–Volmer constants of 8.10 × 104 and 6.68 × 104 M−1, respectively. The limit of detection (LOD toward Fe3+ of the PCaT and PCT was estimated to be 1.31 × 10−6 and 1.81 × 10−6 M, respectively, and the superior LOD of the PCaT was ascribed to its lowly crosslinked structure. The fluorescence of the solutions of these polymers that were quenched by Fe3+ ions recovered when trace CN− anions were added because of the high stability constant of the CN−–Fe3+ complex. Micellar aggregates with a mean diameter of approximately 239.5 nm were formed by dissolving the PCaT in tetrahydrofuran (THF solution. Our results suggest that the PCaT is a promising material for chemosensory applications.

Predicting Residential Exposure to Phthalate Plasticizer Emitted from Vinyl Flooring - A Mechanistic Analysis

Science.gov (United States)

A two-room model is developed to estimate the emission rate of di-2-ethylhexyl phthalate (DEHP) from vinyl flooring and the evolving gas-phase and adsorbed surface concentrations in a realistic indoor environment. Adsorption isotherms for phthalates and plasticizers on interior ...

Effect of a weak magnetic field on the Mizoroki–Heck coupling reaction in the presence of wicker-like palladium-poly(N-vinylpyrrolidone)-iron nanocatalyst

Energy Technology Data Exchange (ETDEWEB)

Rafiee, Ezzat, E-mail: ezzat_rafiee@yahoo.com [Department of Inorganic Chemistry, Faculty of Chemistry, Razi University, Kermanshah 67149 (Iran, Islamic Republic of); Institute of Nano Science and Nano Technology, Razi University, Kermanshah 67149 (Iran, Islamic Republic of); Joshaghani, Mohammad [Department of Inorganic Chemistry, Faculty of Chemistry, Razi University, Kermanshah 67149 (Iran, Islamic Republic of); Institute of Nano Science and Nano Technology, Razi University, Kermanshah 67149 (Iran, Islamic Republic of); Abadi, Parvaneh Ghaderi-Shekhi [Institute of Nano Science and Nano Technology, Razi University, Kermanshah 67149 (Iran, Islamic Republic of)

2016-06-15

The wicker-like Pd-PVP-Fe (palladium-poly(N-vinylpyrrolidone)-iron) was synthesized by the external magnetic field (EMF). The Pd-based catalyst with nano and the face-centered cubic (fcc) structure was obtained at room temperature without using any additive. The resulting composite was characterized. The results show that EMF has a great influence on morphology, particle size, and crystalline structure of the Pd-PVP-Fe composite. The resulting composite (Pd-PVP-Fe), was found to be an effective catalyst for the Mizoroki–Heck reaction while is exposed to EMF with the intensity at 486 µT. The reused catalyst for at least five repeating cycles, shows excellent activity. - Highlights: • The wicker-like Pd-PVP-Fe nanocatalyst was synthesized via external magnetic field. • The resulting catalyst composite was characterized. • The C–C coupling reaction was carried out at magnetic field and room temperature. • Magnetic field affects on the morphology and size of the catalyst. • The catalyst could be reused without significant degradation in activity.

Study on radiation effect of poly (vinyl alcohol) films irradiated by tritium decay

International Nuclear Information System (INIS)

Li Hairong; Peng Shuming; Zhou Xiaosong; Yu Mingming; Xia Lidong; Chen Xiaohua; Liang Jianhua

2014-01-01

The radiation effect of poly(vinyl alcohol) films used as a kind of gas-barrier material for inertial confinement fusion (ICF) targets was studied under the different conditions of β-ray from tritium decay. The changes of physical and chemical properties of the irradiated material samples were analyzed by FTIR, XRD and AFM. The tritium-hydrogen isotopic exchange reaction of the irradiated samples mainly occurs at C-H bond and the IR absorption peak of C-T bond obviously increases with the irradiation dose. For strong hydrogen bonding interaction, the isotopic exchange reaction doesn't occur at O-H bond. The crystallinity degree and surface morphology of the irradiated samples were changed. The tensile properties of irradiated poly(vinyl alcohol) films were measured by universal material testing machine. The results show that the change trend of mechanical properties is in accordance with the microstructures of the irradiated samples. (authors)

Novel route to 5-position vinyl derivatives of thiolactomycin: Olefination vs. deformylation

Science.gov (United States)

Kim, Pilho; Barry, Clifton E.; Dowd*, Cynthia S.

2006-01-01

Vinyl and diene derivatives of thiolactomycin have been prepared via Horner-Wadsworth-Emmons olefination from protected 5-formyl-3,5-dimethylthiotetronic acid. Several 4-position protecting groups and a variety of phosphonates were evaluated, with MOM protection and β-ketophosphonates yielding the highest ratio of desired product to deformylated product. PMID:16699591

Synthesis and reactivity ratios of regioisomeric vinyl-1,2,3-triazoles with styrene

NARCIS (Netherlands)

Lartey, M; Gillissen, M.A.J.; Adzima, B.J.; Takizawa, K.; Luebke, D.R.; Nulwala, H.B.

2013-01-01

The free radical reactivity ratios between styrene and different vinyl-1,2,3-triazole regioisomeric monomers in 1,4-dioxane at 65 degrees C have been established using nonlinear least square method. The results obtained for the reactivity ratio between regioisomers show exceptionally different

Concurrent coordination of ligand in metal chloride complexes with 1-vinyl-2-(2-pyridyl)benzimidazole

International Nuclear Information System (INIS)

Bajkalov, L.V.; Domnina, E.S.

1996-01-01

The properties and structure of bivalent cadmium and 1-vinyl-2-(2-pyridyl)benzimidazole chloride complexes, which have been prepared for the first time, have been studied by the methods of potentiometric titration and PMR, 35 Cl NQR, UV and IR spectroscopy. For the complexes above di- and polymeric structures in crystal phase are suggested, where ligand plays the role of a bridge. N,N-bidentate ligand. In solution the complexes dissociate with formation of monomeric coordination compounds, their metal being bound by different ways, stemming from participation of N benzimidazole or pyridine fragment of the ligand. Adducts of ionic type with second sphere 1-vinyl-2-(2-pyridyl)benzimidazole cation have been obtained in the course of hydrochlorination of the complexes prepared

Evaluation of morphology and cell behaviour of a novel synthesized electrospun poly(vinyl pyrrolidone/poly(vinyl alcohol/hydroxyapatite nanofibers

Directory of Open Access Journals (Sweden)

Raheleh Faridi-Majidi

2017-04-01

Full Text Available Objective(s: Three-dimensional structures such as nanofibrous scaffolds are being used in biomedical engineering as well as provide a site for cells to attach and proliferate leading to tissue formation. In the present study, poly(vinyl pyrrolidone (PVP/ poly(vinyl alcohol(PVA hybrid nanofibrous scaffold was synthesized by electrospinning. Materials and Methods: The effect of adding nano hydroxyapatite (n-HA and also Epoxypropoxy-propyl-trimethoxysilane (EPPTMS as a crosslinking agent on morphology and cell behaviour of the nanofibers was investigated.Results: Scanning electron microscope (SEM observations showed that all kinds of nanofibers represented uniform and well-ordered morphologies without formation of any beads by controlling the synthesis parameters. The average ûber diameter of PVP-PVA was 260 nm. n-HA was synthesized by wet chemical process. The synthesized n-HA was characterized by XRD for structural analysis. Transmission electron microscope (TEM revealed that HA particles had nanosized dimensions (in the range of 40-100 nm. The presence of n-HA within electrospun PVP-PVA nanofibers was confirmed by XRD and Fourier transmission infrared spectroscopy (FTIR analyses. The average ûber diameter was decreased to 136 nm when n-HA was added in the composition of PVP-PVA. FTIR analysis depicted that PVP-PVA nanofibers were linked to EPPTMS as a biocompatible material by the covalent bond. Although adding n-HA caused to decrease the diameter of PVP-PVA nanofibers, addition of EPPTMS within PVP/PVA/n-HA nanofibers induced increasing distribution of fiber diameter as it enhanced to 195nm. In addition, the proper proliferation of G292 osteoblastic cells without any cytotoxicity was observed for the nanofiber.Conclusion: Since these materials have been known as biomaterials, PVP/PVA/n-HA-EPPTMS nanofibers can be propounded as a good candidate for bone tissue engineering application.

Halloysite nanotubes grafted hyperbranched (co)polymers via surface-initiated self-condensing vinyl (co)polymerization

International Nuclear Information System (INIS)

Mu Bin; Zhao Mingfei; Liu Peng

2008-01-01

Halloysite nanotubes (HNTs) grafted hyperbranched polymers were prepared by the self-condensing vinyl polymerization (SCVP) of 2-((bromoacetyl)oxy)ethyl acrylate (BAEA) and the self-condensing vinyl copolymerization of n-butyl acrylate (BA) and BAEA with BAEA as inimer (AB*) respectively, from the surfaces of the 2-bromoisobutyric acid modified halloysite nanotubes (HNTs-Br) via atom transfer radical polymerization (ATRP) technique. The halloysite nanotubes grafted hyperbranched polymer (HNTs-HP) and the halloysite nanotubes grafted hyperbranched copolymer (HNTs-HCP) were characterized by elemental analysis (EA), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscope (TEM). The grafted hyperbranched polymers were characterized with Nuclear magnetic resonance (NMR) and the molecular ratio between the inimer AB* and BA in the grafted hyperbranched copolymers was found to be 3:2, calculated from the TGA and EA results

Halloysite nanotubes grafted hyperbranched (co)polymers via surface-initiated self-condensing vinyl (co)polymerization

Energy Technology Data Exchange (ETDEWEB)

Mu Bin; Zhao Mingfei; Liu Peng [Lanzhou University, State Key Laboratory of Applied Organic Chemistry and Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering (China)], E-mail: pliu@lzu.edu.cn

2008-05-15

Halloysite nanotubes (HNTs) grafted hyperbranched polymers were prepared by the self-condensing vinyl polymerization (SCVP) of 2-((bromoacetyl)oxy)ethyl acrylate (BAEA) and the self-condensing vinyl copolymerization of n-butyl acrylate (BA) and BAEA with BAEA as inimer (AB*) respectively, from the surfaces of the 2-bromoisobutyric acid modified halloysite nanotubes (HNTs-Br) via atom transfer radical polymerization (ATRP) technique. The halloysite nanotubes grafted hyperbranched polymer (HNTs-HP) and the halloysite nanotubes grafted hyperbranched copolymer (HNTs-HCP) were characterized by elemental analysis (EA), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscope (TEM). The grafted hyperbranched polymers were characterized with Nuclear magnetic resonance (NMR) and the molecular ratio between the inimer AB* and BA in the grafted hyperbranched copolymers was found to be 3:2, calculated from the TGA and EA results.

Angiosarcoma of the liver and other occupational diseases in vinyl chloride workers

International Nuclear Information System (INIS)

Halama, J.; Becker-Stone, S.; Halama, J.M.

1985-01-01

Occupational diseases resulting from exposure to vinyl chloride (VC) include angiosarcoma of the liver and other neoplasms. Among workers exposed to VC we have found capillary abnormalities in the extremities, with scleroderma and Raynaud syndrome, acro-osteolysis, neurological and psychiatric diseases and chromosome abnormalities, as well as abnormal liver metabolism and haematological findings.(orig.)

Additive effects on phase transition and interactions in poly(vinyl methyl ether) solutions

Czech Academy of Sciences Publication Activity Database

Starovoytova, Larisa; Šťastná, J.; Šturcová, Adriana; Konefal, Rafal; Dybal, Jiří; Velychkivska, Nadiia; Radecki, M.; Hanyková, L.

2015-01-01

Roč. 7, č. 12 (2015), s. 2572-2583 ISSN 2073-4360 R&D Projects: GA ČR(CZ) GA13-23392S Institutional support: RVO:61389013 Keywords : additives * LCST * poly(vinyl methyl ether) Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.944, year: 2015

Hybrids of ethylene vinyl acetate with Na-montmorillonite and titania: preparation and characterization

International Nuclear Information System (INIS)

Ashfaq, M.

2010-01-01

Hybrids of Ethylene vinyl acetate (EVA) with Na-montmorillonite and titania were formed. Montmorillonite was organically modified by two different modifiers: Pyridinium ions and 4. 4-oxydianilinium ions. X-ray diffraction results revealed that Pyridinium ions increased the .interlayer spacing by 0.33 nm and 4, 4-oxydianilinium by 0.55 nm approximately. These modified organo-clays were successfully exfoliated in EVA using melt blending. These hybrids showed improvement in mechanical and thermal properties. 4, 4-oxydianilinium ions were degraded at higher temperature due to which thermal degradation was enhanced in EVA. In addition to this, EVA/titania hybrids were also prepared using sot-gel technique and modified by triethoxy vinyl silane and (3-aminopropyI)- triethoxy silane to increase their compatibility with EVA. Some portion of unmodified titania was heat treated to 600 degree C to obtain particulate titania. The hybrid of particulate titania and modified titania improved the mechanical properties and thermal properties. Especially in case of modified titania toughness was almost doubled. (author)

The Inhibition of Aluminum Corrosion in Sulfuric Acid by Poly(1-vinyl-3-alkyl-imidazolium Hexafluorophosphate

Directory of Open Access Journals (Sweden)

Paulina Arellanes-Lozada

2014-08-01

Full Text Available Compounds of poly(ionic liquids (PILs, derived from imidazole with different alkylic chain lengths located in the third position of the imidazolium ring (poly(1-vinyl-3-dodecyl-imidazolium (PImC12, poly(1-vinyl-3-octylimidazolium (PImC8 and poly(1-vinyl-3-butylimidazolium (PImC4 hexafluorophosphate were synthesized. These compounds were tested as corrosion inhibitors on aluminum alloy AA6061 in diluted sulfuric acid (0.1–1 M H2SO4 by weight loss tests, polarization resistance measurements and inductively coupled plasma optical emission spectroscopy. Langmuir’s isotherms suggested film formation on bare alloy while standard free energy indicated inhibition by a physisorption process. However, compound efficiencies as inhibitors ranked low (PImC12 > PImC8 > PImC4 to reach 61% for PImC12 in highly diluted acidic solution. Apparently, the high mobility of sulfates favored their adsorption in comparison to PILs. The surface film displayed general corrosion, and pitting occurred as a consequence of PILs’ partial inhibition along with a continuous dissolution of defective patchy film on formation. A slight improvement in efficiency was displayed by compounds having high molecular weight and a long alkyl chain, as a consequence of steric hindrance and PIL interactions.

THE COMPLETE, TEMPERATURE-RESOLVED EXPERIMENTAL SPECTRUM OF VINYL CYANIDE (H2CCHCN) BETWEEN 210 AND 270 GHz

International Nuclear Information System (INIS)

Fortman, Sarah M.; Neese, Christopher F.; De Lucia, Frank C.; Medvedev, Ivan R.

2011-01-01

The results of an experimental approach to the identification and characterization of the astrophysical weed vinyl cyanide in the 210-270 GHz region are reported. This approach is based on spectrally complete, intensity-calibrated spectra taken at more than 400 different temperatures in the 210-270 GHz region and is used to produce catalogs in the usual astrophysical format: line frequency, line strength, and lower state energy. As in our earlier study of ethyl cyanide, we also include the results of a frequency point-by-point analysis, which is especially well suited for characterizing weak lines and blended lines in crowded spectra. This study shows substantial incompleteness in the quantum-mechanical (QM) models used to calculate astrophysical catalogs, primarily due to their omission of many low-lying vibrational states of vinyl cyanide, but also due to the exclusion of perturbed rotational transitions. Unlike ethyl cyanide, the QM catalogs for vinyl cyanide include analyses of perturbed excited vibrational states, whose modeling is more challenging. Accordingly, we include an empirical study of the frequency accuracy of these QM models. We observe modest frequency differences for some vibrationally excited lines.

Characterization of plasma-polymerized 4-vinyl pyridine with silver nanoparticies on poly(ethylene terephthalate) film for anti-microbial properties

DEFF Research Database (Denmark)

Jiang, J.; Winther-Jensen, Bjørn; Kjær, Erik Michael

2006-01-01

scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Different thicknesses Of poly(4-vinyl pyridine) coating under different plasma polymerization conditions were studied. Silver nanoparticles with diameter around 50nm deposit were precipitated...... on the poly(4-vinyl pyridine) coating by UV irradiation in Silver nitride water solution, in order to enhance the anti-microbial properties. Different kinds of modified PET films were tested for anti-microbial properties against yeast (Debaryomyces hansenii) by using microbiological analyser mu-4200...

[1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination.

Science.gov (United States)

Kanchupalli, Vinaykumar; Katukojvala, Sreenivas

2018-05-04

A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal-functionalized 1-pyrroline derivatives was developed. The reaction involves a novel rhodium-catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1-pyrrolines. Structural diversification of the enal-functionalized 1-pyrrolines resulted in the biologically important pyrrolidine-fused oxaziridine, amino acid derivatives, and a 6-azabicyclo[3.2.1]octane motif present in polycyclic alkaloids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of various hydrogels based on poly (Vinyl pyrrolidone) and poly ethylene glycol using gamma and electron irradiation

International Nuclear Information System (INIS)

Ajji, Z.

2006-11-01

Different hydrogels have been prepared using gamma and electron irradiation; the hydrogels are composed of poly(vinyl pyrolidone) (PVP), poly(ethylene glycol) (PEG). The influence of some process parameters on the properties of the hydrogels has been investigated as: the gel fraction, maximum swelling, swelling kinetics, and mechanical properties. In the first part of this study, hydrogel dressings have been prepared using electron irradiation, and the dressings are composed of poly(vinyl pyrrolidone) (PVP), poly(ethylene glycol) (PEG) and agar. The gel fraction increases with increasing PVP concentration due to increased crosslink density, and decreases with increasing the PEG concentration. PEG seems to act not only as plasticizer but also to modify the gel properties as gelation% and maximum swelling. The prepared hydrogels dressings could be considered as a good barrier against microbes. In the second part, different hydrogels have been prepared based on different concentrations of poly(vinyl pyrrolidone) and using gamma irradiation. The gel fraction and maximum swelling of the hydrogels has been determined. In the third part of the study, different hydrogels have been prepared based on different concentrations of poly(vinyl pyrrolidone) and poly(ethylene glycol) (PEG) with various molecular weights, and using gamma irradiation. The gel fraction and maximum swelling of the hydrogels has been determined. The data show that PEG with low molecular weight needs a high dose for the gelation, and the presence of PVP lowers the needed gelation dose. The maximum swelling decreases with increasing irradiation dose and the PVP concentration, which is due to higher crosslinks between the polymer chains. (author)

Bio-Inspired nacre-like nanolignocellulose-poly (vinyl alcohol)-TiO2 composite with superior mechanical and photocatalytic properties.

Science.gov (United States)

Chen, Yipeng; Wang, Hanwei; Dang, Baokang; Xiong, Ye; Yao, Qiufang; Wang, Chao; Sun, Qingfeng; Jin, Chunde

2017-05-12

Nacre, the gold standard for biomimicry, provides an excellent example and guideline for assembling high-performance composites. Inspired by the layered structure and extraordinary strength and toughness of natural nacre, nacre-like nanolignocellulose/poly (vinyl alcohol)/TiO 2 composites possessed the similar layered structure of natural nacre were constructed through hot-pressing process. Poly (vinyl alcohol) and TiO 2 nanoparticles have been used as nanofillers to improve the mechanical performance and synchronously endow the superior photocatalytic activity of the composites. This research would be provided a promising candidate for the photooxidation of volatile organic compounds also combined with outstanding mechanical property.

Biaxial stress-strain behavior of chemical and physical gels of poly(vinyl alcohol)

Czech Academy of Sciences Publication Activity Database

Meissner, Bohumil; Matějka, Libor

2008-01-01

Roč. 49, č. 10 (2008), s. 2560-2567 ISSN 0032-3861 R&D Projects: GA AV ČR IAA400500701 Institutional research plan: CEZ:AV0Z40500505 Keywords : poly(vinyl alcohol) gels * pure shear behavior * constitutive equation Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.331, year: 2008

Fracture behavior of highly toughened poly(lactic acid)/ethylene-co-vinyl acetate blends

NARCIS (Netherlands)

Zeng, Q.; Feng, Y.; Wang, R.; Ma, P.

2018-01-01

Poly(lactic acid) (PLA) is brittle which restricts the range of its applications. The toughness of PLA was effectively improved in this work by incorporation of rubber grade ethylene-co-vinyl acetate (EVM). For example, the elongation at break of PLA increased by about 50 times after the addition of

Analysis of cannabinoids in commercial hemp seed oil and decarboxylation kinetics studies of cannabidiolic acid (CBDA).

Science.gov (United States)

Citti, Cinzia; Pacchetti, Barbara; Vandelli, Maria Angela; Forni, Flavio; Cannazza, Giuseppe

2018-02-05

Hemp seed oil from Cannabis sativa L. is a very rich natural source of important nutrients, not only polyunsaturated fatty acids and proteins, but also terpenes and cannabinoids, which contribute to the overall beneficial effects of the oil. Hence, it is important to have an analytical method for the determination of these components in commercial samples. At the same time, it is also important to assess the safety of the product in terms of amount of any psychoactive cannabinoid present therein. This work presents the development and validation of a highly sensitive, selective and rapid HPLC-UV method for the qualitative and quantitative determination of the main cannabinoids, namely cannabidiolic acid (CBDA), tetrahydrocannabinolic acid (THCA), cannabidiol (CBD), tetrahydrocannabinol (THC), cannabinol (CBN), cannabigerol (CBG) and cannabidivarin (CBDV), present in 13 commercial hemp seed oils. Moreover, since decomposition of cannabinoid acids generally occurs with light, air and heat, decarboxylation studies of the most abundant acid (CBDA) were carried out in both open and closed reactor and the kinetics parameters were evaluated at different temperatures in order to evaluate the stability of hemp seed oil in different storage conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

Temperature-modified photonic bandgap in colloidal photonic crystals fabricated by vinyl functionalized silica spheres

International Nuclear Information System (INIS)

Deng Tiansong; Zhang Junyan; Zhu Kongtao; Zhang Qifeng; Wu Jinlei

2011-01-01

Graphical abstract: A thermal annealing procedure was described for fine modifying the photonic bandgap properties of colloidal photonic crystals, which were self-assembled from vinyl-functionalized silica spheres by a gravity sedimentation process. Highlights: → We described a thermal annealing procedure for fine modifying the photonic bandgap properties of colloidal photonic crystals. → The position of its stop band had more than 25% blue shift by annealing the sample from 60 to 600 deg. C. → The annealing temperature and the Bragg peak values have a linear relationship in the 120-440 deg. C range. → The effects provide a simple and controllable method for modifying the photonic bandgap properties of colloidal photonic crystals. - Abstract: A thermal annealing procedure for fine modifying the photonic bandgap properties of colloidal photonic crystals was described. The colloidal photonic crystals were assembled from monodisperse vinyl functionalized silica spheres by a gravity sedimentation process. The samples diffract light following Bragg's law combined with Snell's law. By annealing the sample at temperatures in the range of 60-600 deg. C, the position of its stop band shifted from 943 to 706 nm. It had more than 25% blue shift. In addition, the annealing temperature and the Bragg peak values have a linear relationship in the 120-440 deg. C range. Fourier transform infrared (FT-IR) spectra and thermo-gravimetric analysis (TGA) curves of vinyl functionalized silica spheres confirmed the above results. The effects provide a simple and controllable method for modifying the photonic bandgap properties of colloidal photonic crystals.

Modeling of the Migration of Glycerol Monoester Plasticizers in Highly Plasticized Poly(vinyl chloride)

DEFF Research Database (Denmark)

Lundsgaard, Rasmus; Kontogeorgis, Georgios; Kristiansen, Jørgen K.

2009-01-01

soybean oil (ESBO) with regard to their migration from three different types of poly(vinyl chloride) into isooctane at 20, 40, and 60 degrees C. Diffusion coefficients derived from the experimental migration data were evaluated against diffusion coefficients estimated from a model based solely...

One-Pot Catalytic Enantio- and Diastereoselective Syntheses of anti-, syn-cis-Disubstituted, and syn-Vinyl Cyclopropyl Alcohols

Science.gov (United States)

Kim, Hun Young; Salvi, Luca; Carroll, Patrick J.; Walsh, Patrick J.

2009-01-01

Highly enantio- and diastereoselective methods for the synthesis of a variety of cyclopropyl alcohols are reported. These methods represent the first one-pot approaches to syn-vinyl cyclopropyl alcohols, syn-cis-disubstituted cyclopropyl alcohols, and anti-cyclopropyl alcohols from achiral precursors. The methods begin with enantioselective C–C bond formations promoted by a MIB-based zinc catalyst to generate allylic alkoxide intermediates. The intermediates are then subjected to in situ alkoxide-directed cyclopropanation to provide cyclopropyl alcohols. In the synthesis of vinyl cyclopropyl alcohols, hydroboration of enynes is followed by transmetalation of the resulting dienylborane to zinc to provide dienylzinc reagents. Enantioselective addition to aldehydes generates the requisite dienyl zinc alkoxides, which are then subjected to in situ cyclopropanation to furnish vinyl cyclopropyl alcohols. Cyclopropanation occurs at the double bond allylic to the alkoxide. Using this method, syn-vinylcyclopropyl alcohols are obtained in 65–85% yield, 76–93% ee, and >19:1 dr. To prepare anti-cyclopropanols, enantioselective addition of alkylzinc reagents to conjugated enals provides allylic zinc alkoxides. Because direct cyclopropanation provides syn-cyclopropyl alcohols, the intermediate allylic alkoxides were treated with TMSCl/Et3N to generate intermediate silyl ethers. In situ cyclopropanation of the allylic silyl ether resulted in cyclopropanation to form the anti-cyclopropyl silyl ether. Workup with TBAF affords the anti-cyclopropyl alcohols in one-pot in 60–82% yield, 89–99% ee, and ≥10:1 dr. For the synthesis of cis-disubstituted cyclopropyl alcohols, in situ generated (Z)-vinyl zinc reagents were employed in asymmetric addition to aldehydes to generate (Z)-allylic zinc alkoxides. In situ cyclopropanation provides syn-cis-disubstituted cyclopropyl alcohols in 42–70% yield, 88–97% ee, and >19:1 dr. These one-pot procedures enable the synthesis of a

Radiation-Induced Graft Polymerization of Vinyl Monomers with Anion Groups onto MWNT Supports and Their Application as Electrogenerated Chemiluminescence (ECL Biosensors

Directory of Open Access Journals (Sweden)

Ji-Hye Park

2014-01-01

Full Text Available Vinyl polymer-grafted multiwalled carbon nanotube (MWNT supports with anion groups were prepared for use as biosensor supports by radiation-induced graft polymerization (RIGP of the vinyl monomers acryloyl diphosphoric acid (ADPA, acrylic acid (AA, sodium styrenesulfonate (NaSS, and methacrylic acid (MA onto the surface of MWNTs. The electrogenerated chemiluminescence sensors based on a glass carbon electrode (ECL-GCE and a screen printed electrode (ECL-SPE were fabricated by immobilization of Ru(bpy3 2+ complex after coating of vinyl polymer-grafted MWNT inks on the surface of the GCE and SPE without any polymer binders in order to obtain high electrogenerated chemiluminescence intensity. For detection of alcohol concentration, alcohol dehydrogenase (ADH was immobilized onto an ECL-GCE sensor prepared by poly(NaSS-g-MWNT supports. The prepared biosensor based on ADH is suitable for the detection of ethanol concentration in commercial drinks.

Synthesis of Lipophilic Antioxidants by a Lipase-B-Catalyzed Addition of Peracids to the Double Bond of 4-Vinyl-2-methoxyphenol.

Science.gov (United States)

Zago, Erika; Durand, Erwann; Barouh, Nathalie; Lecomte, Jérôme; Villeneuve, Pierre; Aouf, Chahinez

2015-10-21

4-Vinyl guaiacol (2) was lipophilized through the electrophilic addition of peracids to its vinylic double bond. Those peracids were formed in situ, by the Candida antarctica lipase-B-assisted perhydrolysis of carboxylic acids ranging from C2 to C18, in hydrogen peroxide solution. The addition of peracids with 4-8 carbons in their alkyl chains led to the formation of two regioisomers, with the prevalence of hydroxyesters bearing a primary free hydroxyl (4c-4e). This prevalence became more pronounced when peracids with longer alkyl chains (C10-C18) were used. In this case, only isomers 4f-4h were formed. The antioxidant activity of the resulting hydroxyesters was assessed by means of the conjugated autoxidizable triene (CAT) assay, and it was found out that the 4-vinyl guaiacol antioxidant activity was significantly increased by grafting alkyl chains with 2-8 carbons.

Synthesis of Poly(N-vinyl-2-pyrrolidone-co-methyl methacrylate by Maghnite-H+ a Non-toxic Catalyst

Directory of Open Access Journals (Sweden)

Mohamed Benadda

2014-10-01

Full Text Available In the present work poly (N-vinyl-2-pyrrolidone-co-methyl methacrylate copolymers were prepared successfully and cleanly by a one step process via cationic copolymerization of N-vinyl-2-pyrrolidone (NVP with methyl methacrylate (MMA, in heterogeneous phase using “Maghnite-H+” (Mag-H+ as catalyst in bulk, Maghnite is a montmorillonite sheet silicate clay exchanged with protons to produce Maghnite-H+. Temperature is varied between 20 and 80 °C. The effects of reaction temperature, amount of Mag-H+ on the yield and the intrinsic viscosity (η were investigated. A typical reaction product of poly (NVP-co- MMA was analyzed by infra red spectroscopy (FTIR and 1H-NMR, 13C-NMR spectroscopy as well as by viscosimetry. © 2014 BCREC UNDIP. All rights reservedReceived: 24th November 2013; Revised: 30th June 2014; Accepted: 8th July 2014How to Cite: Benadda, M., Ferrahi, M.I., Belbachir, M. (2014. Synthesis of Poly(N-vinyl-2-pyrrolidone-co-methyl methacrylate by Maghnite-H+ a Non-toxic Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (3: 201-206. (doi: 10.9767/bcrec.9.3.5743.201-206Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.3.5743.201-206

An Investigation of Chitosan-Grafted-Poly(vinyl alcohol as an Electrolyte Membrane

Directory of Open Access Journals (Sweden)

Panu Danwanichakul

2013-01-01

Full Text Available The membrane of chitosan-grafted-poly(vinyl alcohol/poly(vinyl alcohol (CS-g-PVA/PVA was investigated along with chitosan (CS, PVA, CS/PVA, and Nafion 117 membranes for transport properties of water and methanol, mechanical properties, and ionic conductivity. The ionic conductivity, σ, of the crosslinked CS-g-PVA/PVA membrane was about 4.37 mS cm−1 and the methanol permeability, PS, was 1.8×10−7 cm2s−1. These gave the selectivity, σ/PS, of 23.95 mS·s·cm−3 compared with 16.35 mS·s·cm−3 of Nafion 117 membrane. The conductivity of the crosslinked CS-g-PVA/PVA membrane was greater than others including Nafion 117 when the membranes were saturated with methanol solution of which concentration was greater than 20%. This fact and that the mechanical properties of the wet crosslinked CS-g-PVA/PVA membrane were comparable to those of other membranes made it a promising material to be used as an electrolyte membrane in a direct methanol fuel cell.

Action des copolymères éthylène-acétate de vinyle sur la cinétique de nucléation et de croissance des n-paraffines n milieu hydrocarbure. Effect of Vinyl Ethyleneacetate Copolymers on the Nucleation and Growth Kinetics of N-Paraffins in a Hydrocarbon Medium.

Directory of Open Access Journals (Sweden)

Petinelli J. C.

2006-11-01

Full Text Available On cherche à mettre en évidence le mode d'action des copolymères éthylène-acétate de vinyle sur la cinétique de cristallisation des n-paraffines en milieu hydro-carbure. On s'attache, notamment, à déterminer si l'efficacité de ces additifs est peu ou prou influencée par le nombre de motifs non paraffiniques contenus dans leur chaîne.On décrit deux montages expérimentaux, l'un permettant d'étudier la cinétique de nucléation, l'autre la cinétique de croissance en solution. On observe, grâce à ces deux dispositifs, que la fréquence de germination tridimensionnelle et la vitesse de croissance des n-paraffines diminuent quand la concentration d'acétate de vinyle dans la solution augmente.On établit une relation entre le taux d'acétate de vinyle de la chaîne des copo-lymères et leur efficacité à retarder la cinétique de nucléation. La cinétique de croissance est discutée. On montre l'adsorption très forte de ces additifs sur les faces des cristaux et que le copolymère le plus riche en groupes acétate de vinyle est celui qui retarde le plus la cinétique de nucléation et de croissance des n- paraffines. An effort is made ta détermine how vinyl ethyleneacetate copolymers effect thé crystallization kinetics of n-paraffins in a hydrocarbon medium. In particular, research was done ta see if thé effectiveness of such additives is in thé least bit influenced by thé number of non-paraffinic patterns contained in their chain.Two expérimental assemblies are described, one for investigating nucléation kinetics, thé other growth kinetics in solution. These two devices are used ta observe thot thé theee-dimensional germination fréquency and growth rate of n-paraffins decrease as thé vinyl-acétate concentration in thé solution increases.A relationship is established between thé vinyl-acétate ratio of thé copolymer chain and thé effectiveness of thé copolymer in delaying thé nucléation kinetics. Growth kinetics

Simultaneous FT-NIR and ESR analysis to study of the kinetics of photo induced polymerization of vinyl radical polymers

International Nuclear Information System (INIS)

Le, T.T.; Hill, D.J.T.; Pomery, P.J.

2000-01-01

Full text:The rate parameters for free vinyl radical polymerizations are difficult to determine accurately over the whole range of conversion. For systems which polymerize rapidly and for networks, this is a particular problem, because small differences in polymerization conditions, e.g., temperature, initiator concentration, photon flux, etc., can cause a large change in the time evolution of the concentration of carbon double bonds and radicals if these are monitored in separate experiments. The IUPAC Working Party on the Modeling of kinetics and processes of polymerization has the role of recommending the 'best' values for the kinetic parameters, using pulsed-laser polymerization (PLP) in conjunction with molar mass distribution (MMD) to determine k p as a function of temperature (T deg C) for bulk free-radical polymerization of methyl methacrylate at low conversions and ambient temperature. The vinyl radical polymers used in this study were methyl methacrylate and ethylene glycol dimethacrylate. In the past kinetic studies of vinyl photo-polymerization required the time dependence of the monomer and radical concentrations to be monitored separately by using FT-NIR spectroscopy and ESR spectroscopy, respectively. For the systems which polymerize rapidly, small differences in the conditions for two measurements, e.g. temperature and light intensity, can introduce significant errors. Hyphenated experiments involving in-situ ESR and FT-NIR spectroscopies using fibre optic, can overcome these problems. In this paper, the radical and monomer concentrations were measured under the same experimental conditions using the above techniques. The results obtained were used to evaluate the kinetic parameters for free radical vinyl polymerizations

Bioorthogonal Metabolic DNA Labelling using Vinyl Thioether-Modified Thymidine and o-Quinolinone Quinone Methide.

Science.gov (United States)

Gubu, Amu; Li, Long; Ning, Yan; Zhang, Xiaoyun; Lee, Seonghyun; Feng, Mengke; Li, Qiang; Lei, Xiaoguang; Jo, Kyubong; Tang, Xinjing

2018-04-17

Bioorthogonal metabolic DNA labeling with fluorochromes is a powerful strategy to visualize DNA molecules and their functions. Here, we report the development of a new DNA metabolic labeling strategy enabled by the catalyst-free bioorthogonal ligation using vinyl thioether modified thymidine and o-quinolinone quinone methide. With the newly designed vinyl thioether-modified thymidine (VTdT), we added labeling tags on cellular DNA, which could further be linked to fluorochromes in cells. Therefore, we successfully visualized the DNA localization within cells as well as single DNA molecules without other staining reagents. In addition, we further characterized this bioorthogonal DNA metabolic labeling using DNase I digestion, MS characterization of VTdT as well as VTdT-oQQF conjugate in cell nuclei or mitochondria. This technique provides a powerful strategy to study DNA in cells, which paves the way to achieve future spatiotemporal deciphering of DNA synthesis and functions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocomposites prepared from acrylonitrile butadiene rubber and organically modified montmorillonite with vinyl groups

Science.gov (United States)

Han, Mijeong; Kim, Hoonjung; Kim, Eunkyoung

2006-01-01

Nanocomposites were prepared from acrylonitrile-butadiene rubber (NBR), vinyl groups containing organically modified montmorillonite and additives, such as zinc oxide, stearic acid, and sulfur. The organically modified montmorillonites used in these nanocomposites were prepared by ion exchange reactions of N,N'-dimethylalkyl-(p-vinylbenzyl)-ammonium chlorides (DAVBAs, alkyl = octyl, dodecyl, and octadecyl) with sodium montmorillonite (Na+-MMT). NBR nanocomposites were obtained by controlling both the mixing and vulcanization conditions, by using a Brabender mixer and hot-press process. X-ray diffraction (XRD) analysis shows that, depending on the amount of montmorillonite that is added, both exfoliated and intercalated nanocomposite structures are formed. The NBR/DAVBA-MMT nanocomposites exhibit much higher mechanical properties (e.g., tensile strength, Young's modulus, 300% modulus, and hardness) as well as gas barrier properties as compared to NBR Na+-MMT or NBR composites generated from modified montmorillonites without vinyl groups. Consistent with the results of XRD, transmission electron microscopy (TEM) reveals that the intercalation and exfoliation structures of the nanocomposites coexist and that the DAVBA-MMT layers are well dispersed in NBR.

Sustainability of thermoplastic vinyl roofing membrane systems

Energy Technology Data Exchange (ETDEWEB)

Graveline, S. P. [Sika Sanarfil, Canton, (United States)

2010-07-01

The International Council for Research and Innovation in Building and Construction (CIB-RILEM) has developed a framework for sustainable roofing based on a series of tenets divided into three key areas: preservation of the environment, conservation of energy, and extended roof life. This paper investigated the sustainability of thermoplastic vinyl roof membranes using these guidelines and the relevant tenets for roof system selection. Several tenets provided alternatives for minimizing the burden on the environment using non-renewable raw materials, conserving energy with thermal insulation, and extending the lifespan of all roof components by using long lasting membranes. A life cycle assessment was carried out to provide a quantitative framework for assessing the sustainability of roofing materials. It was found that the PVC membrane systems had a lesser impact on the environment than other competing systems.

The Microwave Spectrum of Methyl Vinyl Ketone Revisited

Science.gov (United States)

Wilcox, David S.; Shirar, Amanda J.; Williams, Owen L.; Dian, Brian C.

2011-06-01

A chirped-pulse Fourier transform microwave spectrometer was used to record the rotational spectrum of methyl vinyl ketone (MVK, 3-butene-2-one) from 6 to 18.9 GHz. Two stable conformations were identified: the previously documented antiperiplanar (ap) conformer and synperiplanar (sp), which is reported for the first time in this microwave study. Methyl torsional analysis with XIAM resulted in V3 barrier heights of 433.8(1) and 376.6(2) Cm-1 for ap- and sp-MVK, respectively. Heavy atom isotopic species were detected in natural abundance allowing bond lengths and angles of the molecular frames to be calculated through Kraitchman analysis. A comparison with ab initio calculations is included.

The influence of stretching on tensile strength and solubility of poly(vinyl alcohol) fibres

NARCIS (Netherlands)

Heikens, D.; Bleijenberg, A.C.A.M.; Hoppenbrouwers, J.J.M.; Barentsen, W.M.

1971-01-01

The strength of wet-spun poly(vinyl alcohol) (pva) fibres is given as function of bath-stretching, wet-stretching and hot-stretching. In the two equations derived for strength of wet-stretching and hot-stretching the complex influence of the bath-stretching and hot-stretching is demonstrated. The

Vinyl Sulfonate/Vinyl Amide Copolymers and Different Surfactants As Suitable Systems in Eorat Higher Temperatures and Salinities Utilisation de mélanges de copolymères vinyl sulfonate/vinyl amide et de différents tensio-actifs en RAP dans des conditions de fortes salinités et de températures élevées

Directory of Open Access Journals (Sweden)

Von Halasz S. P.

2006-11-01

Full Text Available For enhanced oil recovery flooding processes there will be an increasing demand for polymers having high temperature and electrolyte stability. High molecular weight copolymers based on vinyl sulfonate, vinyl amide, and acryl amide show high performances in matching these demanding requirements. Surfactants are also known that are stable under these conditions, resulting in high deoiling rates. The aim of the present article is to demonstrate the influence of alkylphenol ethoxylates and their corresponding ether sulfonates on VS/VA/AM copolymer solutions. Aqueous solutions of such copolymers were added to varying quantities of nonionic and anionic surfactants at different temperatures using salinity scans. This article discusses the results of experiments with solutions of copolymers and surfactants in terms of compatibility, viscosity yield, flow properties, shear stability, injectability, thermostability, and oil recovery. Solutions of alkylphenol ethoxylates and/or ether sulfonates show nearly the same compatibility within a broad range of temperature and salinity, both with and without polymers. Relatively small amounts of surfactants are able to influence the EOR (Enhanced Oil Recovery properties of the polymer solutions, giving several interesting aspects for improved oil recovery. L'utilisation des polymères en récupération assistée du pétrole a fait apparaître un besoin croissant de polymères stables à haute température et à forte salinité. Les performances des terpolymères vinyl sulfonate/vinyl amide/acrylamide (VS/VA/VM ont montré que ces polymères remplissent de tels critères d'utilisation. On connaît également des tensio-actifs chimiquement stables dans ces mêmes conditions qui pourraient donc permettre d'obtenir des taux de récupération d'huile élevés. L'objectif de ce travail est de mettre en évidence l'influence de la présence d'alkylphénols éthoxyIates et des éthers sulfonates correspondants sur les

13C n.m.r. study of solvation mechanisms in the radiation-induced polymerization of vinyl ethers

International Nuclear Information System (INIS)

Deffieux, A.; Subira, F.; Stannett, V.T.

1984-01-01

A 13 C n.m.r. study of the microstructure of ethyl vinyl ether (EVE) and isopropyl vinyl ether (IPVE) polymers prepared under various experimental conditions and using chemical or γ-ray initiation has been made. Long stereo-sequence assignments were conducted for poly EVE allowing determination of the configurational statistics of propagation in the radiation-induced polymerization of EVE in low polar solvents. Stereo-sequence intensities are found in good agreement with the Markovian model. The results are considered as further support for the occurrence of a specific interaction between the growing active centres and the polymer chains. In the case of IPVE polymers much more important overlappings of the resonance patterns are observed thus preventing any similar detailed study. (author)

Disk Refining and Ultrasonication Treated Sugarcane Bagasse Residues for Poly(Vinyl Alcohol) Bio-composites

Science.gov (United States)

Qingzheng Cheng; Zhaohui Tong; Luisa Dempere; Lonnie Ingram; Letian Wang; J.Y. Zhu

2013-01-01

Disk refining and ultrasonication treated sugarcane bagasse residues reclaimed from the waste stream of a simplified bioethanol process after fermentation were used to fabricate biobased composites with poly(vinyl alcohol) (PVA) by film casting. The morphologies and the size distributions of residue particles were characterized by scanning electronic microscopy and...

Synthesis and biological evaluation of cis-locked vinylogous combretastatin-A4 analogues: derivatives with a cyclopropyl-vinyl or a cyclopropyl-amide bridge.

Science.gov (United States)

Ty, Nancy; Kaffy, Julia; Arrault, Alban; Thoret, Sylviane; Pontikis, Renée; Dubois, Joelle; Morin-Allory, Luc; Florent, Jean-Claude

2009-03-01

A series of novel combretastatin A4 analogues, in which the cis-olefinic bridge is replaced by a cyclopropyl-vinyl or a cyclopropyl-amide moiety, were synthesized and evaluated for inhibition of tubulin polymerization and antiproliferative activity. The derivative 9a with a (cis,E)-cyclopropyl-vinyl unit is the most promising compound. As expected, molecular docking of 9a has shown that only one of the cis-cyclopropyl enantiomers is a good ligand for tubulin.

Thermoplastic starch/ethylene vinyl alcohol/forsterite nanocomposite as a candidate material for bone tissue engineering

Energy Technology Data Exchange (ETDEWEB)

Mahdieh, Zahra [Polymeric Materials Research Group (PMRG), Department of Materials Science and Engineering, Sharif University of Technology, Tehran, P.O. Box 11155-9466 (Iran, Islamic Republic of); Bagheri, Reza, E-mail: rezabagh@sharif.edu [Polymeric Materials Research Group (PMRG), Department of Materials Science and Engineering, Sharif University of Technology, Tehran, P.O. Box 11155-9466 (Iran, Islamic Republic of); Eslami, Masoud; Amiri, Mohammad [Polymeric Materials Research Group (PMRG), Department of Materials Science and Engineering, Sharif University of Technology, Tehran, P.O. Box 11155-9466 (Iran, Islamic Republic of); Shokrgozar, Mohammad Ali; Mehrjoo, Morteza [National Cell Bank of Iran, Pasteur Institute of Iran, Tehran (Iran, Islamic Republic of)

2016-12-01

Recently, biodegradable polymers such as starch based blends have been well renowned in the biomedical field. Studies have considered them suitable for bone scaffolds, bone cements, tissue engineering scaffolds, drug delivery systems and hydrogels. The aim of this study was to synthesize nanocomposite biomaterial consisting a blend of thermoplastic starch and ethylene vinyl alcohol as the polymer matrix, and nano-structured forsterite as the ceramic reinforcing phase for bone tissue engineering applications. Furthermore, vitamin E was applied as a thermal stabilizer during melt compounding. Extrusion and injection molding were incorporated for melt blending and shaping of samples, respectively. With blending thermoplastic starch and ethylene vinyl alcohol, some properties of thermoplastic starch such as degradation rate and water absorption were modified. In addition, using nanoforsterite as the ceramic reinforcing phase resulted in the improvement of mechanical and biological traits. The addition of nanoforsterite decreased the weight loss of the thermoplastic starch and ethylene vinyl alcohol blend in simulated body fluid. Moreover, this addition modified the pH in the MTT (methyl thiazolyl tetrazolium) assay and stimulated the cell proliferation. Cell adhesion assays indicated a favorable interaction between cells and the biomaterial. The proposed nanocomposite has appropriate biocompatibility, as well as mechanical properties in order to be used in bone tissue engineering. - Highlights: • A biodegradable nanocomposite is proposed for orthopedic applications. • Vitamin E is used as an antioxidant to prevent the thermomechanical degradations. • Nanoforsterite reduced the composite degradation rate in the simulated body fluid. • Nanoforsterite modified pH in MTT assay and stimulated cell proliferation.

Thermoplastic starch/ethylene vinyl alcohol/forsterite nanocomposite as a candidate material for bone tissue engineering

International Nuclear Information System (INIS)

Mahdieh, Zahra; Bagheri, Reza; Eslami, Masoud; Amiri, Mohammad; Shokrgozar, Mohammad Ali; Mehrjoo, Morteza

2016-01-01

Recently, biodegradable polymers such as starch based blends have been well renowned in the biomedical field. Studies have considered them suitable for bone scaffolds, bone cements, tissue engineering scaffolds, drug delivery systems and hydrogels. The aim of this study was to synthesize nanocomposite biomaterial consisting a blend of thermoplastic starch and ethylene vinyl alcohol as the polymer matrix, and nano-structured forsterite as the ceramic reinforcing phase for bone tissue engineering applications. Furthermore, vitamin E was applied as a thermal stabilizer during melt compounding. Extrusion and injection molding were incorporated for melt blending and shaping of samples, respectively. With blending thermoplastic starch and ethylene vinyl alcohol, some properties of thermoplastic starch such as degradation rate and water absorption were modified. In addition, using nanoforsterite as the ceramic reinforcing phase resulted in the improvement of mechanical and biological traits. The addition of nanoforsterite decreased the weight loss of the thermoplastic starch and ethylene vinyl alcohol blend in simulated body fluid. Moreover, this addition modified the pH in the MTT (methyl thiazolyl tetrazolium) assay and stimulated the cell proliferation. Cell adhesion assays indicated a favorable interaction between cells and the biomaterial. The proposed nanocomposite has appropriate biocompatibility, as well as mechanical properties in order to be used in bone tissue engineering. - Highlights: • A biodegradable nanocomposite is proposed for orthopedic applications. • Vitamin E is used as an antioxidant to prevent the thermomechanical degradations. • Nanoforsterite reduced the composite degradation rate in the simulated body fluid. • Nanoforsterite modified pH in MTT assay and stimulated cell proliferation.

Poly(vinyl alcohol)/poly(acrylic acid)/TiO2/graphene oxide nanocomposite hydrogels for pH-sensitive photocatalytic degradation of organic pollutants

International Nuclear Information System (INIS)

Moon, Young-E; Jung, Gowun; Yun, Jumi; Kim, Hyung-Il

2013-01-01

Graphical abstract: The photocatalytic removal of pollutants was improved by the two-step mechanism based on the adsorption of pollutants by hydrogel and the effective decomposition by combination of TiO 2 and graphene oxide. -- Highlights: • pH sensitive PVA/PAAc hydrogels were prepared by radical polymerization and condensation reaction. • PVA/PAAc/TiO 2 /graphene oxide nanocomposite hydrogels were used for treatment of basic waste water. • Photocatalytic acitivity of TiO 2 was improved by incorporation of graphene oxide. • Photocatalytic decomposition by nanocomposite hydrogel was improved by increasing pH. -- Abstract: Poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 /graphene oxide nanocomposite hydrogels were prepared using radical polymerization and condensation reaction for the photocatalytic treatment of waste water. Graphene oxide was used as an additive to improve the photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 nanocomposite hydrogels. Both TiO 2 and graphene oxide were immobilized in poly(vinyl alcohol)/poly(acrylic acid) hydrogel matrix for an easier recovery after the waste water treatment. The photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 /graphene oxide nanocomposite hydrogels was evaluated on the base of the degradation of pollutants by using UV spectrometer. The improved removal of pollutants was due to the two-step mechanism based on the adsorption of pollutants by nanocomposite hydrogel and the effective decomposition of pollutants by TiO 2 and graphene oxide. The highest swelling of nanocomposite hydrogel was observed at pH 10 indicating that poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 /graphene oxide nanocomposite hydrogels were suitable as a promising system for the treatment of basic waste water

The differences between NAD-ME and NADP-ME subtypes of C4 photosynthesis: more than decarboxylating enzymes

Directory of Open Access Journals (Sweden)

Xiaolan Rao

2016-10-01

Full Text Available As an adaptation to changing climatic conditions that caused high rates of photorespiration, C4 plants have evolved to display higher photosynthetic efficiency than C3 plants under elevated temperature, high light intensities and drought. The C4 plants independently evolved more than 60 times in 19 families of angiosperms to establish similar but not uniform C4 mechanisms to concentrate CO2 around the carboxylating enzyme Rubisco. C4 photosynthesis is divided into at least two basic biochemical subtypes based on the primary decarboxylating enzymes, NAD-dependent malic enzyme (NAD-ME and NADP-dependent malic enzyme (NADP-ME. The multiple polygenetic origins of these subtypes raise questions about the association of C4 variation between biochemical subtypes and diverse lineages. This review addresses the differences in evolutionary scenario, leaf anatomy, and especially C4 metabolic flow, C4 transporters and cell-specific function deduced from recently reported cell-specific transcriptomic, proteomic and metabolic analyses of NAD-ME and NADP-ME subtypes. Current omic analysis has revealed the extent to which component abundances differ between the two biochemical subtypes, leading to a better understanding of C4 photosynthetic mechanisms in NAD-ME and NADP-ME subtypes.

Influence of polymer chain architecture of poly(vinyl alcohol) on the inhibition of ice recrystallization

NARCIS (Netherlands)

Olijve, L.L.C.; Hendrix, M.M.R.M.; Voets, I.K.

2016-01-01

Poly(vinyl alcohol) (PVA) is a water-soluble synthetic polymer well-known to effectively block the recrystallization of ice. The effect of polymer chain architecture on the ice recrystallization inhibition (IRI) by PVA remains unexplored. In this work, the synthesis of PVA molecular bottlebrushes is

Vinyl Acetate/butyl acrylate/acrylate Research of Ternary Soap-free Emulsion Polymerization

Directory of Open Access Journals (Sweden)

Xiao Li-guang

2016-01-01

Full Text Available Through the vinyl acetate/butyl acrylate/acrylic acrylic emulsion preparation without soap vinegar, with solid content, gel, emulsion stability and film forming properties and tensile strength as the main index to study the effect of raw materials on the properties of emulsion. Through the infrared spectrometer soap-free emulsion for microscopic analysis research. Study of the ternary soap-free vinegar acrylic emulsion with good performance.

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

DEFF Research Database (Denmark)

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

1977-01-01

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

Fabrication and properties of poly(polyethylene glycol n-alkyl ether vinyl ether)s as polymeric phase change materials

International Nuclear Information System (INIS)

Pei, Dong-fang; Chen, Sai; Li, Shu-qin; Shi, Hai-feng; Li, Wei; Li, Xuan; Zhang, Xing-xiang

2016-01-01

A series of poly(polyethylene glycol n-alkyl ether vinyl ether)s (PC m E n VEs) with various lengths of alkyl chains and polyethylene glycol spacers as side chain (m = 16,18; n = 1,2) were synthesized via two steps. First, monomers-ethylene glycol hexadecyl ether vinyl ether (C 16 E 1 VE), ethylene glycol octadecyl ether vinyl ether (C 18 E 1 VE), diethylene glycol hexadecyl ether vinyl ether (C 16 E 2 VE) and diethylene glycol octadecyl ether vinyl ether (C 18 E 2 VE) were synthesized by a modified Williamson etherification. Then, four new types of phase change materials were successfully fabricated by a living cationic polymerization. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to characterize their composition, thermal properties and crystallization behavior. The results show that, the side chains of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are in a hexagonal lattice, and the onset temperatures for melting of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are 39.8 °C, 37.4 °C, 51.0 °C and 48.9 °C, the onset temperatures for crystallization are 36.7 °C, 35.2 °C, 47.4 °C and 46.3 °C, respectively. The enthalpy changes of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 100 J/g; on the contrary, it is 96 J/g for PC 16 E 1 VE. The enthalpy decrease is no more than 11% after 10 heating and cooling cycles. The 5 wt% mass loss temperatures of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 300 °C; on the contrary, it’s 283 °C for PC 16 E 1 VE. Using a weak polarity, flexible alkyl ether chain (-OCH 2 CH 2 O-) as a spacer to link the main chain and side chain is conducive to the crystallization of the alkyl side chain. These new phase change materials can be applied in heat storage, energy conservation, and environmental protection.

The influence of Poly-Vinyl-Chloride tubing on the isolated perfused rat´s heart.

NARCIS (Netherlands)

Meijler, F.L.; Durrer, D.

1950-01-01

There are types of poly-vinyl-chloride tubing sold and used for medical and biological purposes which deteriorate heart action in a few minutes. A simple method for testing P.V.C. tubing can be found in the isolated rat's he art perfused according to Langendorff.

Miscibility and Hydrogen Bonding in Blends of Poly(4-vinylphenol/Poly(vinyl methyl ketone

Directory of Open Access Journals (Sweden)

Hana Bourara

2014-10-01

Full Text Available The miscibility and phase behavior of poly(4-vinylphenol (PVPh with poly(vinyl methyl ketone (PVMK was investigated by differential scanning calorimetry (DSC, Fourier transform infrared spectroscopy (FTIR and scanning electron microscopy (SEM. It was shown that all blends of PVPh/PVMK are totally miscible. A DSC study showed the apparition of a single glass transition (Tg over their entire composition range. When the amount of PVPh exceeds 50% in blends, the obtained Tgs are found to be significantly higher than those observed for each individual component of the mixture, indicating that these blends are capable of forming interpolymer complexes. FTIR analysis revealed the existence of preferential specific interactions via hydrogen bonding between the hydroxyl and carbonyl groups, which intensified when the amount of PVPh was increased in blends. Furthermore, the quantitative FTIR study carried out for PVPh/PVMK blends was also performed for the vinylphenol (VPh and vinyl methyl ketone (VMK functional groups. These results were also established by scanning electron microscopy study (SEM.

The inhibition mechanisms of quinones and phenols present in wood for the vinyl polymerization

International Nuclear Information System (INIS)

Nobashi, Kenzo; Yokota, Tokuo

1977-01-01

The inhibitory effects and mechanisms of the quinones and phenols present in wood for the vinyl polymerization initiated with γ-rays and other initiation systems were investigated. The results obtained are summarized as follows; (1) Although phenolic compounds like isotaxiresinol inhibit the γ-ray initiated polymerization of methyl methacrylate (MMA) under the presence of air, they have no inhibitory effects in vacuo. On the other hand, o-benzoquinone and mansonones show strong inhibitory or retarding effects in vacuo. These facts indicate that oxygen may be important for the phenols to inhibit the vinyl polymerization. (2) It is shown qualitatively that there is a relationship between the strength of inhibitory action of quinones and their normal redox potentials. (3) PMMA produced under the presence of o-benzoquinone is found to include the fraction having extremely large chain length based on gel permeation chromatogram. (4) Based on the reaction products of orthoquinones and azobisisobutyronitrile, which was assumed as a model of polymer radicals, the inhibition reaction with polymer chain radical is concluded to take place upon the oxygen atoms of the quinones. (auth.)

DIELECTRIC AND PYROELECTRIC PROPERTIES OF THE COMPOSITES OF FERROELECTRIC CERAMIC AND POLY(VINYL CHLORIDE

Directory of Open Access Journals (Sweden)

M.Olszowy

2003-01-01

Full Text Available The dielectric and pyroelectric properties of lead zirconate titanate/poly(vinyl chloride [PZT/PVC] and barium titanate/poly(vinyl chloride [BaTiO3/ PVC] composites were studied. Flexible composites were fabricated in the thin films form (200-400 μm by hot-pressed method. Powders of PZT or BaTiO3 in the shape of ≤ 75 μm ceramics particles were dispersed in a PVC matrix, providing composites with 0-3} connectivity. Distribution of the ceramic particles in the polymer phase was examined by scanning electron microscopy. The analysis of the thermally stimulated currents (TSC have also been done. The changes of dielectric and pyroelectric data on composites with different contents of ceramics up to 40% volume were investigated. The dielectric constants were measured in the frequency range from 600 Hz to 6 MHz at room temperature. The pyroelectric coefficient for BaTiO3/PVC composite at 343 K is about 35 μC/m2K which is higher than that of β-PVDF (10 μC/m2 K.

Facile preparation of layered double hydroxide/MoS{sub 2}/poly(vinyl alcohol) composites

Energy Technology Data Exchange (ETDEWEB)

Zhou, Keqing, E-mail: zhoukq@cug.edu.cn [Faculty of Engineering, China University of Geosciences (Wuhan), 388 Lumo Road, Wuhan, Hubei, 430074 (China); Hu, Yixin [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Liu, Jiajia [State Key Laboratory of Fire Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui, 230026 (China); Gui, Zhou, E-mail: zgui@ustc.edu.cn [State Key Laboratory of Fire Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui, 230026 (China); Jiang, Saihua [School of Mechanical and Automotive Engineering, South China University of Technology, Wushan Road 381, Guangzhou, 510641 (China); Tang, Gang [School of Architecture and Civil Engineering, Anhui University of Technology, 59 Hudong Road, Ma' anshan, Anhui, 243002 (China)

2016-08-01

In present study, the layered double hydroxide/MoS{sub 2} hybrids are facilely synthesized by self-assembly of exfoliated MoS{sub 2} nanosheets and layered double hydroxide nanoplates via electrostatic interaction, with the aim of combining their physical and chemical functionalities to form a promising nanofiller for flame retardancy in polymer composites. The structure and morphology of the layered double hydroxide/MoS{sub 2} hybrids are probed by X-ray diffraction and transmission electron microscopy. Subsequently, the hybrids are incorporated into poly (vinyl alcohol) to serve as reinforcements. The flame retardant efficiency of MoS{sub 2} nanosheets in poly (vinyl alcohol) is significantly enhanced after the incorporation of layered double hydroxide nanoplates, which can be explained by the forming of a compact and uniform char during combustion. - Highlights: • The LDH/MoS{sub 2} hybrids were facilely synthesized by self-assembly method. • The flame retardant efficiency of LDH/MoS{sub 2} hybrids in PVA was significantly enhanced. • It is a promising strategy for improving the flame retardant efficiency of MoS{sub 2}.

Physicochemical characteristics of gamma irradiation crosslinked poly(vinyl alcohol)/magnetite ferrogel composite

OpenAIRE

Marinović-Cincović, Milena T.; Radosavljević, Aleksandra N.; Krstić, Jelena I.; Spasojević, Jelena P.; Bibić, Nataša M.; Mitrić, Miodrag N.; Kačarević-Popović, Zorica M.

2014-01-01

Magnetic field sensitive gels, ferrogels are new promising class of hydrogels. The coupling of hydrogels and magnetic particles has potential application in soft actuators such as artificial muscles or for hyperthermia application. Here a composite of magnetite particles (Fe3O4) and poly(vinyl alcohol) (PVA) hydrogel is developed using gamma irradiation as a crosslinking agent. PVA and Fe3O4 were chosen because of their well-established biocompatibility, ra...

Fabrication and Characterization of Electrospun Wool Keratin/Poly(vinyl alcohol) Blend Nanofibers

OpenAIRE

Shuai Li; Xu-Hong Yang

2014-01-01

Wool keratin/poly(vinyl alcohol) (PVA) blend nanofibers were fabricated using the electrospinning method in formic acid solutions with different weight ratios of keratin to PVA. The resultant blend nanofibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and tensile test. SEM images showed that the diameter of the blend nanofibers was affected by the content of keratin in blend solution...

A poly(vinyl alcohol)/sodium alginate blend monolith with nanoscale porous structure

OpenAIRE

Sun, Xiaoxia; Uyama, Hiroshi

2013-01-01

A stimuli-responsive poly(vinyl alcohol) (PVA)/sodium alginate (SA) blend monolith with nanoscale porous (mesoporous) structure is successfully fabricated by thermally impacted non-solvent induced phase separation (TINIPS) method. The PVA/SA blend monolith with different SA contents is conveniently fabricated in an aqueous methanol without any templates. The solvent suitable for the fabrication of the present blend monolith by TINIPS is different with that of the PVA monolith. The nanostructu...

Morphological, dielectric and electric conductivity characteristics of clay-containing nanohybrids of Poly(N-Vinyl Carbazole) and Polypyrrole

CSIR Research Space (South Africa)

Haldar, I

2012-10-01

Full Text Available Poly(N-vinyl carbazole) (PNVC) and polypyrrole (PPY)-montmorillonite (MMT) clay hybrids were prepared by mechanical grinding of the respective monomers with MMT followed by subsequent standard processing methods. Fourier transform infrared...

Morphology in binary blends of poly(vinyl methyl ether) and epsilon-caprolactone-trimethylene carbonate diblock copolymer

NARCIS (Netherlands)

Luyten, MC; Bogels, EJF; vanEkenstein, GORA; tenBrinke, G; Bras, W; Komanschek, BE; Ryan, AJ

The morphology of symmetric diblock copolymer of epsilon-caprolactone (PCL) and trimethylene carbonate (PTMC), in blends with poly(vinyl methyl ether) (PVME) is investigated with (modulated) differential scanning calorimetry (d.s.c.), time resolved small angle (SAXS) and wide angle (WAXS) X-ray

Morphology in binary blends of poly(vinyl methyl ether) and ε-caprolactone-trimethylene carbonate diblock copolymer

NARCIS (Netherlands)

Luyten, M.C.; Bögels, E.J.F.; Alberda van Ekenstein, G.O.R.; Brinke, G. ten; Bras, W.; Komanschek, B.E.; Ryan, A.J.

1997-01-01

The morphology of symmetric diblock copolymer of ε-caprolactone (PCL) and trimethylene carbonate (PTMC), in blends with poly(vinyl methyl ether) (PVME) is investigated with (modulated) differential scanning calorimetry (d.s.c.), time resolved small angle (SAXS) and wide angle (WAXS) X-ray

Vinyl ester resin and process for curing same with ionizing radiation in the presence of amines

International Nuclear Information System (INIS)

Mani, I.

1975-01-01

The addition of about 1.5 to 5 weight percent of certain amines to a thermosettable mixture of an alkenyl aromatic monomer and a polymerizable vinyl ester resin reduces the dosage level of ionizing radiation required to cure the mixture. (U.S.)

Angiographic study of digital arteries in workers exposed to vinyl chloride

Energy Technology Data Exchange (ETDEWEB)

Falappa, P; Magnavita, N; Bergamaschi, A; Colavita, N

1982-05-01

Five patients exposed to vinyl chloride were studied by hand angiography and other non-invasive methods, including photoplethysmography, rheography, and thermography. Raynaud's phenomenon was present in all five subjects, while acro-osteolysis affected only one. Organic vascular lesions, such as narrowing, segmentary occlusions of digital arteries and bridge collaterals, were found in angiographic studies. Only one patient did not show clear segmentary occlusions, but his vessels were crooked and diffusely narrowed. Angiographic results appear to correlate well with the changes shown by non-invasive techniques.

Effects of Concentration of Organically Modified Nanoclay on Properties of Sulfonated Poly(vinyl alcohol Nanocomposite Membranes

Directory of Open Access Journals (Sweden)

Apiradee Sanglimsuwan

2011-01-01

Full Text Available Electrolyte nanocomposite membranes for proton exchange membrane fuel cells and direct methanol fuel cells were prepared by carrying out a sulfonation of poly(vinyl alcohol with sulfosuccinic acid and adding a type of organically modified montmorillonite (layered silicate nanoclay commercially known as Cloisite 93A. The effects of the different concentrations (0, 2, 4, 6, 8 wt. % of the organoclay in the membranes on water uptake, ion exchange capacity (IEC, proton conductivity, and methanol permeability were measured, respectively, via gravimetry, titration, impedance analysis, and gas chromatography techniques. The IEC values remained constant for all concentrations. Water uptakes and proton conductivities of the nanocomposite membranes changed with the clay content in a nonlinear fashion. While all the nanocomposite membranes had lower methanol permeability than Nafion115, the 6% concentration of Cloisite 93A in sulfonated poly(vinyl alcohol membrane displayed the greatest proton conductivity to methanol permeability ratio.

Controlling the Plasma-Polymerization Process of N-Vinyl-2-pyrrolidone

DEFF Research Database (Denmark)

Norrman, Kion; Winther-Jensen, Bjørn

2005-01-01

N-vinyl-2-pyrrolidone was plasma-polymerized on glass substrates using a pulsed AC plasma. Pulsed AC plasma produces a chemical surface structure different from that produced by conventional RF plasma; this is ascribed to the different power regimes used. A high degree of control over the structure...... of the chemical surface was obtained using pulsed AC plasma, as shown by ToF-SIMS. It is demonstrated how the experimental conditions to some extent control the chemical structure of the plasma-polymerized film, e.g., film thickness, density of post-plasma-polymerized oligomeric chains, and the density of intact...

Study on properties of poly(vinyl alcohol/polyacrylonitrile blend film

Directory of Open Access Journals (Sweden)

Guoquan Zhu

2013-01-01

Full Text Available In this work, a series of poly(vinyl alcohol (PVA/polyacrylonitrile (PAN blend films with different PAN mole contents were prepared by casting the polymer blend solution in dimethylsulfoxide (DMSO. Surface morphologies of PVA/PAN blend films were analyzed by Scanning Electronic Microscopy (SEM and Atomic Force Microscopy (AFM. Thermal, mechanical, and chemical properties of PVA/PAN blend films were investigated by Differential Scanning Calorimetry (DSC, Thermogravimetric Analysis (TGA, Tensile Tests, and Surface Contact Angle Tests. The results showed that the introduction of PAN could exert marked effects on the properties of PVA films.

Effect of Poly(Vinyl Alcohol) Addition on the Properties of Hydrothermal Derived Calcium Phosphate Cement for Bone Filling Materials

Science.gov (United States)

Razali, N. N.; Sopyan, I.; Mel, M.; Salleh, H. M.; Rahman, M. M.; Singh, R.

2017-06-01

The effect of addition of poly(vinyl alcohol) on hydrothermal derived calcium phosphate cement has been studied. The precursors used to prepare the cement were calcium oxide (CaO) and ammonium dihydrogen phosphate (NH4H2PO4); the reaction was conducted in water at 80-100°C. To improve properties of CPC, poly(vinyl alcohol) (PVA) of 1wt% and 2wt% was added to the liquid phase of CPC and the results were compared to CPC without PVA addition. The addition of PVA was proved to bring remarkable effects on cohesion, setting time and mechanical strength of CPC which make it suitable physically for injectable bone filler applications.

Factors influencing optical 3D scanning of vinyl polysiloxane impression materials.

Science.gov (United States)

DeLong, R; Pintado, M R; Ko, C C; Hodges, J S; Douglas, W H

2001-06-01

Future growth in dental practice lies in digital imaging enhancing many chairside procedures and functions. This revolution requires the fast, accurate, and 3D digitizing of clinical records. One such clinical record is the chairside impression. This study investigated how surface angle and surface roughness affect the digitizing of vinyl polysiloxane impression materials. Seventeen vinyl polysiloxane impression materials were digitized with a white light optical digitizing system. Each sample was digitized at 3 different angles: 0 degrees, 22.5 degrees, and 45 degrees, and 2 digitizer camera f-stops. The digitized images were rendered on a computer monitor using custom software developed under NIH/NIDCR grant DE12225. All the 3D images were rotated to the 0 degrees position, cropped using Corel Photo-Paint 8 (Corel Corp, Ottawa, Ontario, Canada), then saved in the TIFF file format. The impression material area that was successfully digitized was calculated as a percentage of the total sample area, using Optimas 5.22 image processing software (Media Cybernetics, LP, Silver Spring, MD). The dependent variable was a Performance Value calculated for each material by averaging the percentage of area that digitized over the 3 angles. New samples with smooth and rough surfaces were made using the 7 impression materials with the largest Performance Values. These samples were tested as before, but with the additional angle of 60 degrees. Silky-Rock die stone (Whip Mix Corp, Louisville, KY) was used as a control. The Performance Values for the 17 impression materials ranged from 0% to 100%. The Performance Values for the 7 best materials were equivalent to the control at f/11 out to a surface angle of 45 degrees; however, only Examix impression material (GC America Inc, Alsip, IL) was equivalent to the control at f/11/\\16. At the 60 degrees surface angle with f/11/\\16, the Performance Values were 0% for all the impression materials, whereas that for the control was 90

Rhodium/Silver-Cocatalyzed Transannulation of N-Sulfonyl-1,2,3-triazoles with Vinyl Azides: Divergent Synthesis of Pyrroles and 2 H-Pyrazines.

Science.gov (United States)

Zhang, Lin; Sun, Ge; Bi, Xihe

2016-11-07

The first cyclization reaction between vinyl azides and N-sulfonyl-1,2,3-triazoles is reported. A Rh/Ag binary metal catalyst system proved to be necessary for the successful cyclization. By varying the structure of vinyl azides, such reaction allows the divergent synthesis of pyrroles and 2H-pyrazines. The cyclization reactions feature a broad substrate scope, good functional group tolerance, high reaction efficiency, and good to high product yields. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers with Various Molecular Weights as Phase Change Materials

Directory of Open Access Journals (Sweden)

Dongfang Pei

2018-02-01

Full Text Available At present, research on the relationship of comb-like polymer phase change material structures and their heat storage performance is scarce. Therefore, this relationship from both micro and macro perspectives will be studied in this paper. In order to achieve a high phase change enthalpy, ethylene glycol segments were introduced between the vinyl and the alkyl side chains. A series of poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers (PC14EnVEs (n = 1, 2 with various molecular weights were polymerized by living cationic polymerization. The results of PC14E1VE and PC14E2VE showed that the minimum number of carbon atoms required for side-chain crystallization were 7.7 and 7.2, which were lower than that reported in the literature. The phase change enthalpy 89 J/g (for poly(mono ethylene glycol n-tetradecyl ether vinyl ethers and 86 J/g (for poly(hexadecyl acrylate were approximately equal. With the increase of molecular weight, the melting temperature, the melting enthalpy, and the initial thermal decomposition temperature of PC14E1VE changed from 27.0 to 28.0 °C, from 95 to 89 J/g, and from 264 to 287 °C, respectively. When the number average molar mass of PC14EnVEs exceeded 20,000, the enthalpy values remained basically unchanged. The introduction of the ethylene glycol chain was conducive to the crystallization of alkyl side chains.

UV recording with vinyl acetate and muicle dye film

Science.gov (United States)

Toxqui-Lopez, S.; Olivares-Pérez, A.; Santacruz-Vazquez, V.; Fuentes-Tapia, I.; Ordoñez-Padilla, J.

2015-03-01

Nowadays, there are many types of holographic recording medium some of them are photopolymer systems that generally consist of a polymeric host matrix, photopolymerizable momomer, photosensitizing dye and charge transfer agent but some of them have an undesirable feature, the toxicity of their components. Therefore, the present research study material recording, vinyl acetate is selected as polymeric matrix and natural dye from "muicle plant" is used as the photoinitiation these components are not toxic. The films are fabricated using gravity settling method at room temperature by this method, uniform films is obtained with good optical quality. To characterize the medium, been obtained when the coherent reed light (632.8 nm) was sent normally to the grating.

Effect of gamma radiation on the poly(vinyl alcohol)

International Nuclear Information System (INIS)

Terence, M.C.; Guedes, S.M.L.

2000-01-01

The poly(vinyl alcohol) (PVAL) is a polymer used as bio material. The PVAL was used as ocular insert and may be used as a drug delivery system (DDS) for pair PVAL/gancyclovir, where the last one is used for treatment of people with retinitis caused by cytomegalovirus. These inserts are crosslinked systems. The crosslink was induced by gamma radiation applied in polymer. The samples of PVAL was irradiated by gamma rays with doses in the range 0 to 100 kGy. On irradiated PVAL samples was observed a low yellowness, attributed to the formation of polymeric radicals that are stable in the structure of the polymer, from radiolysis of PVAL. (author)

Homogeneity characterization of ethylene-co-vinyl acetate copolymer (EVA) and hydrophobic silica nanocomposite by low field NMR

International Nuclear Information System (INIS)

Stael, Giovanni Chaves; Tavares, Maria I.B.

2005-01-01

This project proposes the characterization of a polymeric matrix composite material using nanometric scale hydrophobic silica as charge element, with the ethylene-vinyl acetate (EVA), by using the spin-lattice relaxation time measurement applying the low field NMR

Highly sensitive and ultrafast response surface acoustic wave humidity sensor based on electrospun polyaniline/poly(vinyl butyral) nanofibers

International Nuclear Information System (INIS)

Lin Qianqian; Li Yang; Yang Mujie

2012-01-01

Highlights: ► Polyanline/poly(vinyl butyral) nanofibers are prepared by electrospinning. ► Nanofiber-based SAW humidity sensor show high sensitivity and ultrafast response. ► The SAW sensor can detect very low humidity. - Abstract: Polyaniline (PANi) composite nanofibers were deposited on surface acoustic wave (SAW) resonator with a central frequency of 433 MHz to construct humidity sensors. Electrospun nanofibers of poly(methyl methacrylate), poly(vinyl pyrrolidone), poly(ethylene oxide), poly(vinylidene fluoride), poly(vinyl butyral) (PVB) were characterized by scanning electron microscopy, and humidity response of corresponding SAW humidity sensors were investigated. The results indicated that PVB was suitable as a matrix to form nanofibers with PANi by electrospinning (ES). Electrospun PANi/PVB nanofibers exhibited a core–sheath structure as revealed by transmittance electron microscopy. Effects of ES collection time on humidity response of SAW sensor based on PANi/PVB nanofibers were examined at room temperature. The composite nanofiber sensor exhibited very high sensitivity of ∼75 kHz/%RH from 20 to 90%RH, ultrafast response (1 s and 2 s for humidification and desiccation, respectively) and good sensing linearity. Furthermore, the sensor could detect humidity as low as 0.5%RH, suggesting its potentials for low humidity detection. Attempts were done to explain the attractive humidity sensing performance of the sensor by considering conductivity, hydrophilicity, viscoelasticity and morphology of the polymer composite nanofibers.

Ethylene vinyl acetate (EVA) as a new drug carrier for 3D printed medical drug delivery devices

DEFF Research Database (Denmark)

Genina, Natalja; Hollander, Jenny; Jukarainen, Harri

2016-01-01

The main purpose of this work was to investigate the printability of different grades of ethylene vinyl acetate (EVA) copolymers as new feedstock material for fused-deposition modeling (FDM™)-based 3D printing technology in fabrication of custom-made T-shaped intrauterine systems (IUS......) and subcutaneous rods (SR). The goal was to select an EVA grade with optimal properties, namely vinyl acetate content, melting index, flexural modulus, for 3D printing of implantable prototypes with the drug incorporated within the entire matrix of the medical devices. Indomethacin was used as a model drug...... affected the drug release profiles from the filaments and printed prototype products: faster release from the prototypes over 30 days in the in vitro tests. To conclude, this study indicates that certain grades of EVA were applicable feedstock material for 3D printing to produce drug-loaded implantable...

IR Laser-Induced Degradation of Poly(vinyl acetate): Novel Thermal Reactions in the Solid Polymers

Czech Academy of Sciences Publication Activity Database

Kupčík, Jaroslav; Blazevska-Gilev, J.; Pola, Josef

2005-01-01

Roč. 26, č. 5 (2005), s. 386-389 ISSN 1022-1336 R&D Projects: GA ČR(CZ) GA104/04/2028 Institutional research plan: CEZ:AV0Z40720504 Keywords : laser ablation * laser-induced polymers * poly(vinyl acetate) Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.126, year: 2005

Uranium Adsorbent Fibers Prepared by Atom-Transfer Radical Polymerization (ATRP) from Poly(vinyl chloride)- co -chlorinated Poly(vinyl chloride) (PVC- co -CPVC) Fiber

Energy Technology Data Exchange (ETDEWEB)

Brown, Suree; Yue, Yanfeng; Kuo, Li-Jung; Mehio, Nada; Li, Meijun; Gill, Gary; Tsouris, Costas; Mayes, Richard T.; Saito, Tomonori; Dai, Sheng

2016-04-20

The need to secure future supplies of energy attracts researchers in several countries to a vast resource of nuclear energy fuel: uranium in seawater (estimated at 4.5 billion tons in seawater). In this study, we developed effective adsorbent fibers for the recovery of uranium from seawater via atom-transfer radical polymerization (ATRP) from a poly- (vinyl chloride)-co-chlorinated poly(vinyl chloride) (PVC-co-CPVC) fiber. ATRP was employed in the surface graft polymerization of acrylonitrile (AN) and tert-butyl acrylate (tBA), precursors for uranium-interacting functional groups, from PVC-co-CPVC fiber. The [tBA]/[AN] was systematically varied to identify the optimal ratio between hydrophilic groups (from tBA) and uranyl-binding ligands (from AN). The best performing adsorbent fiber, the one with the optimal [tBA]/[AN] ratio and a high degree of grafting (1390%), demonstrated uranium adsorption capacities that are significantly greater than those of the Japan Atomic Energy Agency (JAEA) reference fiber in natural seawater tests (2.42-3.24 g/kg in 42 days of seawater exposure and 5.22 g/kg in 49 days of seawater exposure, versus 1.66 g/kg in 42 days of seawater exposure and 1.71 g/kg in 49 days of seawater exposure for JAEA). Adsorption of other metal ions from seawater and their corresponding kinetics were also studied. The grafting of alternative monomers for the recovery of uranium from seawater is now under development by this versatile technique of ATRP.

Solid-phase synthesis of isoxazoles using vinyl ethers as chameleon catches.

Science.gov (United States)

Barrett, A G; Procopiou, P A; Voigtmann, U

2001-10-04

[reaction: see text] Regioselective 1,3-dipolar cycloadditions of supported vinyl ethers R(1)C(=CH(2))O-CH(2)-polymer, prepared by the Tebbe olefination of R(1)CO(2)-CH(2)-polymer, with ethyl cyanoformate N-oxide gave supported isoxazoline derivatives. Release from the support under mild acidic conditions gave the isoxazoles ethyl 5-R(1)-isoxazole-3-carboxylates. Alternatively, further on-resin functionalization of the R(1) substituent using Suzuki coupling reactions and release from the support under acidic conditions gave more structurally diverse isoxazoles.

Process for preventing discoloration in hydrolyzed ethylene-vinyl acetate copolymers by exposure to radiation

International Nuclear Information System (INIS)

Hoyt, J.M.; Koch, K.; Williams, M. Jr.

1975-01-01

A process for the hydrolysis of a solid interpolymer of an ethylenically unsaturated hydrocarbon and a vinyl ester of a 2 to 6 carbon atom aliphatic carboxylic acid to products having a low yellowness index involves contacting of the solid interpolymer with a substantially anhydrous hydrolyzing agent and subjecting at least one of said interpolymer and said hydrolyzing agent to radiation. (U.S.)

Effect of monomer concentration on the kinetics of emulsifier-free emulsion polymerization of Vinyl Acetate and Methyl Acrylate

International Nuclear Information System (INIS)

Mohammad Beigi, H. R.

2001-01-01

The effect of monomer concentration on the kinetics of the emulsifier-free emulsion polymerization of vinyl acetate and methyl acrylate were studied. The polymerizations were carried out using potassium persulfate as the initiator. Form the electron micrographs of the resulting lattices, monodisperse PVAc and PMA lattices with particle diameters varying between 149-443 mm and 112-497 nm, respectively were processed. Uniformity of particle size indicated that nucleation of stable particle occurs early in the polymerization process. The polymerization rate was found to be proportional to the 0.88 and 1.5 power of the initial monomer concentration of vinyl acetate and methyl acrylate, respectively. Higher monomer concentration results in fewer particles and larger final particle diameter. With increasing monomer solubility in water the size of particle decreases and its distribution broadens

In situ electron microscopy of Braille microsystems: photo-actuation of ethylene vinyl acetate/carbon nanotube composites

Science.gov (United States)

Czaniková, Klaudia; Krupa, Igor; Račko, Dušan; Šmatko, Vasilij; Campo, Eva M.; Pavlova, Ewa; Omastová, Mária

2015-02-01

The development of new types of tactile displays based on the actuation of composite materials can aid the visually impaired. Micro/nano systems based on ethylene vinyl acetate (EVA) polymeric matrices enriched with multiwalled carbon nanotubes (MWCNT) can produce ensembles capable of light-induced actuation. In this report, we investigate two types of commercial EVA copolymers matrices containing 28 and 50 wt% vinyl-acetate (VA). Non-covalent modification of carbon nanotubes was achieved through a compatibilization technique that appends the pyrenenyl and cholesteryl groups on the carbon nanotubes (CNTs) surface. EVA/MWCNT nanocomposites were prepared by casting from a solution. These composites were shaped into Braille elements using molds. The deformation of the Braille element (BE) under light-emitting diode (LED) illumination was observed for the first time by in situ scanning electron microscopy (SEM). The superior actuation performance promoted by the EVA/MWCNT nanocomposites indicates that these materials will be useful in the future as light-driven micro/nano system actuators.

In situ electron microscopy of Braille microsystems: photo-actuation of ethylene vinyl acetate/carbon nanotube composites

International Nuclear Information System (INIS)

Czaniková, Klaudia; Krupa, Igor; Račko, Dušan; Omastová, Mária; Šmatko, Vasilij; Campo, Eva M; Pavlova, Ewa

2015-01-01

The development of new types of tactile displays based on the actuation of composite materials can aid the visually impaired. Micro/nano systems based on ethylene vinyl acetate (EVA) polymeric matrices enriched with multiwalled carbon nanotubes (MWCNT) can produce ensembles capable of light-induced actuation. In this report, we investigate two types of commercial EVA copolymers matrices containing 28 and 50 wt% vinyl-acetate (VA). Non-covalent modification of carbon nanotubes was achieved through a compatibilization technique that appends the pyrenenyl and cholesteryl groups on the carbon nanotubes (CNTs) surface. EVA/MWCNT nanocomposites were prepared by casting from a solution. These composites were shaped into Braille elements using molds. The deformation of the Braille element (BE) under light-emitting diode (LED) illumination was observed for the first time by in situ scanning electron microscopy (SEM). The superior actuation performance promoted by the EVA/MWCNT nanocomposites indicates that these materials will be useful in the future as light-driven micro/nano system actuators. (paper)

Fabrication of thermo-responsive cotton fabrics using poly(vinyl caprolactam-co-hydroxyethyl acrylamide) copolymer.

Science.gov (United States)

Xiao, Min; González, Edurne; Monterroza, Alexis Martell; Frey, Margaret

2017-10-15

A thermo-responsive polymer with hydrophilic to hydrophobic transition behavior, poly(vinyl caprolactam-co-hydroxyethyl acrylamide) P(VCL-co-HEAA), was prepared by copolymerization of vinyl caprolactam and N-hydroxyethyl acrylamide via free radical solution polymerization. The resulting copolymer was characterized by Fourier transform infrared spectroscopy (FTIR), 1 H nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The lower critical solution temperature (LCST) of P(VCL-co-HEAA) was determined at 34.5°C. This thermo-responsive polymer was then grafted onto cotton fabrics using 1,2,3,4-butanetetracarboxylic acid (BTCA) as crosslinker and sodium hypophosphite (SHP) as catalyst. FTIR and energy dispersive X-ray spectroscopy (EDS) studies confirmed the successful grafting reaction. The modified cotton fabric exhibited thermo-responsive behavior as evidenced by water vapor permeability measurement confirming decreased permeability at elevated temperature. This is the first demonstration that a PVCL based copolymer is grafted to cotton fabrics. This study provides a new thermo-responsive polymer for fabrication of smart cotton fabrics with thermally switchable hydrophilicity. Copyright © 2017 Elsevier Ltd. All rights reserved.

Miscibility and specific interactions in blends of poly(n-vinyl-2-pyrrolidone) and acid functional polyester resins.

NARCIS (Netherlands)

Senatore, D.; Berix, M.J.A.; Laven, J.; Benthem, van R.A.T.M.; With, de G.; Mezari, B.; Magusin, P.C.M.M.

2008-01-01

Miscibility and intermol. interactions of novel blends of poly(N-vinyl-2-pyrrolidone) (PVP) and acid functional polyester resins (APE) were studied by use of Differential Scanning Calorimetry (DSC), Attenuated Total Reflectance Fourier Transform IR (ATR-FTIR), Cross-Polarization Magic Angle Spinning

Poly(vinyl alcohol) composite films with high percent elongation prepared from amylose-fatty ammonium salt inclusion complexes

Science.gov (United States)

Amylose inclusion complexes prepared from cationic fatty ammonium salts and jet-cooked high amylose starch were combined with poly(vinyl alcohol) (PVOH) to form glycerol-plasticized films. Their tensile properties were compared with similar films prepared previously with analogous anionic fatty acid...

Poly(vinyl acetate-Based Block Copolymer/Clay Nanocomposites Prepared by In Situ Atom Transfer Radical Polymerization

Directory of Open Access Journals (Sweden)

M.A. Semsarzadeh

2009-12-01

Full Text Available Atom transfer radical polymerization of styrene (St and methyl methacrylate (MMA was performed at 90oC in the absence and presence of nanoclay (Cloisite 30B. Trichloromethyl-terminated poly(vinyl acetate telomerand CuCl/ PMDETA were used as a macroinitiator and catalyst system, respectively. The experimental results showed that the atom transfer radical polymerization of St and MMA in the absence or presence of nanoclay proceeds via a controlled/living mode. It was observed that nanoclay significantly enhances the homopolymerization rate of MMA, which was attributed to the activated conjugated C=C bond of MMA monomer via interaction between the carbonyl group of MMA monomer and the hydroxyl moiety (Al-O-H of nanoclay as well as the effect of nanoclay on the dynamic equilibrium between the active (macro radicals and dormant species.Homopolymerization rate of St (a non-coordinative monomer with nanoclay decreased slightly in the presence of nanoclay. This could be explained by insertion of a portion of macroinitiator into the clay galleries, where no sufficient St monomer exists due to the low compatibility or interaction of St monomer with nanoclay to react with the macroinitiator. The results obtained from XRD, TEM and TGA analyses were fully in agreement with the kinetic data. Structure of the poly(vinyl acetate-bpolystyrene nanocomposite was found to be a combination of stacking layers and exfoliated structures while poly(vinyl acetate-b-poly(methyl methacryale nanocomposite had an exfoliated structure. This difference in the structure of nanocomposites was attributed to the different capability of the monomers (styrene and methyl methacrylate to react with the hydroxyl moiety (Al-O-H of nanoclay.

I curse your preoccupation with your record collection: The Fall on vinyl 1978-83

OpenAIRE

Osborne, Richard

2010-01-01

This chapter is in a book that is based upon papers given at the conference Messing Up The Paintwork, Salford University, 9 May 2008, the first conference to be based on the work of the Manchester band, The Fall. My chapter is based on research that I have undertaken for my monograph on the vinyl record, which is then related to the output of the band.

Pervaporation of alcohol-toluene mixtures through polymer blend membranes of poly(acrylic acid) and poly(vinyl alcohol)

NARCIS (Netherlands)

Park, H.C.; Park, H.; Meertens, R.M.; Meertens, R.M.; Mulder, M.H.V.; Smolders, C.A.; Smolders, C.A.

1994-01-01

Homogeneous membranes were prepared by blending poly(acrylic acid) with poly(vinyl alcohol). These blend membranes were evaluated for the selective separation of alcohols from toluene by pervaporation. The flux and selectivity of the membranes were determined both as a function of the blend

Evaluation of the vinyl acetate elimination process in methanogenic sludge with oxygen

International Nuclear Information System (INIS)

Duran, U.; Monroy, O.; Rendon, B.; Gomez, J.; Ramirez, F.

2009-01-01

The vinyl acetate (AV) is a volatile toxic used in the painting manufacture, causing serious problems of contamination in grounds, air and natural bodies of water. Under methanogenic conditions the complete mineralization of the AV has not been obtained, but evidences exist suggesting that with the addition of low oxygen concentrations to methanogenic sludge the elimination of this compound is possible. In this work was studied the respiratory process of elimination of the AV methano genesis and methano genesis with oxygen (1 mg/L-d). (Author)

Effect of borax concentration on the structure of Poly(Vinyl Alcohol) gels

Science.gov (United States)

Lawrence, Mathias B.; Desa, J. A. E.; Aswal, V. K.

2012-06-01

Poly(Vinyl Alcohol) hydrogels cross-linked with varying concentrations of borax have been studied using Small-Angle Neutron Scattering and X-Ray Diffraction. The intensity of scattering increases with borax concentration from 1 mg/ml up to 2 mg/ml and falls thereafter for 4 mg/ml, increasing again for a concentration of 10 mg/ml. The mesoscopic structural changes that cause these trends in the SANS data are in keeping with the variations in the X-ray diffraction patterns pertaining to structures within the PVA chains.

Vinyl ether hydrolysis. VII. Isotope effects on catalysis by aqueous hydrofluoric acid

International Nuclear Information System (INIS)

Kresge, A.J.; Chen, H.J.; Chiang, Y.

1977-01-01

Comparison of rates of hydrolysis of three vinyl ethers catalyzed by HF in H 2 O and DF in D 2 O at 25 0 C gives primary isotope effects in the range k/sub H//k/sub D/ = 3.3 to 3.5. The unexpectedly small size of these effects may be attributed to strong, ω = 1325 to 1450 cm -1 , hydrogenic bending vibrations in the proton transfer transition states of these reactions along with the lack of compensatory bending vibrations in the diatomic proton donor

The Emulsion Polymerization of Each of Vinyl Acetate and Butyl Acrylate Monomers Using bis (2-ethylhexyl) Maleate for Improving the Physicomechanical Properties of Paints and Adhesive Films

International Nuclear Information System (INIS)

Shaffei, K.A.; Moustafa, A.B.; Hamed, A.I.

2009-01-01

Improving the water sensitivity of polyvinyl acetate PVAc films as well as pressure sensitivity, adhesion and washability of poly butyl acrylate were achieved by using bis (2-ethylhexyl) maleate (BEHM). The emulsion polymerization kinetics of vinyl acetate and butyl acrylate in presence of BEHM was studied. The order of the polymerization reaction with respect to the BEHM in presence of each of vinyl acetate and butyl acrylate was studied. The physicomechanical properties of the polyvinyl acetate films and vinyl acetate-butyl acrylate copolymer films were studied in presence of BEHM and the obtained results were matched with those prepared in the presence of pluronic F 108 and showed superior values. The obtained mean average molecular weights were found to be smaller in presence of BEHM assuring the presence of chain transfer reaction.

The Emulsion Polymerization of Each of Vinyl Acetate and Butyl Acrylate Monomers Using bis (2-ethylhexyl Maleate for Improving the Physicomechanical Properties of Paints and Adhesive Films

Directory of Open Access Journals (Sweden)

K. A. Shaffei

2009-01-01

Full Text Available Improving the water sensitivity of polyvinyl acetate PVAc films as well as pressure sensitivity, adhesion and washability of polybutyl acrylate were achieved by using bis (2-ethylhexyl maleate (BEHM. The emulsion polymerization kinetics of vinyl acetate and butyl acrylate in presence of BEHM was studied. The order of the polymerization reaction with respect to the BEHM in presence of each of vinyl acetate and butyl acrylate was studied. The physicomechanical properties of the polyvinyl acetate films and vinyl acetate-butyl acrylate copolymer films were studied in presence of BEHM and the obtained results were matched with those prepared in the presence of pluronic F 108 and showed superior values. The obtained mean average molecular weights were found to be smaller in presence of BEHM assuring the presence of chain transfer reaction.

Effects of adrenergic agents on intracellular ca(2+) homeostasis and metabolism of glucose in astrocytes with an emphasis on pyruvate carboxylation, oxidative decarboxylation and recycling

DEFF Research Database (Denmark)

Obel, Linea Lykke Frimodt; Andersen, Karen M H; Bak, Lasse Kristoffer

2012-01-01

and oxidative decarboxylation in astrocytic glucose metabolism. Importantly, pyruvate carboxylation was best visualized at 10 min of incubation. The abundance and pattern of labeling in lactate and alanine indicated not only an extensive activity of malic enzyme (initial step for pyruvate recycling) but also...... a high degree of compartmentalization of the pyruvate pool. Stimulating with 1 µM NE had no effect on labeling patterns and glycogen metabolism, whereas 100 µM NE increased glutamate labeling and decreased labeling in alanine, the latter supposedly due to dilution from degradation of non-labeled glycogen....... It is suggested that further experiments uncovering the correlation between adrenergic and glutamatergic pathways should be performed in order to gain further insight into the role of astrocytes in brain function and dysfunction, the latter including excitotoxicity....

Studies on the effect of nano-TiO{sub 2} on vinyl acetate-butyl acrylate latex-based surface coating

Energy Technology Data Exchange (ETDEWEB)

Suma, K.K. [Dept. of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kochi 22, Kerala (India); Dept. of Chemistry, Maharaja' s College, Ernakulam, Kerala (India); Jacob, Sinto [Dept. of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kochi 22, Kerala (India); Joseph, Rani, E-mail: rani@cusat.ac.i [Dept. of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kochi 22, Kerala (India)

2010-04-15

Vinyl acetate-butyl acrylate (VAc-BuA) copolymer latex was prepared by emulsion polymerization. The polymerization conditions and the composition were optimized. The 85/15 wt.% (vinyl acetate/butyl acrylate) gave good tensile strength of the order of 15.6 MPa and a glass transition temperature (T{sub g}) value of -6.49 deg. C. This copolymer was used as a binder in the paint formulation. In this formulation nanosized TiO{sub 2} sol was used as a pigment instead of conventional rutile TiO{sub 2}. Nanosized TiO{sub 2} is prepared by wet process. These nanosized TiO{sub 2} rutile colloidal sol has improved properties such as photostability, UV shielding, dispersion stability, etc. The surface properties of paint were found to be superior compared to commercially used paint.

In vitro and in vivo study to the biocompatibility and biodegradation of hydroxyapatite/poly(vinyl alcohol)/gelatin composite.

NARCIS (Netherlands)

Wang, M.; Li, Y.; Wu, J.; Xu, F.; Zuo, Y.; Jansen, J.A.

2008-01-01

A novel porous composite material composed of hydroxyapatite, poly(vinyl alcohol) (PVA), and gelatin (Gel) was fabricated by emulsification. Scanning electron microscopy showed that the material had a well-interconnected porous structure including many macropores (100-500 microm) and micropores

21 CFR 700.14 - Use of vinyl chloride as an ingredient, including propellant of cosmetic aerosol products.

Science.gov (United States)

2010-04-01

... propellant of cosmetic aerosol products. 700.14 Section 700.14 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.14 Use of vinyl chloride as an ingredient, including propellant of cosmetic aerosol products...

Conjugate Addition of Nucleophiles to the Vinyl Function of 2-Chloro-4-vinylpyrimidine Derivatives

Directory of Open Access Journals (Sweden)

Lucjan Strekowski

2010-03-01

Full Text Available Conjugate addition reaction of various nucleophiles across the vinyl group of 2-chloro-4-vinylpyrimidine, 2-chloro-4-(1-phenylvinylpyrimidine and 2-chloro-4-vinylquinazoline provides the corresponding 2-chloro-4-(2-substituted ethylpyrimidines and 2-chloro-4-(2-substituted ethylquinazolines. Treatment of these products, without isolation, with N-methylpiperazine results in nucleophilic displacement of chloride and yields the corresponding 2,4-disubstituted pyrimidines and quinazolines.

Electro–optical properties of poly(vinyl acetate)/polyindole composite film

International Nuclear Information System (INIS)

Bhagat, D. J.; Dhokane, G. R.; Bajaj, N. S.

2016-01-01

In present work, electrical and optical properties of poly(vinyl acetate)/polyindole (PVAc/PIN) composite film are reported. The prepared composite was characterized via X–ray diffraction (XRD), UV–Vis spectroscopy and DC conductivity measurements. The polymer chain separation was determined using XRD analysis. An attempt has been made to study the temperature dependence of DC conductivity of PVAc/PIN composite in temperature range 308–373 K. The DC conductivity initially increases and reaches to 2.45×10–7 S/cm. The optical band gap value of composite is determined as 4.77 eV. The semiconducting nature of composite observed from electronic as well as optical band gap and Arrhenius behavior of DC plot.

Electro–optical properties of poly(vinyl acetate)/polyindole composite film

Energy Technology Data Exchange (ETDEWEB)

Bhagat, D. J., E-mail: bhagatd@rediffmail.com; Dhokane, G. R. [Arts, Science and Commerce College, Chikhaldara, 444807, Maharashtra (India); Bajaj, N. S. [Toshniwal Arts, Science and Commerce College, Sengaon, Maharashtra (India)

2016-05-06

In present work, electrical and optical properties of poly(vinyl acetate)/polyindole (PVAc/PIN) composite film are reported. The prepared composite was characterized via X–ray diffraction (XRD), UV–Vis spectroscopy and DC conductivity measurements. The polymer chain separation was determined using XRD analysis. An attempt has been made to study the temperature dependence of DC conductivity of PVAc/PIN composite in temperature range 308–373 K. The DC conductivity initially increases and reaches to 2.45×10–7 S/cm. The optical band gap value of composite is determined as 4.77 eV. The semiconducting nature of composite observed from electronic as well as optical band gap and Arrhenius behavior of DC plot.

Catalytic effect of different reactor materials under subcritical water conditions: decarboxylation of cysteic acid into taurine

Science.gov (United States)

Faisal, M.

2018-03-01

In order to understand the influence of reactor materials on the catalytic effect for a particular reaction, the decomposition of cysteic acid from Ni/Fe-based alloy reactors under subcritical water conditions was examined. Experiments were carried out in three batch reactors made of Inconel 625, Hastelloy C-22 and SUS 316 over temperatures of 200 to 300 °C. The highest amount of eluted metals was found for SUS 316. The results demonstrated that reactor materials contribute to the resulting product. Under the tested conditions, cysteic acid decomposes readily with SUS 316. However, the Ni-based materials (Inconel 625 and Hastelloy C-22) show better resistance to metal elution. It was found that among the materials used in this work, SUS 316 gave the highest reaction rate constant of 0.1934 s‑1. The same results were obtained at temperatures of 260 and 300 °C. Investigation of the Arrhenius activation energy revealed that the highest activation energy was for Hastelloy C-22 (109 kJ/mol), followed by Inconel 625 (90 kJ/mol) and SUS 316 (70 kJ/mol). The decomposition rate of cysteic acid was found to follow the results for the trend of the eluted metals. Therefore, it can be concluded that the decomposition of cysteic acid was catalyzed by the elution of heavy metals from the surface of the reactor. The highest amount of taurine from the decarboxylation of cysteic acid was obtained from SUS 316.

Laboratory characterization and astrophysical detection of vibrationally excited states of vinyl cyanide in Orion-KL

Science.gov (United States)

López, A.; Tercero, B.; Kisiel, Z.; Daly, A. M.; Bermúdez, C.; Calcutt, H.; Marcelino, N.; Viti, S.; Drouin, B. J.; Medvedev, I. R.; Neese, C. F.; Pszczółkowski, L.; Alonso, J. L.; Cernicharo, J.

2014-12-01

Context. We perform a laboratory characterization in the 18-1893 GHz range and astronomical detection between 80-280 GHz in Orion-KL with IRAM-30 m of CH2CHCN (vinyl cyanide) in its ground and vibrationally excited states. Aims: Our aim is to improve the understanding of rotational spectra of vibrationally excited vinyl cyanide with new laboratory data and analysis. The laboratory results allow searching for these excited state transitions in the Orion-KL line survey. Furthermore, rotational lines of CH2CHCN contribute to the understanding of the physical and chemical properties of the cloud. Methods: Laboratory measurements of CH2CHCN made on several different frequency-modulated spectrometers were combined into a single broadband 50-1900 GHz spectrum and its assignment was confirmed by Stark modulation spectra recorded in the 18-40 GHz region and by ab-initio anharmonic force field calculations. For analyzing the emission lines of vinyl cyanide detected in Orion-KL we used the excitation and radiative transfer code (MADEX) at LTE conditions. Results: Detailed characterization of laboratory spectra of CH2CHCN in nine different excited vibrational states: ν11 = 1, ν15 = 1, ν11 = 2, ν10 = 1 ⇔ (ν11 = 1,ν15 = 1), ν11 = 3/ν15 = 2/ν14 = 1, (ν11 = 1,ν10 = 1) ⇔ (ν11 = 2,ν15 = 1), ν9 = 1, (ν11 = 1,ν15 = 2) ⇔ (ν10 = 1,ν15 = 1) ⇔ (ν11 = 1,ν14 = 1), and ν11 = 4 are determined, as well as the detection of transitions in the ν11 = 2 and ν11 = 3 states for the first time in Orion-KL and of those in the ν10 = 1 ⇔ (ν11 = 1,ν15 = 1) dyad of states for the first time in space. The rotational transitions of the ground state of this molecule emerge from four cloud components of hot core nature, which trace the physical and chemical conditions of high mass star forming regions in the Orion-KL Nebula. The lowest energy vibrationally excited states of vinyl cyanide, such as ν11 = 1 (at 328.5 K), ν15 = 1 (at 478.6 K), ν11 = 2 (at 657.8 K), the ν10

Blends of ethylene-co-vinyl acetate and poly(3-hydroxybutyrate with adhesion property

Directory of Open Access Journals (Sweden)

A. de Lucas-Freile

2018-07-01

Full Text Available The structure and properties of ethylene-co-vinyl acetate (EVA and poly(3-hydroxybutyrate (PHB blends depended on their PHB content, i.e. PHB phase dominated the structure for amounts of PHB higher than 50 wt%, whereas EVA phase is dominant for PHB content lower than 50 wt%. EVA/PHB (70:30 blend showed unexpected different structure because of higher miscibility and the creation of new interfacial interactions between C=O and CH3 groups of PHB and CH3 and C=O groups of EVA, these interactions led changing of the phase structure of ethylene and vinyl acetate domains in EVA. As a consequence, improved thermal, viscoelastic and morphological properties were obtained. EVA+PHB blends containing 60 wt% or more PHB did not show tack and, interestingly, the addition of 20–30 wt% PHB enhanced the tack and displaced the maximum tack of pure EVA to lower temperature. The tack of EVA/PHB (70:30 blend was the highest among all blends because of its particular structure, fibrillation was also shown. Finally, the adhesion of EVA+PHB blends containing 20–30 wt% PHB to polypropylene (PP substrate was higher than the one of pure EVA because of the interactions between the ethylene domains in EVA phase of the blend and PP substrate surface.

Cosolvent gel-like materials from partially hydrolyzed poly(vinyl acetate)s and borax.

Science.gov (United States)

Angelova, Lora V; Terech, Pierre; Natali, Irene; Dei, Luigi; Carretti, Emiliano; Weiss, Richard G

2011-09-20

A gel-like, high-viscosity polymeric dispersion (HVPD) based on cross-linked borate, partially hydrolyzed poly(vinyl acetate) (xPVAc, where x is the percent hydrolysis) is described. Unlike hydro-HVPDs prepared from poly(vinyl alcohol) (PVA) and borate, the liquid portion of these materials can be composed of up to 75% of an organic cosolvent because of the influence of residual acetate groups on the polymer backbone. The effects of the degree of hydrolysis, molecular weight, polymer and cross-linker concentrations, and type and amount of organic cosolvent on the rheological and structural properties of the materials are investigated. The stability of the systems is explored through rheological and melting-range studies. (11)B NMR and small-angle neutron scattering (SANS) are used to probe the structure of the dispersions. The addition of an organic liquid to the xPVAc-borate HVPDs results in a drastic increase in the number of cross-linked borate species as well as the agglomeration of the polymer into bundles. These effects result in an increase in the relaxation time and thermal stability of the networks. The ability to make xPVAc-borate HVPDs with very large amounts of and rather different organic liquids, with very different rheological properties that can be controlled easily, opens new possibilities for applications of PVAc-based dispersions. © 2011 American Chemical Society

Poly(vinyl alcohol)/cellulose nanofibril hybrid aerogels with an aligned microtubular porous structure and their composites with polydimethylsiloxane

Science.gov (United States)

Tianliang Zhai; Qifeng Zheng; Zhiyong Cai; Lih-Sheng Turng; Hesheng Xia; Shaoqin Gong

2015-01-01

Superhydrophobic poly(vinyl alcohol) (PVA)/ cellulose nanofibril (CNF) aerogels with a unidirectionally aligned microtubular porous structure were prepared using a unidirectional freeze-drying process, followed by the thermal chemical vapor deposition of methyltrichlorosilane. The silanized aerogels were characterized using various techniques including scanning...

Synthesis of iron nanoparticles with poly(1-vinylpyrrolidone-co-vinyl acetate) and its application to nitrate reduction

DEFF Research Database (Denmark)

Lee, Nara; Choi, Kyunghoon; Uthuppu, Basil

2014-01-01

This study aimed to synthesize dispersed and reactive nanoscale zero-valent iron (nZVI) with poly(1-vinylpyrrolidone-co-vinyl acetate) (PVP/VA), nontoxic and biodegradable stabilizer. The nZVI used for the experiments was prepared by reduction of ferric solution in the presence of PVP/VA with spe...

Low-temperature radiation-induced polymerization of vinyl monomers in the crystal matrix of polydimethyl siloxane

International Nuclear Information System (INIS)

Mujdinov, M.R.; Kiryukhin, D.P.; Barkalov, I.M.; Gol'danskij, V.I.

1979-01-01

It is shown that in the process of the slow cooling of vinyl monomer solution in dimethyl siloxane rubber (SKT mark) crystallization of SKT takes place, at that, considerable part of vinyl monomers (up to 70 wt. % of rubber) is sorbed in the pores of crystal matrix and it does not form its proper crystal phase. Slight anomalies in heat capacity in the 120-140 K range, the melting of non-sorbed part of MA and the melting of SKT + MA ''complex'' have been observed on the calorimetric curve at the SKT - methylacrylate (MA) system heating. In the process of heating such samples, irradiated at 77 K by γ-rays of 60 Co, heat evolution connected with sorbed monomer polarization, has been observed starting from 125-130 K. In the 140-200 K range already before MA and SKT melting intense polymerization takes place, which results in practically full monomer consumption and formation of graft copolymer. Radiation-chemical yield of monomer reduction reaches G(-M) approximately equal to 2x10 5 molecules for 100 eV, radiation yield of postpolymerization of crystal MA does not exceed G(-M) approximately equal to 50 molecules for 100 eV

Mucoadhesive hydrogel microparticles based on poly (methacrylic acid-vinyl pyrrolidone)-chitosan for oral drug delivery.

Science.gov (United States)

Sajeesh, S; Sharma, Chandra P

2011-05-01

The study was aimed at the evaluation of N-vinyl pyrrolidone (NVP) incorporated polymethacrylic acid-chitosan microparticles for oral drug delivery applications. Poly (methacrylic acid)-chitosan (PMC) and poly(methacrylic acid-vinyl pyrrolidone)-chitosan (PMVC) microparticles were prepared by an ionic-gelation method. Mucoadhesion behaviour of these particles was evaluated by ex-vivo adhesion method using freshly excised rat intestinal tissue. Cytotoxicity and absorption enhancing property of PMC and PMVC particles were evaluated on Caco 2 cell monolayers. Protease enzyme inhibition capability and insulin loading/release properties of these hydrogel particles was evaluated under in vitro experimental conditions. Addition of NVP units enhanced the mucoadhesion behavior of PMC particles on isolated rat intestinal tissue. Both PMC and PMVC particles were found non-toxic on Caco 2 cell monolayers and PMC particles was more effective in improving paracellular transport of fluorescent dextran across Caco 2 cell monolayers as compared to PMVC particles. However, protease inhibition efficacy of PMC particles was not significantly affected with NVP addition. NVP incorporation improved the insulin release properties of PMC microparticles at acidic pH. Hydrophilic modification seems to be an interesting approach in improving mucoadhesion capability of PMC microparticles.

Additional conformer observed in the microwave spectrum of methyl vinyl ketone

Science.gov (United States)

Wilcox, David S.; Shirar, Amanda J.; Williams, Owen L.; Dian, Brian C.

2011-05-01

A chirped-pulse Fourier transform microwave spectrometer was used to record the rotational spectrum of methyl vinyl ketone (MVK, 3-butene-2-one). Two stable conformations were identified: the previously documented antiperiplanar (ap) conformer and synperiplanar (sp), which is reported for the first time in this microwave study. Methyl torsional analysis resulted in V3 barrier heights of 433.8(1) and 376.6(2) cm-1 for ap- and sp-MVK, respectively. Heavy atom isotopic species of both conformers were detected in natural abundance allowing bond lengths and angles of the molecular frames to be calculated through Kraitchman analysis. A comparison with ab initio calculations is included.

Graft Copolymerization of Styrene from Poly(vinyl alcohol via RAFT Process

Directory of Open Access Journals (Sweden)

Gholam Ali Koohmareh

2011-01-01

Full Text Available Polystyrene, PS, was grafted from poly(vinyl alcohol, PVA, backbone by reversible addition-fragmentation chain transfer (RAFT polymerization. The hydroxyl groups of the PVA were converted into aromatic dithioester RAFT agent and polymerization began in the presence of this agent. The structure of compounds was confirmed by FT-IR and 1HNMR spectroscopy. The graft copolymer was characterized by thermogravimetric analysis (TGA, X-ray diffraction (XRD, and scanning electron microscopy (SEM. Grafted polystyrene chains were cleaved from the PVA backbone by acidic hydrolysis of the PVA-g-PS, and its polydispersity index, PDI, was determined by gel permeation chromatography (GPC showing narrow molecular weight distribution.

Synthesis of PbS/poly (vinyl-pyrrolidone) nanocomposite

International Nuclear Information System (INIS)

Patel, Jayesh D.; Chaudhuri, Tapas K.

2009-01-01

A simple solution growth method for synthesis of nanocomposite of PbS nanoparticles in poly(vinyl-pyrrolidone) (PVP) polymer is described. The nanocomposite is prepared from methanolic solution of lead acetate (PbAc), thiourea (TU) and PVP at room temperature (∼27 deg. C). Optical absorption spectrum of PbS/PVP nanocomposite solution shows strong absorption from 300 to 650 nm with significant bands at 400 and 590 nm which is characteristic of nanoscale PbS. Spin-coated nanocomposite films on glass have an absorption edge at ∼650 nm with band gap of 2.55 eV. Fourier transform infrared (FTIR) spectroscopy of PbS/PVP nanocomposite and PVP shows strong chemical bond between PbS nanoparticles and host PVP polymer. The transmission electron microscope (TEM) images reveal that 5-10 nm PbS particles are evenly embedded in PVP polymer. The formation of PbS is confirmed by selective area electron diffraction (SAED) of a typical nanoparticle.

Analysis of phthalate ester content in poly(vinyl chloride) plastics by means of Fourier transform Raman spectroscopy

DEFF Research Database (Denmark)

Nørbygaard, Thomas; Berg, Rolf W.

2004-01-01

Fourier transform (FT) Raman spectroscopy is applied to a range of phthalate ester plasticizers in pure form as well as in poly(vinyl chloride) (PVC) samples. It is found that phthalate esters as a group can be identified by a set of six characteristic Raman bands. FT-Raman spectra of 22 phthalate...

Hydrogels based on chemically modified poly(vinyl alcohol (PVA-GMA and PVA-GMA/chondroitin sulfate: Preparation and characterization

Directory of Open Access Journals (Sweden)

E. C. Muniz

2012-05-01

Full Text Available This work reports the preparation of hydrogels based on PVA-GMA, PVA-GMA is poly(vinyl alcohol (PVA functionalized with vinyl groups from glycidyl methacrylate (GMA, and on PVA-GMA with different content of chondroitin sulfate (CS. The degrees of swelling of PVA-GMA and PVA-GMA/CS hydrogels were evaluated in distilled water and the swelling kinetics was performed in simulated gastric and intestinal fluids (SGF and SIF. PVA-GMA and PVAGMA/CS hydrogels demonstrated to be resistant on SGF and SIF fluids. The elastic modulus, E, of swollen-hydrogels were determined through compressive tests and, according to the obtained results, the hydrogels presented good mechanical properties. At last, the presence of CS enhances the hydrogel cell compatibility as gathered by cytotoxicity assays. It was concluded that the hydrogels prepared through this work presented characteristics that allow them to be used as biomaterial, as a carrier in drug delivery system or to act as scaffolds in tissue engineering as well.

An organic dye-polymer (phenol red-poly (vinyl alcohol)) composite architecture towards tunable -optical and -saturable absorption characteristics

Energy Technology Data Exchange (ETDEWEB)

Sreedhar, Sreeja, E-mail: sreejasreedhar83@gmail.com; Muneera, C. I., E-mail: drcimuneera@hotmail.com [Department of Physics, University of Kerala, Kariavattom, Thiruvananthapuram 695581, Kerala (India); Illyaskutty, Navas [Institute for Sensorics and Information Systems (ISIS), Karlsruhe University of Applied Sciences, Moltkestr. 30, D-76133 Karlsruhe (Germany); Sreedhanya, S. [School of Chemical Sciences, M. G. University, Kottayam, Kerala 686560 (India); Philip, Reji [Light and Matter Physics Group, Raman Research Institute, Bangalore 560080 (India)

2016-05-21

Herein, we demonstrate that blending an organic dye (guest/filler), with a vinyl polymer (host template), is an inexpensive and simple approach for the fabrication of multifunctional photonic materials which could display an enhancement in the desirable properties of the constituent materials and, at the same time provide novel synergistic properties for the guest-host system. A new guest-host nanocomposite system comprising Phenol Red dye and poly (vinyl alcohol) as guest and host template, respectively, which exhibits tunable optical characteristics and saturable absorption behavior, is introduced. The dependence of local electronic environment provided by the polymer template and the interactions of the polymer molecules with the encapsulated guest molecules on the observed optical/nonlinear absorption behavior is discussed. An understanding of the tunability of the optical/ photophysical processes, with respect to the filler content, as discussed herein could help in the design of improved optical materials for several photonic device applications like organic light emitting diodes and saturable absorbers.

Acute effects of sodium valproate and gamma-vinyl GABA on regional amino acid metabolism in the rat brain: incorporation of 2-[14C]glucose into amino acids.

Science.gov (United States)

Chapman, A G; Riley, K; Evans, M C; Meldrum, B S

1982-09-01

Amino acid concentrations have been determined in rat brain regions (cortex, striatum, cerebellum, and hippocampus) by HPLC after administration of acute anticonvulsant doses of sodium valproate (400 mg/kg, i.p.) and gamma-vinyl-GABA (1 g/kg, i.p.). After valproate administration the GABA level increases only in the cortex; aspartic acid concentration decreases in the cortex and hippocampus, and glutamic acid decreases in the hippocampus and striatum and increases in the cortex and cerebellum. There are no changes in the concentrations of glutamine, taurine, glycine, serine, and alanine following valproate administration. Only the GABA level increases in all the regions after gamma-vinyl-GABA administration. Cortical analyses 2, 4 and 10 minutes after pulse labeling with 2-[14C]glucose, i.v., show no change in the rate of cortical glucose utilization in the valproate treated group. The rate of labeling of glutamic acid is also unchanged, but the rate of labeling of GABA is reduced following valproate administration. After gamma-vinyl-GABA administration there is no change in the rate of labeling of GABA. These biochemical findings can be interpreted in terms of a primary anticonvulsant action of valproate on membrane receptors with secondary effects on the metabolism of amino acid neurotransmitters. This contrasts with the primary action of gamma-vinyl-GABA on GABA-transaminase activity.

Inclusion polymerization of vinyl chloride monomer in deoxycholic acid host via {gamma}-ray irradiation

Energy Technology Data Exchange (ETDEWEB)

Chirachanchai, S.; Kumkrong, A. [The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok (Thailand); Ishida, Hatsuo [Department of Macromolecular Science, Case Western Reserve University, Cleveland, OH (United States)

2000-03-01

Inclusion polymerization of vinyl chloride monomer (VCM) was studied in the system of 3{alpha}, 12{alpha} -dihydroxy-5{beta}-cholan-24-oic acid (deoxycholic acid, DCA). DCA-VCM inclusion compound system was originally prepared by guest intercalation technique in DCA guest free crystal. The inclusion polymerization of DCA-VCM by {gamma}-irradiation at total dose 2 Mrad, gives a syndiotactic rich polyvinyl chloride (PVC) as can be confirmed by FT-IR and FT-NMR. (author)

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

International Nuclear Information System (INIS)

Chirachanchai, S.; Kumkrong, A.; Ishida, Hatsuo

2000-01-01

Inclusion polymerization of vinyl chloride monomer (VCM) was studied in the system of 3α, 12α -dihydroxy-5β-cholan-24-oic acid (deoxycholic acid, DCA). DCA-VCM inclusion compound system was originally prepared by guest intercalation technique in DCA guest free crystal. The inclusion polymerization of DCA-VCM by γ-irradiation at total dose 2 Mrad, gives a syndiotactic rich polyvinyl chloride (PVC) as can be confirmed by FT-IR and FT-NMR. (author)

Synthesis and Nrf2 Activating Ability of Thiourea and Vinyl Sulfoxide Derivatives

Energy Technology Data Exchange (ETDEWEB)

Shim, Young Sun; Hwang, Hyun Sook; Nam, Ghilsoo; Choi, Kyung Il [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

2013-08-15

Thiourea and vinyl sulfoxide derivatives were designed based on the structures of sulforaphene and gallic acid, prepared and tested for HO-1 inducing activity as a measure of Nrf2 activation, and inhibitory effect on NO production as a measure of anti-inflammatory activity. Both series of compounds showed moderate activity on HO-1 induction, and no inhibitory effect on NO production. Interestingly the thiourea compound 6d showed better HO-1 induction (71% SFN) than the corresponding isothiocyanate compound 6a (55% SFN). Overall, it seemed that more efficient electrophile is needed to get more effective Nrf2 activator.

Poly(vinyl acetate)/clay nanocomposite materials for organic thin film transistor application.

Science.gov (United States)

Park, B J; Sung, J H; Park, J H; Choi, J S; Choi, H J

2008-05-01

Nanocomposite materials of poly(vinyl acetate) (PVAc) and organoclay were fabricated, in order to be utilized as dielectric materials of the organic thin film transistor (OTFT). Spin coating condition of the nanocomposite solution was examined considering shear viscosity of the composite materials dissolved in chloroform. Intercalated structure of the PVAc/clay nanocomposites was characterized using both wide-angle X-ray diffraction and TEM. Fracture morphology of the composite film on silicon wafer was also observed by SEM. Dielectric constant (4.15) of the nanocomposite materials shows that the PVAc/clay nanocomposites are applicable for the gate dielectric materials.

Intermolecular Dehydrative Coupling Reaction of Arylketones with Cyclic Alkenes Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: A Novel Ketone Olefination Method via Vinyl C–H Bond Activation

Science.gov (United States)

Yi, Chae S.; Lee, Do W.

2010-01-01

Summary The cationic ruthenium-hydride complex [(η6-C6H6)(PCy3)(CO)RuH]+BF4− was found to be a highly effective catalyst for the intermolecular olefination reaction of arylketones with cycloalkenes. The preliminary mechanistic analysis revealed that electrophilic ruthenium-vinyl complex is the key species for mediating both vinyl C–H bond activation and the dehydrative olefination steps of the coupling reaction. PMID:20567607

Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediate

Directory of Open Access Journals (Sweden)

Ambrósio João Carlos L.

2003-01-01

Full Text Available Two concise and enantioselective syntheses of the necine base precursors (1R,5R-N-Cbz and N-Boc-2-oxa-6-azabicyclo[3.3.0]octan-3-ones (Geissman-Waiss lactones were carried out from two enantiomerically pure endocyclic five-membered enecarbamates with overall yields of 23% and 26%, respectively. The synthetic strategy made use of a highly effective and stereoselective [2+2]cycloaddition of enantiomerically pure endocyclic enecarbamates with dichloroketene, as well as an efficient decarboxylation step of a bicyclic alpha-amino acid employing Boger's acyl selenide protocol employing tributyltin hydride. Interesting aspects concerning the regiochemical outcome of Baeyer-Villiger oxidations of bicyclic cyclobutanones are also reported, in which the usual stereoelectronic bias of Baeyer-Villiger oxidation seems to be counterbalanced by steric effects on the putative Criegee intermediate.

Crossover from Rouse dynamics to the α- relaxation in a poly(vinyl ethylene)

International Nuclear Information System (INIS)

Arbe, A.; Colmenero, J.; Richter, D.; Monkenbusch, M.; Willner, L.; Farago, B.

2004-01-01

By means of neutron spin echo (NSE) we have explored the dynamics of poly(vinyl ethylene) on length scales covering Rouse dynamics and below. The results establish the simultaneous existence of a generic sublinear diffusion regime which underlies the α-process in addition to the Rouse process. Both regimes are separated by a well- defined dynamic crossover. From that the size of the Gaussian blobs making up the Rouse model is determined directly. The glassy dynamics may thus be identified with subdiffusive motions occurring within these Gaussian blobs. (author)

Convenient synthesis of N,N'-dibenzyl-2,4-diaminopyrimidine-2'-deoxyribonucleoside and 1-methyl-2'-deoxypseudoisocytidine

CSIR Research Space (South Africa)

Wellington, Kevin W

2009-04-01

Full Text Available The syntheses of N,N'-dibenzyl-2,4-diaminopyrimidine-2'-deoxyribonucleoside and 1-methyl-2'- deoxypseudoisocytidine via Heck coupling are described. A survey of the attempts to use the Heck coupling to synthesize N,N'-dibenzyl-2,4-diaminopyrimidine...

De Novo Biosynthesis of Glutarate via α-Keto Acid Carbon Chain Extension and Decarboxylation Pathway in Escherichia coli.

Science.gov (United States)

Wang, Jian; Wu, Yifei; Sun, Xinxiao; Yuan, Qipeng; Yan, Yajun

2017-10-20

Microbial based bioplastics are promising alternatives to petroleum based synthetic plastics due to their renewability and economic feasibility. Glutarate is one of the most potential building blocks for bioplastics. The recent biosynthetic routes for glutarate were mostly based on the l-lysine degradation pathway from Pseudomonas putida that required lysine either by feeding or lysine overproduction via genetic manipulations. Herein, we established a novel glutarate biosynthetic pathway by incorporation of a "+1" carbon chain extension pathway from α-ketoglutarate (α-KG) in combination with α-keto acid decarboxylation pathway in Escherichia coli. Introduction of homocitrate synthase (HCS), homoaconitase (HA) and homoisocitrate dehydrogenase (HICDH) from Saccharomyces cerevisiae into E. coli enabled "+1" carbon extension from α-KG to α-ketoadipate (α-KA), which was subsequently converted into glutarate by a promiscuous α-keto acid decarboxylase (KivD) and a succinate semialdehyde dehydrogenase (GabD). The recombinant E. coli coexpressing all five genes produced 0.3 g/L glutarate from glucose. To further improve the titers, α-KG was rechanneled into carbon chain extension pathway via the clustered regularly interspersed palindromic repeats system mediated interference (CRISPRi) of essential genes sucA and sucB in tricarboxylic acid (TCA) cycle. The final strain could produce 0.42 g/L glutarate, which was increased by 40% compared with the parental strain.

Synthesis and properties of the metallo-supramolecular polymer hydrogel poly[methyl vinyl ether-alt-mono-sodium maleate]·AgNO3: Ag+/Cu2+ ion exchange and effective antibacterial activity

KAUST Repository

Xu, Feng

2014-01-01

The commercial polymeric anhydride poly(methyl vinyl ether-alt-maleic anhydride) (PVM/MA) is converted by reaction with NaOH to give poly(methyl vinyl ether-alt-mono-sodium maleate) (PVM/Na-MA). By addition of AgNO 3-solution, the formation of the silver(i) supramolecular polymer hydrogel poly[methyl vinyl ether-alt-mono-sodium maleate]·AgNO 3 is reported. Freeze-dried samples of the hydrogel show a mesoporous network of polycarboxylate ligands that are crosslinked by silver(i) cations. In the intact hydrogel, ion-exchange studies are reported and it is shown that Ag+ ions can be exchanged by copper(ii) cations without disintegration of the hydrogel. The silver(i) hydrogel shows effective antibacterial activity and potential application as burn wound dressing. © the Partner Organisations 2014.

Practical synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides via conventional and decarboxylative copper-free Sonogashira coupling reactions

Directory of Open Access Journals (Sweden)

Andrea Caporale

2014-02-01

Full Text Available Two efficient protocols for the palladium-catalyzed synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides in the absence of copper were developed. A simple catalytic system consisting of Pd(OAc2 and P(p-tol3 using DBU as the base and THF as the solvent was found to be highly effective for the coupling reaction of 2-methyl-3-butyn-2-ol (4 with a wide range of aryl bromides in good to excellent yields. Analogously, the synthesis of aryl-2-methyl-3-butyn-2-ols was performed also through the decarboxylative coupling reaction of 4-hydroxy-4-methyl-2-pentynoic acid with aryl bromides, using a catalyst containing Pd(OAc2 in combination with SPhos or XPhos in the presence of tetra-n-butylammonium fluoride (TBAF as the base and THF as the solvent. Therefore, new efficient approaches to the synthesis of terminal acetylenes from widely available aryl bromides rather than expensive iodides and using 4 or propiolic acid rather than TMS-acetylene as inexpensive alkyne sources are described.

Novel proton exchange membrane based on crosslinked poly(vinyl alcohol) for direct methanol fuel cells

Science.gov (United States)

Liu, Chien-Pan; Dai, Chi-An; Chao, Chi-Yang; Chang, Shoou-Jinn

2014-03-01

In this study, we report the synthesis and the characterization of poly (vinyl alcohol) based proton conducting membranes. In particular, we describe a novel physically and chemically PVA/HFA (poly (vinyl alcohol)/hexafluoroglutaric acid) blending membranes with BASANa (Benzenesulfonic acid sodium salt) and GA (Glutaraldehyde) as binary reaction agents. The key PEM parameters such as ion exchange capacity (IEC), water uptake, proton conductivity, and methanol permeability were controlled by adjusting the chemical composition of the membranes. The IEC value of the membrane is found to be an important parameter in affecting water uptake, conductivity as well as the permeability of the resulting membrane. Plots of the water uptake, conductivity, and methanol permeability vs. IEC of the membranes show a distinct change in the slope of their curves at roughly the same IEC value which suggests a transition of structural changes in the network. The proton conductivities and the methanol permeability of all the membranes are in the range of 10-3-10-2 S cm-1 and 10-8-10-7 cm2 s-1, respectively, depending on its binary crosslinking density, and it shows great selectivity compared with those of Nafion®-117. The membranes display good mechanical properties which suggest a good lifetime usage of the membranes applied in DMFCs.

Tailoring the morphology and properties of poly(lactic acid)/poly(ethylene-co-vinyl acetate)/starch blends via reactive compatibilization

NARCIS (Netherlands)

Ma, P.; Hristova - Bogaerds, D.G.; Schmit, P.; Goossens, J.G.P.; Lemstra, P.J.

2012-01-01

Poly(lactic acid)/poly(ethylene-co-vinyl acetate)/starch (PLA/EVA/starch) ternary blends were prepared by multi-step melt processing (reactive extrusion) in the presence of maleic anhydride (MA), benzoyl peroxide and glycerol. The effects of MA and glycerol concentration on the morphology and

Birefringence and dichroism of poly(vinyl-alcohol) foils containing phthalazinium ylids

Science.gov (United States)

Rogojanu, Alina; Dascalu, Carmen Felicia; Zelinschi, Beatrice Carmen; Caprosu, Maria; Dorohoi, Dana Ortansa

2011-10-01

Pure and colored with phthalazinium ylids poly(vinyl-alcohol) (PVA) foils were stretched under gentile heating. The birefringence of the thin foils was determined with a Babinet compensator standardized for yellow radiation of a Sodium lamp. The determined birefringence of the colored PVA foils is higher than that of the pure PVA foils. This fact indicates that the phthalazinium ylids facilitate the increase in the anisotropy of the stretched foils. The visible absorption electronic band of phthalazinium ylids was used to estimate the dichroic ratio and the degree of order of the ylid molecules in the stretched PVA foils. An increase in dichroism and birefringence with the degree of stretching has been evidenced for uncolored and colored PVA foils.

A photo-crosslinked poly(vinyl alcohol) hydrogel growth factor release vehicle for wound healing applications

OpenAIRE

Bourke, Sharon L.; Al-Khalili, Mohammad; Briggs, Tonye; Michniak, Bozena B.; Kohn, Joachim; Poole-Warren, Laura A.

2003-01-01

The objective of this study was to develop and evaluate a hydrogel vehicle for sustained release of growth factors for wound healing applications. Hydrogels were fabricated using ultraviolet photo-crosslinking of acrylamide-functionalized nondegradable poly(vinyl alcohol) (PVA). Protein permeability was initially assessed using trypsin inhibitor (TI), a 21 000 MW model protein drug. TI permeability was altered by changing the solids content of the gel and by adding hydrophilic PVA fillers. As...

Heck and Heckle Seamounts, northeast Pacific Ocean: High extrusion rates of primitive and highly depleted mid-ocean ridge basalt on off-ridge seamounts

Science.gov (United States)

Leybourne, M. I.; van Wagoner, N. A.

1991-09-01

We analyzed, petrographically and chemically, basalt from eight dredge hauls from the Heck and Heckle seamounts, northeast Pacific Ocean. Major elements were determined for mineral, glass, and whole rock samples, and trace and rare earth elements were determined for glass and whole rock samples. The dredge hauls included hyaloclastites and fragments from sheet flows and pillows. The clinkery fragments are interpreted to be deformed sheet flow tops, characteristic of high effusion rates. The hyaloclastites recovered are reworked deposits, as indicated by the wide compositional range of the glass shards, abundance of clay and calcite matrix, and bedding. Most rocks are aphyric, but the analyzed plagioclase and olivine phenocrysts and microcrysts are equilibrium compositions and show minor compositional zonation (up to 7.5% An, chains have a limited range of incompatible element ratios, whereas the adjacent West Valley Segment of the Juan de Fuca Ridge is highly heterogeneous. In contrast, lavas from the East Pacific near-ridge seamounts exhibit a wider range of incompatible element ratios than do the adjacent East Pacific Rise basalts. On the West Valley Segment, magma supply is less robust associated with lower spreading rates compared to the East Pacific Rise at 10°N. In contrast, at fast spreading centers robust melting produces a mixed mantle signature in axial lavas, while suppressed melting at the seamounts reveals the heterogeneities. We suggest that at some spreading ridges, more fertile portions of the mantle are preferentially melted such that the outwelled portions of the mantle tapped by the seamounts are more depleted.

Methyl internal rotation in the microwave spectrum of vinyl acetate.

Science.gov (United States)

Nguyen, Ha Vinh Lam; Jabri, Atef; Van, Vinh; Stahl, Wolfgang

2014-12-26

The rotational spectrum of vinyl acetate, CH3(CO)OCH═CH2, was measured using two molecular beam Fourier transform microwave spectrometers operating in the frequency range from 2 to 40 GHz. Large splittings up to 2 GHz occurred due to the internal rotation of the acetyl methyl group CH3CO with a V3 potential of 151.492(34) cm(-1), much larger than the barrier of approximately 100 cm(-1) often found in acetates. The torsional transitions were fitted using three different programs XIAM, ERHAM, and BELGI-Cs, whereby the rotational constants, centrifugal distortion constants, and the internal rotation parameters could be determined with very high accuracy. The experimental results were supported by quantum chemical calculations. For a conformational analysis, potential energy surfaces were calculated.

Poly(vinyl pyrrolidone) (PVP) hydrogels study for ophthalmologic area utilization

International Nuclear Information System (INIS)

Amaral, Renata Hage; Rogero, Sizue Ota; Lugao, Ademar Benevolo; Cruz, Aurea S.; Sacramento, Rogerio S.; Lima Filho, Acacio A. Souza; Schor, Paulo

2005-01-01

Poly (vinyl pyrrolidone) (PVP) hydrogels produced by radiation-induced crosslinking were studied to compose drug delivery system to be used in the eye surface and to manufacture ophthalmic plugs. Some formulations with PVP and poly ethylene glycol (PEG) with different molar mass (300 and 600) were prepared utilizing 0.85% sodium chloride aimed to control the swelling capacity. The obtained hydrogels were characterized by gel fraction and swelling assays. The gel fraction and swelling results indicated no difference in the formulation containing or not NaCl. The gel fraction results varied from 62 to 81% and the swelling degree from 130 to 420%. In vitro assay of cytotoxicity by neutral red uptake method was the first biocompatibility test performed. The results showed no evidence of toxicity in the studied hydrogels. (author)

Data from one test "Semi-Volatile Organic Compound Small Chamber for bis (2-Ethylhexyl) phthalate in Vinyl Flooring Test 2"

Science.gov (United States)

This data was generated from a small chamber bis(2-ethylhexyl) phthalate (DEHP) emission test. It was to participate an interaboratory study of DEHP emissions from vinyl flooring in a SVOC emission chamber organized by Virginia Polytechnic Institute and State University (VT).

Transcatheter Embolization of a Renal Artery Aneurysm Using Ethylene Vinyl Alcohol Copolymer

International Nuclear Information System (INIS)

Rautio, Riitta; Haapanen, Arto

2007-01-01

Our aim was to treat a clinically silent renal artery aneurysm. The patient was a 76-year-old man with elevated prostate-specific antigen and prostata biopsies with a gradus II-III adenocarcinoma who was incidentally found to have an aneurysm in his right renal artery. We performed a successful transcatheter embolization of the aneurysm using ethylene vinyl alcohol copolymer (Onyx). To avoid migration of the liquid material into the parent artery, a balloon was inflated in the orifice of the neck of the aneurysm while the liquid was injected. Five-month follow-up computed tomography (CT) imaging confirmed total occlusion of the aneurysm

Study on dehydrochlorination of waste poly (vinyl chloride) resins by microwave irradiation

Science.gov (United States)

Moriwaki, Saburo; Qian, Qingrong; Sunohara, Satoshi; Machida, Motoi; Tatsumoto, Hideki

Waste poly (vinyl chloride: PVC) resins are experimentally dehydrochlorinated by microwave irradiation. The following unique results are obtained: (1) plasticizer in PVC resin absorbs microwave power more effectively than PVC polymer. The higher the plasticizer content in PVC resin, the higher is the dehydrochlorination reaction (2) low PVC polymer content materials such as cushion floor require high microwave irradiation power to secure a high dehydrochlorination yield, (3) calcium carbonate in PVC resin reacts with released hydrochloric acid gas and results calcium chloride during microwave irradiation, (4) additives in PVC resin strongly influence dehydrochlorination yield, (5) it is evidenced that the PVC copolymer is also dehydrochlorinated by microwave irradiation.