WorldWideScience

Sample records for pyrrolidinones

  1. Atmospheric chemistry of 1-methyl-2-pyrrolidinone

    Science.gov (United States)

    Aschmann, Sara M.; Atkinson, Roger

    Rate constants for the atmospheric reactions of 1-methyl-2-pyrrolidinone with OH radicals, NO 3 radicals and O 3 have been measured at 296±2 K and atmospheric pressure of air, and the products of the OH radical and NO 3 radical reactions investigated. Using relative rate techniques, rate constants for the gas-phase reactions of OH and NO 3 radicals with 1-methyl-2-pyrrolidinone of (2.15±0.36)×10 -11 cm 3 molecule -1 s -1 and (1.26±0.40)×10 -13 cm 3 molecule -1 s -1, respectively, were measured, where the indicated errors include the estimated overall uncertainties in the rate constants for the reference compounds. An upper limit to the rate constant for the O 3 reaction of radical reaction and the nighttime NO 3 radical reaction being important loss processes. Products of the OH radical and NO 3 radical reactions were analyzed by gas chromatography with flame ionization detection and combined gas chromatography-mass spectrometry. N-methylsuccinimide and (tentatively) 1-formyl-2-pyrrolidinone were identified as products of both of these reactions. The measured formation yields of N-methylsuccinimide and 1-formyl-2-pyrrolidinone were 44±12% and 41±12%, respectively, from the OH radical reaction and 59±16% and ˜4%, respectively, from the NO 3 radical reaction. Reaction mechanisms consistent with formation of these products are presented.

  2. Infrared Study of Solvent-Solute Interactions of 1-Substituted 2-Pyrrolidinones and Related Compounds

    NARCIS (Netherlands)

    Perjéssy, A.; Engberts, J.B.F.N.

    1995-01-01

    The wavenumbers of the carbonyl stretching vibrations of 2-pyrrolidinone (P), 1-methyl-2-pyrrolidinone (MP), 1-isopropyl-2-pyrrolidinone (IPP), 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), 2-oxobenzothiazole (OBT), and 3-octyl-2-oxobenzothiazole (OOBT) were measured in n-hexane/CDCl3, acetonitrile/D2O,

  3. Challenges in Catalytic Manufacture of Renewable Pyrrolidinones from Fermentation Derived Succinate

    Energy Technology Data Exchange (ETDEWEB)

    White, James F.; Holladay, Johnathan E.; Zacher, Alan H.; Frye, John G.; Werpy, Todd A.

    2014-09-05

    Fermentation derived succinic acid ammonium salt is an ideal precursor for manufacture of renewable N-methyl pyrrolidinone (NMP) or 2-pyrrolidinone (2P) via heterogeneous catalysis. However, there are many challenges to making this a practical reality. Chief among the challenges is avoiding catalyst poisoning by fermentation by- and co-products. Battelle / Pacific Northwest National Laboratory (PNNL) have developed an economically effective technology strategy for this purpose. The technology is a combination of purely thermal processing, followed by simple catalytic hydrogenation that together avoids catalyst poisoning from fermentation impurities and provides high selectivity and yields of NMP or 2P.

  4. Solvent effects on C=O stretching frequencies of some 1-substituted 2-pyrrolidinones

    NARCIS (Netherlands)

    Engberts, J.B.F.N.; Famini, G.R.; Perjéssy, A.; Wilson, L.Y.

    1998-01-01

    In an effort to model solute–solvent interactions, the C=O stretching frequencies of five 1-substituted 2-pyrrolidinones and four other carbonyl-containing compounds were measured for 30 common solvents. These were then correlated with four empirical parameter sets and one theoretical

  5. Pyrrolidinone derivatives as processing additives for solution processed organic solar cells

    Science.gov (United States)

    Vongsaysy, Uyxing; Pavageau, Bertrand; Servant, Laurent; Aziz, Hany

    2014-10-01

    Processing additives are widely used to increase the efficiency of solution processed organic solar cells. We use the Hansen solubility parameters (HSPs) to investigate novel processing additives. The HSPs predict pyrrolidinone derivatives to be efficient processing additives for OSC systems based on poly(3-hexylthiophene)/[6,6]-phenyl-C61- butyric acid methyl ester (P3HT/PCBM). Two pyrrolidinone derivatives are identified: 1-methyl-2-pyrrolidinone and 1- benzyl-2-pyrrolidinone. The processing additives are introduced with various concentrations in the formulation of P3HT and PCBM solution. The electrical characterizations show that the two processing additives significantly increase the short circuit current and thus the power conversion efficiency of the OSCs. The results thus highlight HSPs as an effective and relatively straightforward tool that can be employed to optimize OSC morphology from a theoretical standpoint. Such a tool will be invaluable for identifying additives for novel high efficiency polymer species as they are synthesized, and thus to streamline the device fabrication and device optimization process.

  6. The Solvent Mixture Sensitivity of Carbonyl Stretching Frequencies of 2-Pyrrolidinones and Related Compounds

    NARCIS (Netherlands)

    Perjessy, A.; Engberts, J.B.F.N.; Blandamer, M.J.

    1995-01-01

    The carbonyl stretching frequencies of 1-substituted 2-pyrrolidinones and related compounds were measured in binary mixtures of hexane-CDCl3 and acetonitrile-D2O and plotted against the mole fraction of the less polar co-solvent The v(C=O) vs. mole fraction correlations enabled to recognize and assi

  7. Solvent effects on C=O stretching frequencies of some 1-substituted 2-pyrrolidinones

    NARCIS (Netherlands)

    Engberts, J.B.F.N.; Famini, G.R.; Perjéssy, A.; Wilson, L.Y.

    1998-01-01

    In an effort to model solute–solvent interactions, the C=O stretching frequencies of five 1-substituted 2-pyrrolidinones and four other carbonyl-containing compounds were measured for 30 common solvents. These were then correlated with four empirical parameter sets and one theoretical (computational

  8. Noninnocent role of N-methyl pyrrolidinone in thiazolidinethione-promoted asymmetric aldol reactions.

    Science.gov (United States)

    Sreenithya, A; Sunoj, Raghavan B

    2012-11-16

    The origin of stereoselectivity in the reaction between α-azido titanium enolate derived from chiral auxiliary N-acyl thiazolidinethione and benzaldehyde is established using the DFT(B3LYP) method. A nonchelated transition state with N-methyl-2-pyrrolidinone (NMP) bound to a TiCl(3) enolate is found to be energetically the most preferred model responsible for the formation of an Evans syn aldol product. The TS model devoid of NMP, although of higher energy, is found to be successful in predicting the right stereochemical outcome.

  9. Thermodynamic Properties of Ternary Liquid Mixtures of 2-Pyrrolidinone with Aromatic Hydrocarbons

    Science.gov (United States)

    Yadav, Jaibir S.; Sharma, Dimple; Sharma, Vinod Kumar

    2010-02-01

    Molar excess volumes, {V^E_{ijk}}, and speeds of sound, u ijk , of 2-pyrrolidinone (2-Py) ( i) + toluene ( j) + o-xylene or p-xylene ( k) ternary mixtures have been determined by using a dilatometer and interferometer as a function of composition at 308.15 K. The speeds of sound of ternary mixtures have been utilized to predict their excess isentropic compressibilities. The Redlich-Kister equation has been fitted to the molar excess volumes, {V^E_{ijk}}, and excess isentropic compressibilities, {left( {kappa _S^E}right)_{ijk}}, to predict ternary adjustable parameters and standard deviations. The observed data have been analyzed in terms of the Flory theory and the Sanchez and Lacombe theory.

  10. Probing binding and cellular activity of pyrrolidinone and piperidinone small molecules targeting the urokinase receptor.

    Science.gov (United States)

    Mani, Timmy; Liu, Degang; Zhou, Donghui; Li, Liwei; Knabe, William Eric; Wang, Fang; Oh, Kyungsoo; Meroueh, Samy O

    2013-12-01

    The urokinase receptor (uPAR) is a cell-surface protein that is part of an intricate web of transient and tight protein interactions that promote cancer cell invasion and metastasis. Here, we evaluate the binding and biological activity of a new class of pyrrolidinone and piperidinone compounds, along with derivatives of previously-identified pyrazole and propylamine compounds. Competition assays revealed that the compounds displace a fluorescently labeled peptide (AE147-FAM) with inhibition constant (Ki ) values ranging from 6 to 63 μM. Structure-based computational pharmacophore analysis followed by extensive explicit-solvent molecular dynamics (MD) simulations and free energy calculations suggested the pyrazole-based and piperidinone-based compounds adopt different binding modes, despite their similar two-dimensional structures. In cells, pyrazole-based compounds showed significant inhibition of breast adenocarcinoma (MDA-MB-231) and pancreatic ductal adenocarcinoma (PDAC) cell proliferation, but piperidinone-containing compounds exhibited no cytotoxicity even at concentrations of 100 μM. One pyrazole-based compound impaired MDA-MB-231 invasion, adhesion, and migration in a concentration-dependent manner, while the piperidinone inhibited only invasion. The pyrazole derivative inhibited matrix metalloprotease-9 (gelatinase) activity in a concentration-dependent manner, while the piperidinone showed no effect suggesting different mechanisms for inhibition of cell invasion. Signaling studies further highlighted these differences, showing that pyrazole compounds completely inhibited ERK phosphorylation and impaired HIF1α and NF-κB signaling, while pyrrolidinones and piperidinones had no effect. Annexin V staining suggested that the effect of the pyrazole-based compound on proliferation was due to cell killing through an apoptotic mechanism. The compounds identified represent valuable leads in the design of further derivatives with higher affinities and

  11. Pairwise Gibbs energies of interaction involving N-alkyl-2- pyrrolidinones and related compounds in aqueous solution obtained from kinetic medium effects

    NARCIS (Netherlands)

    Apperloo, Joke J.; Streefland, Lisette; Engberts, Jan B.F.N.; Blandamer, Michael J.

    2000-01-01

    Kinetic solvent effects of N-alkyl-2-pyrrolidinones and structurally related compounds on the water-catalyzed hydrolysis reactions of p-methoxyphenyl dichloroacetate (MPDA), 1-benzoyl-3-phenyl-1,2,4-triazole (BPhT), and 1-benzoyl-1,2,4-triazole (BT) in highly dilute aqueous solutions at pH 4 and 298

  12. Substrate-induced coagulation (SIC) of nano-disperse alumina in non-aqueous media: The dispersibility and stability of alumina in N-methyl-2-pyrrolidinone

    OpenAIRE

    Basch, Angelika; Strnad, Simona

    2011-01-01

    This work investigated colloidal properties such as the zeta-potential, the electrophoretic mobilities and the wetting behaviour of alumina dispersed in non-aqueous media. Non-aqueous dispersions of alumina were prepared in the solvent N-methyl-2-pyrrolidinone (NMP). The wetting behaviour of alumina in NMP was characterized by the powder contact angle method and the Wilhemy plate method. The behaviour of the dispersion should provide information for the development of a substrate-induced coag...

  13. Optical evidence for chemical interaction of the polyaniline/fullerene composites with N-methyl-2-pyrrolidinone

    Science.gov (United States)

    Baibarac, M.; Baltog, I.; Daescu, M.; Lefrant, S.; Chirita, P.

    2016-12-01

    Surface enhanced Raman scattering (SERS) spectroscopic studies reveal a particular chemical interaction of the polyaniline/fullerene (PANI/C60) composite with N-methyl-2-pyrrolidinone (NMP). The chemical polymerization of aniline in the presence of sulfuric acid, potassium dichromate and fullerene has been used for the preparation of the PANI/C60 composite. The polymerization reaction involves a doping of PANI with C60 anion radicals. The interaction of the composite with NMP leads to a de-doping of PANI that involves a transformation of leucoemeraldine salt (LS) repeating units into leucoemeraldine base (LB). Additionally, a gradual increasing in the intensity of the Raman line at 1452 cm-1 associated to the Ag(2) pentagonal pinch mode of fullerene and a decrease in the intensity of the Raman lines of PANI are reported. This change arises from the formation of a charge-transfer complex C60-NMP. The subsequent chemical treatment of PANI-LB with FeCl3 leads to the formation PANI-emeraldine salt. An inhibition of the transformation of PANI doped with C60 anion radicals into a PANI-LB and the C60-NMP charge transfer complex in the presence of CdS particles dispersed in NMP is demonstrated by SERS spectroscopy.

  14. Preliminary studies towards the preparation of reactive 3-pyrrolin-2-ones in conjugate addition reactions for the syntheses of potentially bioactive 2-pyrrolidinones and pyrrolidines

    Energy Technology Data Exchange (ETDEWEB)

    Alves, Jose C.F. [Universidade Federal Fluminense, (UFF) Niteroi, RJ (Brazil). Inst. de Quimica]. E-mail: alvesjcf@yahoo.com.br

    2007-07-01

    Pyrrolin-2-ones and 2-pyrrolidinones are moieties often found in the structure of several biologically active natural products and 3-pyrrolin-2-ones are valuable starting materials in organic synthesis due to their ability to react as acceptors in conjugate addition reactions. In this article we report the initial results about the performed study aiming at the syntheses of reactive 3-pyrrolin-2-ones in conjugate addition reactions and the preparation of a potential precursor for the synthesis of the nootropic (+/-)-nebracetam. (author)

  15. Potent Antiviral HIV-1 Protease Inhibitor GRL-02031 Adapts to the Structures of Drug Resistant Mutants with Its P1;#8242;-Pyrrolidinone Ring

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Yu-Chung E.; Yu, XiaXia; Zhang, Ying; Tie, Yunfeng; Wang, Yuan-Fang; Yashchuk, Sofiya; Ghosh, Arun K.; Harrison, Robert W.; Weber, Irene T. (GSU); (Purdue); (GSI); (CDC)

    2012-11-14

    GRL-02031 (1) is an HIV-1 protease (PR) inhibitor containing a novel P1' (R)-aminomethyl-2-pyrrolidinone group. Crystal structures at resolutions of 1.25-1.55 {angstrom} were analyzed for complexes of 1 with the PR containing major drug resistant mutations, PR{sub I47V}, PR{sub L76V}, PR{sub V82A}, and PR{sub N88D}. Mutations of I47V and V82A alter residues in the inhibitor-binding site, while L76V and N88D are distal mutations having no direct contact with the inhibitor. Substitution of a smaller amino acid in PR{sub I47V} and PR{sub L76V} and the altered charge of PR{sub N88D} are associated with significant local structural changes compared to the wild-type PR{sub WT}, while substitution of alanine in PR{sub V82A} increases the size of the S1' subsite. The P1' pyrrolidinone group of 1 accommodates to these local changes by assuming two different conformations. Overall, the conformation and interactions of 1 with PR mutants resemble those of PR{sub WT} with similar inhibition constants in good agreement with the antiviral potency on multidrug resistant HIV-1.

  16. Role of N-vinyl-2-pyrrolidinone on the thermoresponsive behavior of PNIPAm hydrogel and its release kinetics using dye and vitamin-B12 as model drug.

    Science.gov (United States)

    Maheswari, B; Babu, P E Jagadeesh; Agarwal, Mayank

    2014-01-01

    Temperature-sensitive hydrogels hold great promise in biological applications as they can respond to changes in physiological temperature to produce a desired effect like controlled drug delivery. In this study, a series of poly(N-isopropylacrylamide-co-N-vinyl-2-pyrrolidinone) thermosensitive hydrogels were synthesized by radical copolymerization of NIPAm with 1-vinyl-2-pyrrolidinone (NVP). By altering the initial NIPAm/NVP mole ratios, copolymers were synthesized to have their own distinctive lower critical solution temperature which was established using differential scanning calorimetry. The swelling behavior of the hydrogel was analyzed gravimetrically and it was observed that reswelling rate increases with increasing NVP mole ratio. Further characterizations of the hydrogels were performed using Fourier transform infrared spectroscopy and scanning electron microscopy. Release kinetics with respect to temperature was studied using methylene blue dye solution and vitamin B12. Kinetic modeling of the release profile revealed that the release mechanism is a non-Fickian diffusion mechanism. These results suggested that this material has potential application as intelligent drug carriers. The quantities of residual monomers in the PIV4 hydrogel were determined by HPLC method, and the results show almost complete conversion.

  17. SOLVENT SENSITIVITY OF THE WAVE-NUMBER CHARACTERIZING THE CARBONYL STRETCHING VIBRATION OF N-CYCLOHEXYL-2-PYRROLIDINONE DISSOLVED IN PURE LIQUIDS AND IN MIXTURES FORMED BY HEXANE AND DEUTERIOTRICHLOROMETHANE AT 298.2-K

    NARCIS (Netherlands)

    ENGBERTS, JBFN; PERJESSY, A; BLANDAMER, MJ

    1993-01-01

    The dependence of nuBAR(C=O) on solvent for N-cyclohexyl-2-pyrrolidinone (NCP) as solute in 18 pure solvents can be described using a two-parameter equation based on the Taft-Kamlet pi* (dipolarity/polarisability) and alpha proton donor parameters. In alcoholic solvents two bands are recorded, the b

  18. The use of J-coupling as a sole criterion to assign the total absolute stereochemistry of new pyrrolidinone class synthetic analogs, derived from S-pyroglutamic acid

    Science.gov (United States)

    Kellici, Tahsin F.; Ntountaniotis, Dimitrios; Vanioti, Marianna; Golic Grdadolnik, Simona; Simcic, Mihael; Michas, Georgios; Moutevelis-Minakakis, Panagiota; Mavromoustakos, Thomas

    2017-02-01

    During the synthesis of new pyrrolidinone analogs possessing biological activity it is intriguing to assign their absolute stereochemistry as it is well known that drug potency is influenced by the stereochemistry. The combination of J-coupling information with theoretical results was used in order to establish their total stereochemistry when the chiral center of the starting material has known absolute stereochemistry. The J-coupling can be used as a sole criterion for novel synthetic analogs to identify the right stereochemistry. This approach is extremely useful especially in the case of analogs whose 2D NOESY spectra cannot provide this information. Few synthetic examples are given to prove the significance of this approach.

  19. Substrate-induced coagulation (SIC) of nano-disperse alumina in non-aqueous media: The dispersibility and stability of alumina in N-methyl-2-pyrrolidinone.

    Science.gov (United States)

    Basch, Angelika; Strnad, Simona

    2011-01-20

    This work investigated colloidal properties such as the zeta-potential, the electrophoretic mobilities and the wetting behaviour of alumina dispersed in non-aqueous media. Non-aqueous dispersions of alumina were prepared in the solvent N-methyl-2-pyrrolidinone (NMP). The wetting behaviour of alumina in NMP was characterized by the powder contact angle method and the Wilhemy plate method. The behaviour of the dispersion should provide information for the development of a substrate-induced coagulation (SIC) coating process of nano-sized alumina in non-aqeous media. SIC is a dip-coating process that coats pretreated but chemically different surfaces with nano-sized particles. It was found that the anionic surfactant dioctyl sulfosuccinate (AOT) had no stabilizing effect on alumina dispersed in NMP.

  20. Design of HIV-1 protease inhibitors with pyrrolidinones and oxazolidinones as novel P1'-ligands to enhance backbone-binding interactions with protease: synthesis, biological evaluation, and protein-ligand X-ray studies

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Arun K.; Leshchenko-Yashchuk, Sofiya; Anderson, David D.; Baldridge, Abigail; Noetzel, Marcus; Miller, Heather B.; Tie, Yunfeng; Wang, Yuan-Fang; Koh, Yasuhiro; Weber, Irene T.; Mitsuya, Hiroaki; (GSU); (Purdue); (NCI); (Kumamoto University School of Medicine)

    2009-09-02

    Structure-based design, synthesis, and biological evaluation of a series of novel HIV-1 protease inhibitors are described. In an effort to enhance interactions with protease backbone atoms, we have incorporated stereochemically defined methyl-2-pyrrolidinone and methyl oxazolidinone as the P1{prime}-ligands. These ligands are designed to interact with Gly-27{prime} carbonyl and Arg-8 side chain in the S1{prime}-subsite of the HIV protease. We have investigated the potential of these ligands in combination with our previously developed bis-tetrahydrofuran (bis-THF) and cyclopentanyltetrahydrofuran (Cp-THF) as the P2-ligands. Inhibitor 19b with a (R)-aminomethyl-2-pyrrolidinone and a Cp-THF was shown to be the most potent compound. This inhibitor maintained near full potency against multi-PI-resistant clinical HIV-1 variants. A high resolution protein-ligand X-ray crystal structure of 19b-bound HIV-1 protease revealed that the P1{prime}-pyrrolidinone heterocycle and the P2-Cp-ligand are involved in several critical interactions with the backbone atoms in the S1{prime} and S2 subsites of HIV-1 protease.

  1. Partial dissolution of ACQ-treated wood in lithium chloride/N-methyl-2-pyrrolidinone: separation of copper from potential lignocellulosic feedstocks.

    Science.gov (United States)

    Eberhardt, Thomas L; Lebow, Stan; Reed, Karen G

    2012-02-01

    A cellulose solvent system based on lithium chloride (LiCl) in N-methyl-2-pyrrolidinone (NMP) was used to assess the merits of partial dissolutions of coarsely ground wood samples. Alkaline Copper Quaternary (ACQ)-treated pine wood was of particular interest for treatment given the potential to generate a copper-rich stream apart from solid and/or liquid lignocellulosic feedstocks. Treatment with NMP alone gave yields of soluble materials that were higher than typical extractives contents thereby suggesting a limited degree of wood dissolution. Inclusion of LiCl, which disrupts hydrogen bonding, gave lower wood residue recoveries (i.e., higher dissolution) with higher LiCl concentration. Lower wood residue recoveries coincided with lower Klason lignin and hemicellulose-derived sugar contents in the wood residues. After treatment with 8% LiCl in NMP, subsequent filtration afforded 34% of the ACQ-treated sapwood as a wood residue retaining only 2% of the original copper. Pouring the filtrate over an excess of water resulted in the recovery of 30% of the solids and 50% of the copper together as a copper-enriched lignocellulosic precipitate. Results demonstrate a solvent system showing potential as a means to separate heavy metals from preservative-treated wood and to recover lignocellulosic feedstocks that may be suitable for use in a biorefinery. Published by Elsevier Ltd.

  2. 1-芳基-2-吡咯烷酮衍生物的合成研究%Study on the Synthesis of 1-Aryl-2-pyrrolidinone Derivatives

    Institute of Scientific and Technical Information of China (English)

    赵军; 王德传; 曹燕

    2012-01-01

    1-芳基-2-吡咯烷酮衍生物是重要的有机合成中间体.以苯佐卡因为原料,经溴代、缩合、环合合成了目标产物,产物总收率达72.25%.其结构经1H NMR,MS进行了确证.该方法具有操作简便、成本低、收率高等优点.%1-Aryl-2-pyrrolidinone derivatives are important intermediates for organic synthesis. A novel process was developed for the synthesis of the title compound in an overall yield of 72.2% starting from benzocaine via bromination,nucleophilic substitution and cyclization. The structure of the target compound was confirmed with 1H NMR and MS. This method shows advantages of easy operation,low cost and high yield.

  3. Examination of soil contaminated by coal-liquids by size exclusion chromatography in 1-methyl-2-pyrrolidinone solution to evaluate interference from humic and fulvic acids and extracts from peat.

    Science.gov (United States)

    Morgan, T J; Herod, A A; Brain, S A; Chambers, F M; Kandiyoti, R

    2005-11-18

    Soil from a redundant coke oven site has been examined by extraction of soluble materials using 1-methyl-2-pyrrolidinone (NMP) followed by size exclusion chromatography (SEC) of the extracted material. The extracted material was found to closely resemble a high temperature coal tar pitch. Standard humic and fulvic acids were also examined since these materials are very soluble in NMP and would be extracted with pitch if present in the soil. Humic substances derived from peat samples and NMP-extracts of peats were also examined. The results show that the humic and fulvic substances were not extracted directly by NMP from peats. They were extracted using caustic soda solution and were different from the peat extracts in NMP. These results indicate that humic and fulvic acids were soluble in NMP in the protonated polyelectrolyte form but not in the original native polyelectrolyte form. The extraction of soil using NMP followed by SEC appears to be a promising method for identifying contamination by coal-based industries.

  4. Preparation of hydrophilic monolithic capillary column by in situ photo-polymerization of N-vinyl-2-pyrrolidinone and acrylamide for highly selective and sensitive enrichment of N-linked glycopeptides.

    Science.gov (United States)

    Jiang, Hao; Yuan, Huiming; Qu, Yanyan; Liang, Yu; Jiang, Bo; Wu, Qi; Deng, Nan; Liang, Zhen; Zhang, Lihua; Zhang, Yukui

    2016-01-01

    In this study, a novel kind of amide functionalized hydrophilic monolith was synthesized by the in situ photo-polymerization of N-vinyl-2-pyrrolidinone (NVP), acrylamide (AM), and N, N'-methylenebisacrylamide (MBA) in a UV transparent capillary, and successfully applied for hydrophilic interaction chromatography (HILIC) based enrichment of N-linked glycopeptides. With 2 μg of the tryptic digests of IgG as the sample, after enrichment, 18 glycopeptides could be identified by MALDI-TOF/TOF MS analysis. Furthermore, with the mixture of BSA and IgG digests (10,000:1, m/m) as the sample, 6 N-linked glycopeptides were unambiguously identified after enrichment, indicating the high selectivity and good specificity of such material. Moreover, such a monolithic capillary column was also applied for the N-glycosylation sites profiling of 6 μg protein digests from HeLa cells and 1 μL human serum. In total, 530 and 262 unique N-glycosylated peptides were identified, respectively, corresponding to 282 and 124N-glycoproteins, demonstrating its great potential for the large scale glycoproteomics analysis.

  5. Comparison of Analysis Methods for 1-Methyl-2-pyrrolidinone Residual in Poly Urethane Leather by GC-MS and HPLC-PDA%GC-MS和HPLC-PDA测定PU革中N-甲基吡咯烷酮残留的比较

    Institute of Scientific and Technical Information of China (English)

    王良贵; 杨明华

    2015-01-01

    分别建立PU革中N-甲基吡咯烷酮残留量的气-质联用法(GC-MS)和高效液相色谱-二极管阵列检测器(HPLC-PDA)检测法,并比较了2种方法在实际检测过程中的优缺点,2种方法均可满足生态纺织品标准(Oeko-Tex Standard 100)对NMP检测要求,但中等极性色谱柱的GC-MS法的灵敏度和色谱峰分离度均好于HPLC-PDA法.%Two methods for 1-methyl-2-pyrrolidinone ( NMP ) analysis in the poly urethane leather were developed by gas chromatography with mass spectrometry detector ( GC - MS ) and high performance liquid chromatography with photodiode array detector ( HPLC-PDA ) , respectively. The virtues and limitations of the above approaches were compared during the actual application. Both testing methods can meet the demand for determination of NMP residual in poly urethane leather according to Oeko-Tex Standard 100. The GC-MS on a column of medium polarity had higher sensitivity and better separating resolution for chromatographic peak of NMP with other peaks than HPLC-PDA.

  6. Solubility parameter of poly(1-vinyl-2-pyrrolidinone)

    Science.gov (United States)

    Wohlfarth, Ch.

    This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.

  7. Synthesis of (Arylamido)pyrrolidinone Libraries through Ritter-Type Cascade Reactions of Dihydroxylactams

    DEFF Research Database (Denmark)

    Wu, Peng; Petersen, Michael Åxman; Petersen, Rico

    2015-01-01

    diastereoselectivity. A combined one-step Ritter–hydrolysis procedure proved to be of equal efficiency. This versatile method, which was successfully used for the construction of a screening library containing 706 molecules within the European Lead Factory consortium, provides a simple way to access new compounds...

  8. Facile synthesis of MOF-177 by a sonochemical method using 1-methyl-2-pyrrolidinone as a solvent.

    Science.gov (United States)

    Jung, Da-Won; Yang, Da-Ae; Kim, Jun; Kim, Jaheon; Ahn, Wha-Seung

    2010-03-21

    High quality MOF-177 crystals in the size range of 5-20 microm were successfully synthesized via a sonochemical route in a substantially reduced synthesis time (40 min) in the presence of low-cost NMP (1-methyl-2-pyrrolidone) as a solvent. Microwave heating in NMP also produced MOF-177 under similar conditions (35 min, 5-50 microm) but exhibited inferior crystallinity. In comparison, a conventional solvothermal route in DEF (diethylformamide) took 48 h to produce MOF-177 crystals 0.5-1.5 mm in size. The BET surface areas of the MOF-177 samples decreased in the order of sonochemical (4898 m(2) g(-1)) > conventional (4833 m(2) g(-1)) > microwave route (4197 m(2) g(-1)). In line with this trend, MOF-177 prepared via the sonochemical route resulted in the highest CO(2) adsorption capacity, 1315 mg g(-1) at 30 bar and 298 K. The product yield of MOF-177 synthesized via the sonochemical route was 95.6%, and was significantly higher than the product yields of other methods.

  9. SOLUTION RHEOLOGY OF HYPERBRANCHED POLYESTERS AND THEIR BLENDS WITH LINEAR POLYMERS

    Science.gov (United States)

    In this study, the rheological properties of different generations of hyperbranched polyesters in 1-methyl-2-pyrrolidinone solvent and their blends with poly(2-hydroxyethyl methacrylate) have ben investigated. All the hyperbranched polyester solutions exhibited Newtonian behavior...

  10. SOLUTION RHEOLOGY OF HYPERBRANCHED POLYESTERS AND THEIR BLENDS WITH LINEAR POLYMERS

    Science.gov (United States)

    In this study, the rheological properties of different generations of hyperbranched polyesters in 1-methyl-2-pyrrolidinone solvent and their blends with poly(2-hydroxyethyl methacrylate) have ben investigated. All the hyperbranched polyester solutions exhibited Newtonian behavior...

  11. Biocompatible and Bioeliminable Hydrophilic Polymers

    Institute of Scientific and Technical Information of China (English)

    Paolo; FerrutiUniversità

    2007-01-01

    1 Introduction This presentation will report on some recent results obtained in Milan on two polymer families of biomedical interest, namely poly(N-vinyl-2-pyrrolidinone) and polyamidoamines. 2 Results and DiscussionPoly(N-vinyl-2-pyrrolidinone) (PVP) is a well known bioactive and biocompatible polymer. In its soluble form, it is largely used as excipient of oral pharmaceutical formulations, especially for its high water solubilising power.In its crosslinked form, it plays a relevant role as biomateria...

  12. One-pot nitro-Mannich cascade reactions: new methodologies and synthetic applications

    OpenAIRE

    2011-01-01

    Pyrrolidine and pyrrolidinone rings are common motifs found in many biologically active natural products and drugs. Accordingly, our work focuses on the development of new methodologies for their one-pot synthesis. An efficient diastereoselective nitro-Mannich / lactamisation reaction cascade of methyl 3-nitropropanoate with cyclic and acyclic imines for the direct preparation of trans-monocyclic and fused tricyclic pyrrolidinone derivatives was developed. The reaction is easy to perform, ...

  13. Tandem Ring-Closing Metathesis/Isomerization Reactions for the Total Synthesis of Violacein

    DEFF Research Database (Denmark)

    Petersen, Mette T.; Nielsen, Thomas Eiland

    2013-01-01

    A series of 5-substituted 2-pyrrolidinones was synthesized through a one-pot ruthenium alkylidene-catalyzed tandem RCM/isomerization/nucleophilic addition sequence. The intermediates resulting from RCM/isomerization showed reactivity toward electrophiles in aldol condensation reactions which prov...

  14. RHEOLOGY OF CONCENTRATED SOLUTIONS OF HYPERBRANCHED POLYESTERS

    Science.gov (United States)

    The solution rheology of different generations of hyperbranched polyesters in N-methyl-2- pyrrolidinone (NMP) solvent was examined in this study. The solutions exhibited Newtonian behavior over a wide range of polyester concentrations. Also, the relative viscosities of poly(amido...

  15. Synthesis of (R)-3-Methylpyrrolidine Alkaloids Using (S)-Malic Acid as a Chiral Pool

    Institute of Scientific and Technical Information of China (English)

    ZHENG; Xiao

    2001-01-01

    Previous work in our laboratory was around the development of chiral 2-pyrrolidinone synthon A. Malimides 1 and 2, which can be easily prepared from (S)-malic acid, have been shown to be versatile chiral synthetic intermediates. All the reactivities showed in synthon A have been exploited.1  ……

  16. Aza-Morita-Baylis-Hillman reaction of maleimides with azodicarboxylates under neat conditions

    Indian Academy of Sciences (India)

    Subramani Kandhasamy; Kesavan Karthikeyan; Krishnan Ramachandiran; Doraiswamy Muralidharan; Paramasivan Thirumalai Perumal

    2013-09-01

    Green approach on reaction of diisopropylazodicarboxylate or diethyl azodicarboxylate with maleimides proceeded smoothly under neat condition at 70°C to give the corresponding hydrazine substituted pyrrolidinone as aza-Morita-Baylis-Hillman adducts in moderate to good yields in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as nitrogen Lewis base.

  17. Studies toward the Synthesis of (R)-(+)-Harmicine%Studies toward the Synthesis of (R)-(+)-Harmicine

    Institute of Scientific and Technical Information of China (English)

    莫凡洋; 李飞; 邱頔; 张艳; 王剑波

    2012-01-01

    The study toward the total synthesis of (R)-(+)-harmicine is reported in this paper. The enantioselective syn- thesis of pyrrolidinone, the main backbone of of (R)-(+)-harmicine, has been completed by the methodology based on photo-induced Wolff rearrangement of α-diazo-β-carbonyl compounds.

  18. Hydrophobicity as a design criterion for polymer scaffolds in bone tissue engineering

    NARCIS (Netherlands)

    Jansen, EJP; Sladek, REJ; Bahar, H; Yaffe, A; Gijbels, MJ; Kuijer, R; Bulstra, SK; Guldemond, NA; Binderman, [No Value; Koole, LH

    2005-01-01

    Porous polymeric scaffolds play a key role in most tissue-engineering strategies. A series of non-degrading porous scaffolds was prepared, based on bulk-copolymerisation of 1-vinyl-2-pyrrolidinone (NVP) and n-butyl methacrylate (BMA), followed by a particulate-leaching step to generate porosity. Bio

  19. RHEOLOGY OF CONCENTRATED SOLUTIONS OF HYPERBRANCHED POLYESTERS

    Science.gov (United States)

    The solution rheology of different generations of hyperbranched polyesters in N-methyl-2- pyrrolidinone (NMP) solvent was examined in this study. The solutions exhibited Newtonian behavior over a wide range of polyester concentrations. Also, the relative viscosities of poly(amido...

  20. Manufacturing Methods and Technology Project Summary Reports

    Science.gov (United States)

    1984-06-01

    methyl pyrrolidinone, benezaldehyde, nitroguanyl hydrazone, melamine , formaldehyde , and methyl cellulose. None appeared to be adequately effective...and other by-products. However, addi- tional analysis using gas chromatography/mass spectrometry identified other compounds such as dimethyl- sulfone ...additional analysis, as stated earlier, led to the detection of three additional compounds: dimethyl sulfone , benzothiazole and diacetone alcohol. Both

  1. Preparation of 4- and 6-desphenyl analogues of (-)-clausenamide and alternative synthesis of (+)-epi-clausenamide

    Institute of Scientific and Technical Information of China (English)

    Jian Jun Xue; Yu Mei Zhou; Xiao Ming Yu

    2011-01-01

    4- and 6-desphenyl analogues of (-)-clausenamide, 6 and 7, were prepared in optical active form from commercially available D-pyroglutamic acid and the known racemic pyrrolidinone 13, respectively. In order to confirm the absolute stereochemistry of (+)-and (-)-7, intermediate 19b was transferred into the (+)-epi-clausenamide 8.

  2. Synthesis and Antibacterial Activity of Novel 2-Oxo-pyrrolidinyl Oxazolidinones

    Energy Technology Data Exchange (ETDEWEB)

    Bhattarai, Deepak; Lee, Sun Hee; Kim, Hyeong Kyu; Kang, Soon Bang; Pae, Ae Nim; Kim, Eunice Eunkyeong; Keum, Gyo Chang [Korea Institute of Science and Technology, Seoul (Korea, Republic of); Oh, Tae Gwon; Cho, Sang Nae [Yonsei University College of Medicine, Seoul (Korea, Republic of)

    2012-04-15

    Novel antibacterial oxazolidinones bearing pyrrolidinone ring system at the C-5 side chain were synthesized and their in vitro antibacterial activities were evaluated. Most of the synthesized oxazolidinones showed good antibacterial activity against the Gram-positive and Gram-negative bacteria tested

  3. An Investigation of Pore Collapse in Asymmetric Polysulfone Membranes

    OpenAIRE

    Subrahmanyan, Sumitra

    2003-01-01

    Abstract Porous polysulfone membranes prepared by phase inversion can be tailored to suit filtration requirements by the choice of solvent and coagulant. In the current research polysulfone membranes were prepared by inverting a solution in N-methyl pyrrolidinone (NMP) in isopropanol to form uniform sized pores. Phase inversion resulted in the formation of an asymmetric membrane. The membranes have a characteristic "skin" which is supported by a highly porous substructure. Water-wet membra...

  4. CLSM and UV-VIS researches on polyoxadiazoles thin films

    OpenAIRE

    J. Weszka; M.M. Szindler; M. Chwastek-Ogierman; BRUMA M.; P. Jarka

    2012-01-01

    Purpose: The purpose of this paper was to analyse the surface morphology and optical properties of polyoxadiazoles thin films.Design/methodology/approach: A few different conducting polymers were dissolved in N-methyl-2-pyrrolid(in)one. Then the solutions were deposited on a glass substrate by spin coating method with a different spin rate. Changes in surface topography and optical properties were observed. A confocal laser scanning microscope CLSM Zeiss LSM 5 Exciter has been used. Photos ha...

  5. A novel property of spider silk: chemical defence against ants.

    Science.gov (United States)

    Zhang, Shichang; Koh, Teck Hui; Seah, Wee Khee; Lai, Yee Hing; Elgar, Mark A; Li, Daiqin

    2012-05-07

    Spider webs are made of silk, the properties of which ensure remarkable efficiency at capturing prey. However, remaining on, or near, the web exposes the resident spiders to many potential predators, such as ants. Surprisingly, ants are rarely reported foraging on the webs of orb-weaving spiders, despite the formidable capacity of ants to subdue prey and repel enemies, the diversity and abundance of orb-web spiders, and the nutritional value of the web and resident spider. We explain this paradox by reporting a novel property of the silk produced by the orb-web spider Nephila antipodiana (Walckenaer). These spiders deposit on the silk a pyrrolidine alkaloid (2-pyrrolidinone) that provides protection from ant invasion. Furthermore, the ontogenetic change in the production of 2-pyrrolidinone suggests that this compound represents an adaptive response to the threat of natural enemies, rather than a simple by-product of silk synthesis: while 2-pyrrolidinone occurs on the silk threads produced by adult and large juvenile spiders, it is absent on threads produced by small juvenile spiders, whose threads are sufficiently thin to be inaccessible to ants.

  6. The influence of oxygen-containing functional groups on the dispersion of single-walled carbon nanotubes in amide solvents

    Science.gov (United States)

    Brandão, S. D. F.; Andrada, D.; Mesquita, A. F.; Santos, A. P.; Gorgulho, H. F.; Paniago, R.; Pimenta, M. A.; Fantini, C.; Furtado, C. A.

    2010-08-01

    Surface composition plays an important role in carbon nanotube dispersibility in different environments. Indeed, it determines the choice of dispersion medium. In this paper the effect of oxidation on the dispersion of HiPCO single-walled carbon nanotubes (SWNTs) in N-methyl-pyrrolidinone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), N-dodecyl-pyrrolidinone (N12P) and cyclohexyl-pyrrolidinone (CHP) was systematically studied. During the oxidation process, similar amounts of carboxylic acid and phenolic groups were introduced to mostly already existing defects. For each solvent the dispersion limits and the absorption coefficients were estimated by optical absorption analysis over a range of SWNT concentrations. The presence of acid oxygenated groups increased SWNT dispersibility in NMP, DMF and DMA, but decreased in N12P and CHP. The absorption coefficients, however, decreased for all solvents after oxidation, reflecting the weakening of the effective transition dipole of the π-π transition with even limited extension functionalization and solvent interaction. The analysis of the results in terms of Hansen and Flory-Huggins solubility parameters evidenced the influence of dipolar interactions and hydrogen bonding on the dispersibility of oxidized SWNTs.

  7. (11aS-7-Bromo-2,3,5,10,11,11a-hexahydro-1H-pyrrolo[2,1-c][1,4]benzodiazepine-3,11-dione

    Directory of Open Access Journals (Sweden)

    Chao Ma

    2012-01-01

    Full Text Available The title compound, C12H11BrN2O2, was prepared by an intra-cyclization reaction of (S-1-(5-bromo-2-nitrobenzyl-5-oxopyrrolidine-2-carboxylic acid methyl ester in the presence of EtOH/Fe. The five-membered pyrrolidinone ring adopts an approximate envelope conformation, while the seven-membered diazepanone ring displays a twisted boat conformation. Intermolecular classical N—H...O hydrogen bonds and weak C—H...O interactions help to stabilize the crystal structure.

  8. Protection of Polymer from Atomic-Oxygen Erosion using Al2O3 Atomic Layer Deposition Coatings

    Science.gov (United States)

    2008-01-01

    polyimide was Pyralin® PI5878G from HD Microsystems. This polyamic acid as pur- chased was dissolved in 1-methyl-2-pyrrolidinone. The polya- mic acid was...coatings with various thicknesses were applied to the polyimide substrates using sequential, self-limiting exposures to trimethylaluminum ( TMA ...Aldrich) and water (Fisher HPLC-grade). The Al2O3 ALD was performed at 177 °C in a viscous flow, hot-wall ALD flow reactor [25]. The TMA and H2O yield

  9. Physicochemical Evaluations of Selected Solvents for Use in Decontaminating Agent: Multipurpose (DAM) Formulation

    Science.gov (United States)

    1994-03-01

    the N-substituted pyrrolidinones and sulfolanes, were searched in more detail. The N-substituted derivatives of a 5-member ring with two heteroatoms ...separation into two or more phases. 4. Start analysis for residual HTH within 10 min of start of mixing. Repeat HTH analysis at 0.5, 2.0, 4.0, and 6.0 hr...failed if more than 1% HTH (by weight based on water content) was present. The data shown in Fioure 5 are based on a two -phase system kept under

  10. High exposures to organic solvents among graffiti removers.

    Science.gov (United States)

    Anundi, H; Lind, M L; Friis, L; Itkes, N; Langworth, S; Edling, C

    1993-01-01

    The exposure to organic solvents among 12 graffiti removers was studied. Health effects were also assessed by structured interview and a symptom questionnaire. Blood and urine samples were collected at the end of the day of air sampling. The concentrations of dichloromethane, glycol ethers, trimethylbenzenes and N-methyl-2-pyrrolidinone in the breathing zone of each worker were measured during one working day. The 8-h time-weighted average exposure to dichloromethane ranged from 18 to 1200 mg/m3. The Swedish Permissible Exposure Limit value for dichloromethane is 120 mg/m3. The air concentrations of glycol ethers, trimethylbenzenes and N-methyl-2-pyrrolidinone were low or not detectable. No exposure-related deviations in the serum concentrations of creatinine, aspartate transaminase, alanine transaminase, gamma-glutamyl transpeptidase or hyaluronan or the urine concentrations of alpha 1-microglobulin, beta 2-microglobulin or N-acetyl-beta-glucosaminidase were found. Irritative symptoms of the eyes and upper respiratory tract were more prevalent than in the general population. This study demonstrates that old knowledge about work hazards is not automatically transferred to new professions. Another aspect is that the public is also exposed as the job is performed during daytime in underground stations. At least for short periods, bystanders may be exposed to high concentrations of organic solvent vapours. People with predisposing conditions, e.g. asthmatics, may risk adverse reactions.

  11. Crystal structure of methyl (3RS,4SR,4aRS,11aRS,11bSR-5-oxo-3,4,4a,5,7,8,9,10,11,11a-decahydro-3,11b-epoxyazepino[2,1-a]isoindole-4-carboxylate

    Directory of Open Access Journals (Sweden)

    Flavien A. A. Toze

    2015-10-01

    Full Text Available The title compound, C15H19NO4, is the a product of the esterification of the corresponding carbonic acid with methanol. The molecule comprises a fused tetracyclic system containing three five-membered rings (2-pyrrolidinone, tetrahydrofuran and dihydrofuran and one seven-membered ring (azepane. The five-membered rings have the usual envelope conformations, with the quaternary C atom being the flap atom for the 2-pyrrolidinone ring, and the ether O atom being the common flap atom for the remaining rings. The seven-membered azepane ring adopts a chair conformation with the methine and middle methylene C atoms lying above and below the mean plane defined by the remaining five atoms. The carboxylate substituent is rotated by 77.56 (5° with respect to the base plane of the tetrahydrofuran ring. In the crystal, the molecules are bound by weak C—H...O hydrogen-bonding interactions into puckered layers parallel to (001.

  12. Development and validation of a liquid chromatographic method for the simultaneous determination of aniracetam and its related substances in the bulk drug and a tablet formulation.

    Science.gov (United States)

    Papandreou, Georgios; Zorpas, Kostas; Archontaki, Helen

    2011-11-01

    Simultaneous determination of aniracetam and its related impurities (2-pyrrolidinone, p-anisic acid, 4-p-anisamidobutyric acid and (p-anisoyl)-4-methyl-2-pyrrolidinone) was accomplished in the bulk drug and in a tablet formulation using a high performance liquid chromatographic method with UV detection. Separation was achieved on a Hypersil BDS-CN column (150 mm × 4.0 mm, 5 μm) using a gradient elution program with solvent A composed of phosphate buffer (pH 4.0; 0.010 M) and solvent B of acetonitrile-phosphate buffer (pH 4.0; 0.010 M) (90:10, v/v). The flow rate of the mobile phase was 1.0 mL min(-1) and the total elution time, including the column re-equilibration, was approximately 20 min. The UV detection wavelength was varied appropriately among 210, 250 and 280 nm. Injection volume was 20 μL and experiments were conducted at ambient temperature. The developed method was validated in terms of system suitability, selectivity, linearity, range, precision, accuracy, limits of detection and quantification for the impurities, short term and long term stability of the analytes in the prepared solutions and robustness, following the ICH guidelines. Therefore, the proposed method was suitable for the simultaneous determination of aniracetam and its studied related impurities.

  13. Crystal structures of the two epimers from the unusual thermal C6-epimerization of 5-oxo-1,2,3,5,5a,6,7,9b-octahydro-7,9a-epoxypyrrolo[2,1-a]isoindole-6-carboxylic acid, 5a(RS,6(SR,7(RS,9a(SR,9b(SR and 5a(RS,6(RS,7(RS,9a(SR,9b(SR

    Directory of Open Access Journals (Sweden)

    Dmitry S. Poplevin

    2016-10-01

    Full Text Available The isomeric title compounds, C12H13NO4 (Ia and C12H13NO4 (IIa, the products of an usual thermal C6-epimerization of 5-oxo-1,2,3,5,5a,6,7,9b-octahydro-7,9a-epoxypyrrolo[2,1-a]isoindole-6-carboxylic acid, represent the two different diastereomers and have very similar molecular geometries. The molecules of both compounds comprise a fused tetracyclic system containing four five-membered rings (pyrrolidine, pyrrolidinone, dihydrofuran and tetrahydrofuran, all of which adopt the usual envelope conformations. The dihedral angle between the basal planes of the pyrrolidine and pyrrolidinone rings are 14.3 (2 and 16.50 (11°, respectively, for (Ia and (IIa. The nitrogen atom has a slightly pyramidalized geometry [bond-angle sum = 355.9 and 355.3°, for (Ia and (IIa], respectively. In the crystal of (Ia, molecules form zigzag-like hydrogen-bonded chains along [010] through strong O—H...O hydrogen bonds and are further linked by weak C—H...O hydrogen bonds into complex two-tier layers parallel to (100. Unlike (Ia, the crystal of (IIa contains centrosymmetric cyclic hydrogen-bonded dimers [graph set R22(14], formed through strong O—H...O hydrogen bonds and are further linked by weak C—H...O hydrogen bonds into ribbons extending across [101].

  14. 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.

  15. Synthesis of Poly(aryl amide imide)s Derived from o-diphenyltrimellitic Anhydride

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The synthesis and characterization of a series of novel poly(aryl amide imide)s based on o-diphenyltrimellitic anhydride are described.The poly(aryl amide-imide)s having inherent viscosities of 0.39-1.43dL/g in N-methyl-2-pyrrolidinone at 30℃,were prepared by polymerization with aromatic diamines in N,N-dimethylacetamide and subsequent chemical imidization.All the polymers were amorphous,readily soluble in aprotic polar solvents such as DMAC,NMP,DMF,DMSO,and m-cresol,and could be cast to form flexible and tough films.The glass trsanition temperatures were in the range of 284-336℃,and the temperatures for 5% weight loss in nitrogen were above 468℃.

  16. Novel Conformationally Constrained Analogues of Agomelatine as New Melatoninergic Ligands

    Directory of Open Access Journals (Sweden)

    Marouan Rami

    2012-12-01

    Full Text Available Novel conformationally restricted analogues of agomelatine were synthesized and pharmacologically evaluated at MT1 and MT2 melatoninergic receptors. Replacement of the N-acetyl side chain of agomelatine by oxathiadiazole-2-oxide (compound 3, oxadiazole-5(4H-one (compound 4, tetrazole (compound 5, oxazolidinone (compound 7a, pyrrolidinone (compound 7b, imidazolidinedione (compound 12, thiazole (compounds 13 and 14 and isoxazole moieties (compound 15 led to a decrease of the melatoninergic binding affinities, particularly at MT1. Compounds 7a and 7b exhibiting nanomolar affinity towards the MT2 receptors subtypes have shown the most interesting pharmacological results of this series with the appearance of a weak MT2-selectivity.

  17. Synthesis of Spiroisoxazolines by 1,3-Dipolar Cycloaddition

    Directory of Open Access Journals (Sweden)

    Peter Ertl

    1997-04-01

    Full Text Available The cycloaddition of the chiral nitrile oxide 1 to 1-R-substituted 3,3-methylene-5,5-dimethyl-2-pyrrolidinones 2 (where R is H, n-butyl-, 1,1-dimethylethoxycarbonyl-, 1-methylethenyl- and acetyl- proceeds regioselectively under the formation of spiroisoxazolines, namely 7-R-substituted-6-oxo-8,8-dimethyl-1-oxa-2,7-diazaspiro[4,4]non-2-enes 5 and 6. The asymmetric induction expected by the a-chiral centre of the nitrile oxide 1 was not very effective, diastereoisomers 5 and 6 were formed in an approximate 50:50 ratio. The stereoselectivity of the 1,3-dipolar cycloaddition of the arylnitrile oxide 7 with the chiral lactam 3 and the achiral lactone 4 are investigated. The attack of the 1,3-dipole occurred from the less hindered face of the dipolarophile 3 and 4, giving the major isomer 8 and 10, respectively.

  18. A New Asymmetric α-Amido-hydroxyalkylation Mediated by SmI2

    Institute of Scientific and Technical Information of China (English)

    ZHENG Xiao; FENG Chen-Guo; HUNG Pei-Qiang

    2004-01-01

    Polyhydroxylated indolizidine alkaloids, such as castanospermine (Ⅰ) and swainsonine (H)are of longstanding interest due to their powerful glycosidase inhibitory activity. Asymmetric hydroxyatkylation via α-amido carbanions to form C-C bands would provide a convenient approach to these compounds.In continuation of our efforts in developing asyrmmetric o-amido-hydroxyalkylation method,1 we report a new SmI2 mediated flexible asymmetric α-amido-hydroxyalkylation method. Starting from the known (S)-3-hydroxy-2-pyrrolidinone 1,2 sulfide 2 and 3 were prepared. SmI2-mediated reductive metallation of these sulfides followed by reaction with ketones or aldehydes under Barbier conditions provided C2 hydroxyalkylated products 4 in yields ranged from 30% to 83%. High C2/C3 trans diastereoselectivity and mediocre diastereoselectivity at newly formed carbinolic center have been observed. The present method will open an avenue for the asymmetric synthesis of polyhydroxylated indolizidine alkaloids.

  19. Epoxy-photopolymer composites: thick recording media for holographic data storage

    Science.gov (United States)

    Trentler, Timothy J.; Boyd, Joel E.; Colvin, Vicki L.

    2001-06-01

    Archival data-storage based on holographic methods requires high performance recording materials. Here, we describe an epoxy-photopolymer composite material which is sensitive to visible light and can be fabricated as thick films. These materials are prepared by combining photopolymerizable vinyl monomers with a liquid epoxy resin and an amine hardener. As the epoxy cures at room temperature, a solid matrix is formed which surrounds the unreacted photopolymer. These vinyl monomers are subsequently photopolymerized during hologram recording. Typically the material consists of a low index matrix, composed of diethylenetriamine and 1,4- butanediol diglycidyl ether, and a high index photopolymer mixture of N-vinylcarbazole and N-vinyl-2-pyrrolidinone. Because the polymers can be prepared in thick formats, narrow angular bandwidth holograms with high diffraction efficiency can be recorded. A dynamic range up to 13 has been measured in these materials.

  20. Controlling macrovoid formation in wet-spun polyaniline fibers

    Science.gov (United States)

    Yang, Dali; Fadeev, Andrei; Adams, Phillip N.; Mattes, Benjamin R.

    2001-07-01

    The mesoscopic morphology of wet-spun polyaniline fibers determines their mechanical strength. Macrovoid formation in the coagulation bath is responsible for poor mechanical properties of these fibers. The effects of polymer concentration, coagulation bath temperature, polymer molecular weight and coagulant on the morphology of wet-spun polyaniline fibers have been investigated. The fibers were spun from concentrated solutions of low/medium and medium molecular weight emeraldine base dissolved in N-methyl-2- pyrrolidinone containing heptamethyleneimine as a gel inhibitor. The impact of the fiber morphology on the mechanical properties of the fibers prepared under different conditions is studied. A wet-spinning method, which minimizes macrovoid formation in the polyaniline fiber, is reported, and consequently the strength of the unstretched polyaniline fibers increased dramatically.

  1. ORGANO-SOLUBLE FLUORINATED POLYIMIDES DERIVED FROM α,α-BIS(4-AMINO-3,5- DIMETHYLPHENYL)-4'-FLUOROPHENYL METHANE AND VARIOUS AROMATIC DIANHYDRIDES

    Institute of Scientific and Technical Information of China (English)

    Jin-gang Liu; Yang-xi Peng; Hong-shen Li; Lin Fan; Shi-yong Yang

    2005-01-01

    Organo-soluble fluorinated polyimides were synthesized by the polycondensation of a new aromatic diamine α,αbis(4-amino-3,5-dimethylphenyl)-4'-fluorophenyl methane with several aromatic dianhydrides. The one-step polymerization polyimides could be soluble not only in polar aprotic solvents, such as N-methyl-2-pyrrolidinone, and N,Ndimethylacetamide, but also in common organic solvents, such as chloroform, cyclopentanone, m-cresol and so on. The polyimide films show excellent transparency with the UV-Vis cut-off lengths of 310-360 nm and light transmittances of higher than 80% in the visible region. In addition, the polyimides exhibit good thermal stability with an initial decomposition temperature (Td) higher than 530℃ and have more than 60% of residual weight retentions at 700 ℃.

  2. Investigation of ageing effects on the electrical properties of polyaniline/silver nanocomposites

    Institute of Scientific and Technical Information of China (English)

    Asma Binat Afzala; Muhammad Javed Akhtara

    2011-01-01

    Polyaniline(PANI)/Ag nanocomposites, synthesized by incorporation of separately prepared silver nanoparticles in l-methyl-2-pyrrolidinone(NMP) solution of PANI, have been aged at the accelerated temperature of 120 ℃ to simulate a storage period of 2 years at 25 ℃ The accelerated ageing of these materials is done by using the activation energy calculated from data collected using heat flow calorimetry (HFC). The impedance spectroscopic studies of NMP plasticized aged nanocomposite films suggest a microphase separation into reduced and oxidized repeat units. There is crosslinking of the PANI films during ageing thereby obstructing the charge transfer between PANI chains and silver nanoparticles. As a result, the resistivity is increased.

  3. Synthesis of novel poly(aryl ether amide)s containing the phthalazinone moiety

    Institute of Scientific and Technical Information of China (English)

    CHENG, Lin(程琳); JIAN, Xi- Gao(蹇锡高)

    2000-01-01

    Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4- [ 4-( 4-aminophenoxy ) phenyl ]-( 2H )-phtha-lazin-1-one and 1, 2-dihydro-2-( 4-aminophenyl)-4-[ 4-( 4-aminophenoxy)-3, 5-dimethylphenyl]-(2H)-phthalazin-1-one were successfully synthesized using readily available heterocyclic bisphenol-like monomers through two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety with inherent viscosities of 1.16-1.67 dL/g were prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. The polymers were readily soluble in a variety of solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc),dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidinone (NMP), and pyridine. The polymers had high glass transition tenperatured(Tg) in the 291-329℃ range.

  4. SYNTHESIS OF NEW AROMATIC POLY(AMIDE IMIDE)S FROM UNSYMMETRICAL EXTENDED DIAMINE CONTAINING A PHTHALAZINONE MOIETY

    Institute of Scientific and Technical Information of China (English)

    Lin Cheng; Xi-gao Jian

    2004-01-01

    The direct polymerization of an unsymmetrical kink non-coplanar heterocyclic diarnine (1) with various aromatic bis(trimellitimide)s (2a-e) using triphenyl phosphite and pyridine as condensing agents could generate a series of new aromatic poly(amide imide)s (3a-e) containing the kink non-coplanar phthalazinone heterocyclic units in the polymer main chains with inherent viscosities of 0.58-0.66 dL/g. The polymers are readily soluble in a variety of solvents such as N,Ndimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methy1-2-pyrrolidinone, pyridine and m-cresol and can be cast to form flexible and tough films. The glass transition temperatures of polymers (Ts) are in the range of 301-327℃,and the temperatures for 5% weight loss in nitrogen are in the range of 498-521 ℃.

  5. SYNTHESIS AND CHARACTERIZATION OF ORGANO-SOLUBLE FLUORINATED POLYIMIDES FROM 4,4'-BIS(3-AMINO-5-TRIFLUOROMETHYLPHENOXY)-BIPHENYL AND VARIOUS AROMATIC DIANHYDRIDES

    Institute of Scientific and Technical Information of China (English)

    Gui-long Wu; Jin-gang Liu; Zuo-bang Li; Zi-yi Ge; Lin Fan; Shi-yong Yang

    2005-01-01

    An aromatic diamine monomer, 4,4'-bis(3-amino-5-trifluoromethyl phenoxy)-biphenyl (TFBPDA), was synthesized via the nucleophilic displacement reaction of 3,5-dinitrobenzotrifluoride and 4,4'-biphenol. The monomer was reacted with various aromatic dianhydrides via the high temperature polycondensation procedure to provide a series of polyimides. The polyimides, PI-1 to PI-4, show good solubility not only in aprotic solvents, such as N-methyl-2-pyrrolidinone and N,N-dimethylacetamide, but also in many common solvents, such as m-cresol, chloroform and cyclopentanone. PI-4, derived from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and TFBPDA, was even soluble in toluene. Moreover, PI films exhibit good thermal stability, outstanding transparency in the visible light region and acceptable mechanical and electrical properties. The excellent combined properties of the polyimides make them as a good candidate for fabricating microelectronics.

  6. Heat treatment of medium-temperature Sasol-Lurgi gasifier coal-tar pitch for polymerizing to higher value products

    Energy Technology Data Exchange (ETDEWEB)

    K. Mokoena; T.J. Van der Walt; T.J. Morgan; A.A. Herod; R. Kandiyoti [Sasol Technology (Pty) Ltd., Sasolburg (South Africa). R& amp; D Division

    2008-05-15

    Two coal-derived pitch samples, one a medium temperature pitch from a Sasol-Lurgi gasifier and the other from a high temperature coking process, have been heat treated to induce polymerization, both separately and as a mixture of pitches (co-pyrolysis). The initial pitch samples and the heat-treated samples have been examined by size exclusion chromatography (SEC) in 1-methyl-2-pyrrolidinone (NMP), by UV-fluorescence spectroscopy (UV-F), by solid state {sup 13}C NMR; elemental analyses of the initial pitch samples have been carried out. The Sasol-Lurgi pitch showed larger apparent sizes, more alkyl and carbonyl functions, and smaller polycyclic aromatic hydrocarbon (PAH) groups than the high temperature pitch. Co-pyrolysis of the two pitches indicated that polymerized product from the Sasol-Lurgi pitch can be used as an extender for high-temperature binder pitch. 16 refs., 7 figs., 2 tabs.

  7. Ni nanoparticles prepared by simple chemical method for the synthesis of Ni/NiO-multi-layered graphene by chemical vapor deposition

    Science.gov (United States)

    Ali, Mokhtar; Remalli, Nagarjuna; Gedela, Venkataramana; Padya, Balaji; Jain, Pawan Kumar; Al-Fatesh, Ahmed; Rana, Usman Ali; Srikanth, Vadali V. S. S.

    2017-02-01

    A new chemical method was used to obtain a high yield of nickel nanoparticles (Ni-NPs). The effect of solvent (distilled water, ethylene glycol, and ethanol) and surfactant (oleic acid and polyvinyl pyrrolidinone) on the morphology and crystallinity of the synthesized Ni-NPs has been investigated. The experimental results revealed that among the solvents mentioned above, ethanol gives the best results in terms of complete reduction, controlled morphology and size distribution of Ni-NPs. The surfactants played an important role in impeding the agglomeration and surface oxidation of Ni-NPs. The surfactants also affected the morphology of the Ni-NPs. The synthesized Ni-NPs are found to be quite stable in air. The best of the synthesized Ni-NPs were effectively used as catalysts for the synthesis of Ni/NiO-multi-layered graphene using catalytic chemical vapor deposition technique.

  8. Highly functionalized 1,2-diamino compounds through reductive amination of amino acid-derived β-keto esters.

    Directory of Open Access Journals (Sweden)

    Paula Pérez-Faginas

    Full Text Available 1,2-Diamine derivatives are valuable building blocks to heterocyclic compounds and important precursors of biologically relevant compounds. In this respect, amino acid-derived β-keto esters are a suitable starting point for the synthesis of β,γ-diamino ester derivatives through a two-step reductive amination procedure with either simple amines or α-amino esters. AcOH and NaBH(3CN are the additive and reducing agents of choice. The stereoselectivity of the reaction is still an issue, due to the slow imine-enamine equilibria through which the reaction occurs, affording mixtures of diastereoisomers that can be chromatographically separated. Transformation of the β,γ-diamino esters into pyrrolidinone derivatives allows the configuration assignment of the linear compounds, and constitutes an example of their potential application in the generation of molecular diversity.

  9. A soft and conductive PDMS-PEG block copolymer as a compliant electrode for dielectric elastomers

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Szabo, Peter; Skov, Anne Ladegaard

    -methyl pyrrolidinone) with 1 wt% of surfactant (Triton X-100). The dispersion of MWCNTs in PDMS-PEG systemis shown in figure 2 where MWCNTs (dark areas) are well-distributed in the system indicating an acceptable dispersional though some big clusters appear in the optical microscope image. The conductivity of 4 phr...... MWCNTs is 10-3 S/cm compared to 10-1 S/cm of a non-stretchable reference conducting silicone elastomer (LR3162 from Wacker). Furthermore, PDMS-PEG block copolymer with 4 phr MWCNTs (Young’s modulus, Y = 0.26 MPa) is softer and more stretchable thanLR3162 (Y = 1.17 MPa)....

  10. Crosslinked polyurethanes based on hyperbranched polymers

    Directory of Open Access Journals (Sweden)

    Vuković Jasna

    2008-01-01

    Full Text Available In this paper, two samples of polyurethane (PU crosslinked with hydroxy -functonal hyperbranched aliphatic polyester of the second pseudo generation were investigated. For the synthesis of these crosslinked PUs two different macrodiols were used: poly(tetramethyleneoxide (PTMO for PUPTMO and ethylene oxide-poly(dimethylsiloxane-ethylene oxide (PDMS-EO for PUPDMS-EO sample. Synthesized samples behave as elastomers and have yellow color. Obtained results show that swelling degree of the sample PUPDMS-EO in N-methyl-2-pyrrolidinon (NMP determined at room temperature is higher than for the sample PUPTMO. It has been also observed that thermal properties of these polyurethane networks can be changed by incorporation of siloxane sequences in their structure.

  11. Optimization of cellulose acrylate and grafted 4-vinylpyridine and 1-vinylimidazole synthesis

    Directory of Open Access Journals (Sweden)

    Bojanić Vaso

    2010-01-01

    Full Text Available Optimization of cellulose acrylate synthesis by reaction with sodium cellulosate and acryloyl chloride was carried out. Optimal conditions for conducting the synthesis reaction of cellulose acrylate were as follows: the molar ratio of cellulose/potassium-t-butoxide/acryloyl chloride was 1:3:10 and the optimal reaction time was 10 h. On the basis of elemental analysis with optimal conditions for conducting the reaction of cellulose acrylate, the percentage of substitution of glucose units in cellulose Y = 80.7%, and the degree of substitution of cellulose acrylate DS = 2.4 was determined. The grafting reaction of acrylate vinyl monomers onto cellulose in acetonitrile with initiator azoisobutyronitrile (AIBN in a nitrogen atmosphere was performed, by mixing for 5 h at acetonitrile boiling temperature. Radical copolymerization of synthesized cellulose acrylate and 4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone and 9-vinylcarbazole, cellulose-poly-4-vinylpyridine (Cell-PVP, cellulose-poly-1- vinylimidazole (Cell-PVIm and cellulose-poly-1-vinyl-2-pyrrolidinone (Cell-P1V2P and cellulose-poly-9-vinylcarbazole (Cell-P9VK were synthesized. Acrylate cellulose and cellulose grafted copolymers were confirmed by IR spectroscopy, based on elementary analysis and the characteristics of grafted copolymers of cellulose were determined. The mass share of grafted copolymers, X, the relationship of derivative parts/cellulose vinyl group, Z, and the degree of grafting copolymers of cellulose (mass% were determined. In reaction of methyl iodide and cellulose-poly-4-vinylpyridine (Cell-PVP the cellulose-1-methyl-poly-4-vinylpyridine iodide (Cell-1-Me-PVPJ was synthesized. Cellulose acrylate and grafted copolymers were obtained with better thermal, electrochemical and ion-emulation properties for bonding of noble metals Au, Pt, Pd from water solutions. The synthesis optimization of cellulose acrylate was applied as a model for the synthesis of grafted

  12. Crystal structures of the two epimers from the unusual thermal C6-epimerization of 5-oxo-1,2,3,5,5a,6,7,9b-octa-hydro-7,9a-ep-oxy-pyrrolo-[2,1-a]iso-indole-6-carb-oxy-lic acid, 5a(RS),6(SR),7(RS),9a(SR),9b(SR) and 5a(RS),6(RS),7(RS),9a(SR),9b(SR).

    Science.gov (United States)

    Poplevin, Dmitry S; Zubkov, Fedor I; Dorovatovskii, Pavel V; Zubavichus, Yan V; Khrustalev, Victor N

    2016-10-01

    The isomeric title compounds, C12H13NO4 (Ia) and C12H13NO4 (IIa), the products of an usual thermal C6-epimerization of 5-oxo-1,2,3,5,5a,6,7,9b-octa-hydro-7,9a-ep-oxy-pyrrolo-[2,1-a]iso-indole-6-carb-oxy-lic acid, represent the two different diastereomers and have very similar mol-ecular geometries. The mol-ecules of both compounds comprise a fused tetra-cyclic system containing four five-membered rings (pyrrolidine, pyrrolidinone, di-hydro-furan and tetra-hydro-furan), all of which adopt the usual envelope conformations. The dihedral angle between the basal planes of the pyrrolidine and pyrrolidinone rings are 14.3 (2) and 16.50 (11)°, respectively, for (Ia) and (IIa). The nitro-gen atom has a slightly pyramidalized geometry [bond-angle sum = 355.9 and 355.3°, for (Ia) and (IIa)], respectively. In the crystal of (Ia), mol-ecules form zigzag-like hydrogen-bonded chains along [010] through strong O-H⋯O hydrogen bonds and are further linked by weak C-H⋯O hydrogen bonds into complex two-tier layers parallel to (100). Unlike (Ia), the crystal of (IIa) contains centrosymmetric cyclic hydrogen-bonded dimers [graph set R(2)2(14)], formed through strong O-H⋯O hydrogen bonds and are further linked by weak C-H⋯O hydrogen bonds into ribbons extending across [101].

  13. Molecular structure of cotinine studied by gas electron diffraction combined with theoretical calculations

    Science.gov (United States)

    Takeshima, Tsuguhide; Takeuchi, Hiroshi; Egawa, Toru; Konaka, Shigehiro

    2007-09-01

    The molecular structure of cotinine (( S)-1-methyl-5-(3-pyridinyl)-2-pyrrolidinone), the major metabolite of nicotine, has been determined at about 182 °C by gas electron diffraction combined with MP2 and DFT calculations. The diffraction data are consistent with the existence of the (ax, sc), (ax, ap), (eq, sp) and (eq, ap) conformers, where ax and eq indicate the configuration of the pyrrolidinone ring by means of the position (axial and equatorial) of the pyridine ring, and sc, sp and ap distinguish the isomers arising from the internal rotation around the bond connecting the two rings. The (CH 3)NCCC(N) dihedral angles, ϕ, of the (ax, sc) and (eq, sp) conformers were determined independently to be 158(12)° and 129(13)°, respectively, where the numbers in parentheses are three times the standard errors, 3 σ. According to the MP2 calculations, the corresponding dihedral angles for the (ax, ap) and (eq, ap) conformers were assumed to differ by 180° from their syn counterparts. The ratios x(ax, sc)/ x(ax, ap) and x(eq, sp)/ x(eq, ap) were taken from the theoretically estimated free energy differences, Δ G, where x is the abundance of the conformer. The resultant abundances of (ax, sc), (ax, ap), (eq, sp) and (eq, ap) conformers are 34(6)%, 21% (d.p.), 28% (d.p.), and 17% (d.p.), respectively, where d.p. represents dependent parameters. The determined structural parameters ( rg (Å) and ∠ α (°)) of the most abundant conformer, (ax, sc), are as follows: r(N sbnd C) pyrrol = 1.463(5); r(N sbnd C methyl) = 1.457(←); r(N sbnd C( dbnd O)) = 1.384(12); r(C dbnd O) = 1.219(5); = 1.541(3); r(C pyrrolsbnd C pyrid) = 1.521(←); = 1.396(2); = 1.343(←); ∠(CNC) pyrrol = 113.9(11); ∠CCC pyrrol(-C pyrid) = 103.6(←); ∠NCO = 124.1(13); ∠NC pyrrolC pyrid = 113.1(12); ∠C pyrrolC pyrrolC pyrid = 113.3(←); ∠(CNC) pyrid = 117.1(2); = 124.4(←); ∠C methylNC( dbnd O) = ∠C methylNC(-C pyrid) = 122.8(d.p.); ∠NC( dbnd O)C = 107.1(d.p.); ∠NC pyrrol

  14. Cotinine inhibits the pro-inflammatory response initiated by multiple cell surface Toll-like receptors in monocytic THP cells

    Directory of Open Access Journals (Sweden)

    Bagaitkar Juhi

    2012-11-01

    Full Text Available Abstract Background The primary, stable metabolite of nicotine [(S-3-(1-methyl-2-pyrrolidinyl pyridine] in humans is cotinine [(S-1-methyl-5-(3-pyridinyl-2-pyrrolidinone]. We have previously shown that cotinine exposure induces convergence and amplification of the GSK3β-dependent PI3 kinase and cholinergic anti-inflammatory systems. The consequence is reduced pro-inflammatory cytokine secretion by human monocytes responding to bacteria or LPS, a TLR4 agonist. Findings Here we show that cotinine-induced inflammatory suppression may not be restricted to individual Toll-like receptors (TLRs. Indeed, in monocytic cells, cotinine suppresses the cytokine production that is normally resultant upon agonist-specific engagement of all of the major surface exposed TLRs (TLR 2/1; 2/6; 4 and 5, although the degree of suppression varies by TLR. Conclusions These results provide further mechanistic insight into the increased susceptibility to multiple bacterial infections known to occur in smokers. They also establish THP-1 cells as a potentially suitable model with which to study the influence of tobacco components and metabolites on TLR-initiated inflammatory events.

  15. Effect of hydrothermal treatment of coal on its associative structure

    Energy Technology Data Exchange (ETDEWEB)

    Shui Heng-fu; Wang Zhi-cai; Wang Gao-qiang; Niu Min-feng [Anhui University of Technology, Maanshan (China). School of Chemistry & Chemical Engineering

    2006-10-15

    4 bituminous coals with different ranks were thermally and hydrothermally treated under different conditions, and the raw and treated coals were extracted with carbon disulfide/N-2-pyrrolidinone (CS{sub 2}/NMP) mixed solvent (1:1 by volume). It is found that the extraction yields of the thermal or hydrothermal treated coals at proper conditions increase in different extent. The increments of extraction yields for hydrothermal treated coals are higher than those of thermal treated coals. FT-IR shows that the adsorption peaks at 3410 cm{sup -1} attributed to OH group for the hydrothermal treated coals decrease, suggesting the dissociation of the coal aggregation structure due to the breakage of hydrogen bonds, resulting in the increase of extraction yields for the treated coals. For higher rank coal, the removal of minerals and the dissociation of {pi}-cation association after hydrothermal treatment of coal may be responsible for the increase of extraction yield. In addition, the mechanism of hydrothermal treatment of coal was discussed. 15 refs., 2 figs., 5 tabs.

  16. Biofuel and chemical production by recombinant microorganisms via fermentation of proteinaceous biomass

    Energy Technology Data Exchange (ETDEWEB)

    Liao, James C.; Cho, Kwang Myung; Yan, Yajun; Huo, Yixin

    2016-03-15

    Provided herein are metabolically modified microorganisms characterized by having an increased keto-acid flux when compared with the wild-type organism and comprising at least one polynucleotide encoding an enzyme that when expressed results in the production of a greater quantity of a chemical product when compared with the wild-type organism. The recombinant microorganisms are useful for producing a large number of chemical compositions from various nitrogen containing biomass compositions and other carbon sources. More specifically, provided herein are methods of producing alcohols, acetaldehyde, acetate, isobutyraldehyde, isobutyric acid, n-butyraldehyde, n-butyric acid, 2-methyl-1-butyraldehyde, 2-methyl-1-butyric acid, 3-methyl-1-butyraldehyde, 3-methyl-1-butyric acid, ammonia, ammonium, amino acids, 2,3-butanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 2-methyl-1,4-butanediamine, isobutene, itaconate, acetoin, acetone, isobutene, 1,5-diaminopentane, L-lactic acid, D-lactic acid, shikimic acid, mevalonate, polyhydroxybutyrate (PHB), isoprenoids, fatty acids, homoalanine, 4-aminobutyric acid (GABA), succinic acid, malic acid, citric acid, adipic acid, p-hydroxy-cinnamic acid, tetrahydrofuran, 3-methyl-tetrahydrofuran, gamma-butyrolactone, pyrrolidinone, n-methylpyrrolidone, aspartic acid, lysine, cadeverine, 2-ketoadipic acid, and/or S-adenosyl-methionine (SAM) from a suitable nitrogen rich biomass.

  17. Evaluation of the Antihyperuricemic Activity of Phytochemicals from Davallia formosana by Enzyme Assay and Hyperuricemic Mice Model

    Directory of Open Access Journals (Sweden)

    Chen-Yu Chen

    2014-01-01

    Full Text Available Abnormal serum urate levels are recognized as a critical factor in the progression of several chronic diseases. To evaluate the antihyperuricemic effect of Davallia formosana, the inhibitory activities of 15 isolated phytochemicals, including five novel compounds of 6,8-dihydroxychromone-7-C-β-d-glucopyranoside (1, 6,8,3′,4′-tetrahydroxyflavanone-7-C-β-d-glucopyranoside (2, 6,8,4′-trihydroxyflavanone-7-C-β-d-glucopyranoside (3, 8-(2-pyrrolidinone-5-yl-catechin-3-O-β-d-allopyranoside (4, and epiphyllocoumarin-3-O-β-d-allopyranoside (5, were examined against xanthine oxidase (XOD and in a potassium oxonate-(PTO- induced acute hyperuricemic mice model. The results indicated that compounds 3 and 5 significantly inhibited XOD activity in vitro and reduced serum uric acid levels in vivo. This is the first report providing new insights into the antihyperuricemic activities of flavonoid glycosides which can possibly be developed into potential hypouricemic agents.

  18. Preparation of Nafion-sulfonated clay nanocomposite membrane for direct menthol fuel cells via a film coating process

    Science.gov (United States)

    Kim, Tae Kyoung; Kang, Myeongsoon; Choi, Yeong Suk; Kim, Hae Kyung; Lee, Wonmok; Chang, Hyuk; Seung, Doyoung

    Nafion sulfonated clay nanocomposite membranes were successfully produced via a film coating process using a pilot coating machine. For producing the composite membranes, we optimized the solvent ratio of N-methyl-2-pyrrolidinone (NMP) to N, N‧-dimethylacetamide (DMAc), the amount of sulfonated montmorillonite (S-MMT) in composite membranes and the overall concentration of composite dispersions. Based on the optimized viscosity and composition, the composite dispersions were coated on a poly(ethylene terephthalate) (PET) substrate film. The distance between a metering roll and a PET film and the ratio of metering roll speed versus coating roll speed of the pilot coating machine were varied to control membrane thickness. The film coated composite membrane exhibited enhanced properties in the swelling behavior against MeOH solution, ion conductivity and MeOH permeability, compared to the cast Nafion composite membrane due to the higher dispersion state of S-MMT in Nafion matrix and the uniform distribution of small-size ion clusters. These properties influenced a cell performance test of a direct methanol fuel cell (DMFC), showing the film coated composite membrane had a higher power density than that of Nafion 115. The power density was also related with the higher selectivity of the composite membrane than Nafion 115.

  19. Relationship between the fluidity of heat-treated coals and molecular weight distributions of their solvent-soluble component; Netsushoritan no yobai kayo seibun no bunshiryo bunpu to ryudosei no kanren

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, T.; Takanohashi, T.; Iino, M. [Tohoku University, Sendai (Japan). Institute for Chemical Reaction Science; Kato, K. [Nippon Steel Co. Ltd., Tokyo (Japan); Fukada, K. [NKK Corp., Tokyo (Japan)

    1996-10-28

    In order to improve the coke manufacturing process, considerations were given on fluidity manifestation mechanism of heat-treated coals from molecular weight distributions of extracts of a solvent mixed with CS2-N-methyl-2-pyrrolidinone (CS2-NMP). The heat treatment was performed in an autoclave under nitrogen atmosphere at a rate of 3{degree}C/min to settings of 200 to 550{degree}C. The resultant heat-treated coal was quenched, and then extracted by using the CS2-NMP mixed solvent. The fluidity was measured by using a Gieseler plastometer. Maximum extraction rate and the highest fluidity are in linear relationship, which suggests that the extracts govern the fluidity. Since heavy caking coal has no difference in the extraction rates due to heat treatment temperature, and its molecular weight distribution trend does not change, the extracted components which have existed primarily in the original coal govern the fluidity. In semi-caking coals, polymer molecular components are extracted in a large quantity at the softening starting temperature, but the quantity decreases as the temperature rises. However, low-molecular components present no quantitative change, while polymer molecular components decompose, decrease in molecular weight, get solubilized with rising temperature, and act as a binder to cause a flow. 7 figs., 1 tab.

  20. Viscoelasticity of various gel films prepared from solvent-soluble constituents in coal; Sekitanchu no yobai kayoseibun kara sakuseishita shushu no gel maku no nendansei

    Energy Technology Data Exchange (ETDEWEB)

    Takanohashi, T.; Isoda, S.; Doi, S.; Iino, M. [Tohoku University, Sendai (Japan). Institute for Chemical Reaction Science

    1996-10-28

    Viscoelasticity of gel films prepared from solvent-soluble constituents without ash of coal using the mixed solvent of carbon disulfide and N-methyl-2-pyrrolidinone (CS2-NMP) was measured to study the network structure of the constituents. In experiment, Upper Freeport coal and Zao Zhuang coal were used as specimens. Viscoelasticity of various gels with different weight fractions of solvent was measured by creep measurement under a fixed load and stress-strain analysis under variable loads. In the 2nd and 3rd creep measurements, although no large changes in elastic strain and viscoelastic strain were found, viscous strain gradually decreased with an increase in viscosity. In the case of small weight fraction of solvent, small viscous strain and viscoelastic strain were found, while slightly large elastic strain was found. It was thus suggested that this elastic strain is derived from not only physical cross-linked networks by coal-solvent interaction but also those by coal-coal interaction in polymer chains of coal itself. 9 refs., 4 figs., 1 tab.

  1. Surface tension of a coal extract in an organic solvent; Sekitan chushutsu seibun no kaigo to hyomen choryoku

    Energy Technology Data Exchange (ETDEWEB)

    Kikuchi, T.; Hayasaka, K.; Takanohashi, T.; Iino, M. [Tohoku University, Sendai (Japan). Institute for Chemical Reaction Science

    1996-10-28

    The behavior and properties of associated bodies were studied through measurement of surface tension considering acetone-soluble fraction relatively light among various solvent extracts of coal. In experiment, the acetone-soluble fraction was extracted from the substances extracted from Upper Freeport coal as standard specimen using the mixed solvent of carbon disulfide (CS2) and N-methyl-2-pyrrolidinone (NMP), and it was dissolved into NMP after drying. Surface tension was measured by Wilhelmy method. The experimental results are as follows. Equilibrium surface tension is equal to the surface tension of pure solvent in a low concentration range of solution, and decreases with an increase in concentration approaching a fixed value at 0 in log concentration, nearly showing an S curve. Adsorption of species with non-polar aromatic ring of the acetone-soluble fraction on a solution surface probably decreases surface tension. Change with time in surface tension is observed which suggests fast initial reaction and slow subsequent reaction. 4 figs.

  2. Fabrication of cost effective iron ore slime ceramic membrane for the recovery of organic solvent used in coke production

    Institute of Scientific and Technical Information of China (English)

    V.Singh; N.K.Meena; A.K.Golder; C.Das

    2016-01-01

    Improvement of coking properties of sub-bituminous coal (A) and bituminous coal (B) was done using blended organic solvents,namely,n-methyl-2-pyrrolidinone (NMP) and ethylenediamine (EDA).Various solvent blends were employed for the coal extraction under the total reflux condition.A low-cost ceramic membrane was fabricated using industrial waste iron ore slime of M/s TATA steel R&D,Jamshedpur (India) to separate out the dissolved coking fraction from the solvent-coal mixture.Membrane separations were carried out in a batch cell,and around 75 % recovered NMP was reused.The fractionated coal properties were determined using proximate and ultimate analyses.In the case of bituminous coal,the ash and sulfur contents were decreased by 99.3 % and 79.2 %,respectively,whereas,the carbon content was increased by 23.9 % in the separated coal fraction.Three different cleaning agents,namely deionized water,sodium dodecyl sulphate and NMP were used to regain the original membrane permeability for the reusing.

  3. Chitosan-based dressings loaded with neurotensin--an efficient strategy to improve early diabetic wound healing.

    Science.gov (United States)

    Moura, Liane I F; Dias, Ana M A; Leal, Ermelindo C; Carvalho, Lina; de Sousa, Hermínio C; Carvalho, Eugénia

    2014-02-01

    One important complication of diabetes mellitus is chronic, non-healing diabetic foot ulcers (DFUs). This study aims to develop and use dressings based on chitosan derivatives for the sustained delivery of neurotensin (NT), a neuropeptide that acts as an inflammatory modulator in wound healing. Three different derivatives, namely N-carboxymethyl chitosan, 5-methyl pyrrolidinone chitosan (MPC) and N-succinyl chitosan, are presented as potential biomaterials for wound healing applications. Our results show that MPC has the best fluid handling capacity and delivery profile, also being non-toxic to Raw 264.7 and HaCaT cells. NT-loaded and non-loaded MPC dressings were applied to control/diabetic wounds to evaluate their in vitro/in vivo performance. The results show that the former induced more rapid healing (50% wound area reduction) in the early phases of wound healing in diabetic mice. A NT-loaded MPC foam also reduced expression of the inflammatory cytokine TNF-α (P<0.001) and decreased the amount of inflammatory infiltrate on day 3. On day 10 MMP-9 was reduced in diabetic skin (P<0.001), significantly increasing fibroblast migration and collagen (COL1A1, COL1A2 and COL3A1) expression and deposition. These results suggest that MPC-based dressings may work as an effective support for sustained NT release to reduce DFUs.

  4. Design, Synthesis, and Biological and Structural Evaluations of Novel HIV-1 Protease Inhibitors To Combat Drug Resistance

    Energy Technology Data Exchange (ETDEWEB)

    Parai, Maloy Kumar; Huggins, David J.; Cao, Hong; Nalam, Madhavi N.L.; Ali, Akbar; Schiffer, Celia A.; Tidor, Bruce; Rana, Tariq M. (MIT); (UMASS, MED); (Sanford-Burnham)

    2012-09-11

    A series of new HIV-1 protease inhibitors (PIs) were designed using a general strategy that combines computational structure-based design with substrate-envelope constraints. The PIs incorporate various alcohol-derived P2 carbamates with acyclic and cyclic heteroatomic functionalities into the (R)-hydroxyethylamine isostere. Most of the new PIs show potent binding affinities against wild-type HIV-1 protease and three multidrug resistant (MDR) variants. In particular, inhibitors containing the 2,2-dichloroacetamide, pyrrolidinone, imidazolidinone, and oxazolidinone moieties at P2 are the most potent with Ki values in the picomolar range. Several new PIs exhibit nanomolar antiviral potencies against patient-derived wild-type viruses from HIV-1 clades A, B, and C and two MDR variants. Crystal structure analyses of four potent inhibitors revealed that carbonyl groups of the new P2 moieties promote extensive hydrogen bond interactions with the invariant Asp29 residue of the protease. These structure-activity relationship findings can be utilized to design new PIs with enhanced enzyme inhibitory and antiviral potencies.

  5. Controlling fungal biofilms with functional drug delivery denture biomaterials.

    Science.gov (United States)

    Wen, Jianchuan; Jiang, Fuguang; Yeh, Chih-Ko; Sun, Yuyu

    2016-04-01

    Candida-associated denture stomatitis (CADS), caused by colonization and biofilm-formation of Candida species on denture surfaces, is a significant clinical concern. We show here that modification of conventional denture materials with functional groups can significantly increase drug binding capacity and control drug release rate of the resulting denture materials for potentially managing CADS. In our approach, poly(methyl methacrylate) (PMMA)-based denture resins were surface grafted with three kinds of polymers, poly(1-vinyl-2-pyrrolidinone) (PNVP), poly(methacrylic acid) (PMAA), and poly(2-hydroxyethyl methacrylate) (PHEMA), through plasma-initiated grafting polymerization. With a grafting yield as low as 2 wt%, the three classes of new functionalized denture materials showed significantly higher drug binding capacities toward miconazole, a widely used antifungal drug, than the original PMMA denture resin control, leading to sustained drug release and potent biofilm-controlling effects against Candida. Among the three classes of functionalized denture materials, PNVP-grafted resin provided the highest miconazole binding capability and the most powerful antifungal and biofilm-controlling activities. Drug binding mechanisms were studied. These results demonstrated the importance of specific interactions between drug molecules and functional groups on biomaterials, shedding lights on future design of CADS-managing denture materials and other related devices for controlled drug delivery.

  6. Molecular simplification of 1,4-diazabicyclo[4.3.0]nonan-9-ones gives piperazine derivatives that maintain high nootropic activity.

    Science.gov (United States)

    Manetti, D; Ghelardini, C; Bartolini, A; Dei, S; Galeotti, N; Gualtieri, F; Romanelli, M N; Teodori, E

    2000-11-16

    Several 4-substituted 1-acylpiperazines, obtained by molecular simplification of 4-substituted 1,4-diazabicyclo[4.3.0]nonan-9-ones, have been synthesized and tested in vivo on the mouse passive avoidance test, to evaluate their nootropic activity. The results show that, apparently, an N-acylpiperazine group can mimic the 2-pyrrolidinone ring of 1,4-diazabicyclo[4.3.0]nonan-9-one, as the compounds of the new series maintain high nootropic activity. Moreover molecular simplification produces more clear-cut structure-activity relationships with respect to the parent series. The mechanism of action also appears to be similar in the two series. In fact, although the molecular mechanism remains to be elucidated, the most potent compound of each class (DM232 and 13, DM235) is able to increase acetylcholine release in rat brain. Piperazine derivatives represent a new class of nootropic drugs with an in vivo pharmacological profile very similar to that of piracetam, showing much higher potency with respect to the reference compound. Among the compounds studied, 13 (DM235) shows outstanding potency, being active at a dose of 0.001 mg kg(-1) sc.

  7. Molecular structures and conformations of 1-benzenesulphonyl-2-oxo-5-alkoxypyrrolidines with anti-amnesic activity. X-ray, 1H-NMR and quantum mechanical (PM3) studies

    Science.gov (United States)

    Amato, Maria E.; Bandoli, Giuliano; Dolmella, Alessandro; Grassi, Antonio; Pappalardo, Giuseppe C.; Toja, Emilio

    1991-04-01

    The crystal and molecular structures of the nootropic agents RU-47001 ((±) 1-(4-nitrobenzenesulphonyl)-2-oxo-5-ethoxypyrrolidine) and RU-47064 ((±) 1-(4-nitrobenzenesulphonyl)-2-oxo-5-isopropyloxypyrrolidine) have been determined by X-ray analysis and their solution conformation has been investigated using 1H NMR spectroscopy. The conformations of these molecules together with those of their analogues RU-35929 ((±) 1-benzenesulphonyl-2-oxo-5-ethoxypyrrolidine), RU-47010 ((±) 1-(3-pyridinylsulphonyl)-2-oxo-5-ethoxypyrrolidine) and RU-35965 ((±) 1-benzenesulphonyl-2-oxo-5-isopropyloxypyrrolidine) have been deduced from semi-quantitative PM3 type theoretical calculations. The main feature of all compounds consists of a common envelope conformation with C (4) at the flap of the pyrrolidinone ring in the solid, that in solution changes into the analogous, but opposite, possible puckered conformational isomer. The 5-alkoxy groups were found rather flexible in solution. Theoretical preferred conformations about NS and SC bonds were in acceptable agreement with those of the solid state. The calculated torsional energetics suggested that 1- 5 do not undergo conformational interconversion.

  8. X-ray and 1H-NMR spectroscopic studies of the structures and conformations of the new nootropic agents RU-35929, RU-47010 and RU-35965

    Science.gov (United States)

    Amato, Maria E.; Bandoli, Giuliano; Casellato, Umberto; Pappalardo, Giuseppe C.; Toja, Emilio

    1990-10-01

    The crystal and molecular structures of the nootropics (±)1-benzenesulphonyl-2-oxo-5-ethoxypyrrolidine ( 1), (±)1-(3-pyridinylsulphonyl)-2-oxo-5-ethoxypyrrolidine ( 2) and (±)1-benzenesulphonyl-2-oxo-5-isopropyloxypyrrolidine ( 3) have been determined by X-ray analysis. The solution conformation of 1, 2 and 3 has been investigated by 1H NMR spectroscopy. In the solid state, the main feature consists of the similar structural parameters and conformations, with the exception of the conformation adopted by the 5-ethoxy moiety which changes on passing from 1 to 2. The solid state overall enveloped conformation of the 2-pyrrolidinone ring for the three nootropics is found to be retained in solution on the basis of NMR evidence. Comparison between calculated and experimental coupling constant values shows that one of the two possible puckered opposite conformational isomers (half-chair shapes) occurs in solution. The relative pharmacological potencies of 1, 2 and 3 cannot therefore be interpreted in terms of the different conformation features presently detectable by available experimental methods.

  9. Cellulose multilayer Membranes manufacture with Ionic liquid

    KAUST Repository

    Livazovic, Sara

    2015-05-09

    Membrane processes are considered energy-efficient for water desalination and treatment. However most membranes are based on polymers prepared from fossil petrochemical sources. The development of multilayer membranes for nanofiltration and ultrafiltration, with thin selective layers of naturally available cellulose has been hampered by the availability of non-aggressive solvents. We propose the manufacture of cellulose membranes based on two approaches: (i) silylation, coating from solutions in tetrahydrofuran, followed by solvent evaporation and cellulose regeneration by acid treatment; (ii) casting from solution in 1-ethyl-3-methylimidazolum acetate ([C2mim]OAc), an ionic liquid, followed by phase inversion in water. By these methods porous supports could be easily coated with semi-crystalline cellulose. The membranes were hydrophilic with contact angles as low as 22.0°, molecular weight cut-off as low as 3000 g mol-1 with corresponding water permeance of 13.8 Lm−2 h−1 bar−1. Self-standing cellulose membranes were also manufactured without porous substrate, using only ionic liquid as green solvent. This membrane was insoluble in water, tetrahydrofuran, hexane, N,N-dimethylformamide, 1-methyl-2-pyrrolidinone and N,N-dimethylacetamide.

  10. A controlled wet-spinning and dip-coating process for preparation of high-permeable TiO2 hollow fiber membranes.

    Science.gov (United States)

    Zhang, Qi; Wang, Hua; Fan, Xinfei; Chen, Shuo; Yu, Hongtao; Quan, Xie

    2016-01-01

    In order to improve the permeate flux of photocatalytic membranes, we present an approach for coupling TiO2 with ceramic hollow fiber membranes. The ceramic hollow fiber membranes with high permeate flux were fabricated by a controlled wet-spinning process using polyethersulfone (PESf) and ceramic powder as precursors and 1-methyl-2-pyrrolidinone as solvent, and the subsequent TiO2 coating was performed by a dip-coating process using tetra-n-butyl titanate as precursor. It has been found that the PESf/ceramic powder ratio could influence the structure of the membranes. Here the as-prepared TiO2 hollow fiber membranes had a pure water flux of 4,450 L/(m(2)·h). The performance of the TiO2 hollow fiber membrane was evaluated using humic acid (HA) as a test substance. The results demonstrated that this membrane exhibited a higher permeate flux under UV irradiation than in the dark and the HA removal efficiency was enhanced. The approach described here provides an operable route to the development of high-permeable photocatalytic membranes for water treatment.

  11. Actuation behaviour of polyaniline films and tubes prepared by phase inversion technique

    Science.gov (United States)

    Xi, Binbin; Truong, Van-Tan; Mottaghitalab, Vahid; Whitten, Philip; Spinks, Geoffrey M.; Wallace, Gordon G.

    2005-02-01

    The phase inversion technique was used to produce polyaniline (PAn) actuators with different geometries that cannot be obtained by PAn cast from N-methyl-2-pyrrolidinone (NMP) solution in a conventional way. PAn was cast and coagulated in a water bath forming films and tubes with or without a platinum (Pt) wire helix as an interconnect. PAn was doped with hydrochloric solution (HCl, 1 M) (PAn/HCl) or methanesulfonic acid (MSA, 1 M) (PAn/MSA). In nitric acid (HNO3, 1 M) aqueous electrolyte, the actuation strain of PAn/HCl was 0.9% which increased to 2.0% and 2.7% for the tubes without and with the Pt helix, respectively. The Pt helix helped prevent the IR drop along the actuator. Comparing with NaNO3 (1 M) aqueous electrolyte, the use of HNO3 aqueous electrolyte gave better actuation stability where at least 100 cycles were observed and the final actuation strain was determined by the size of dopant. Change of coagulation bath from water to NMP (30% w/w)/water resulted in subtle difference in the Young"s modulus of PAn/MSA in oxidized and reduced states. PAn prepared by phase inversion technique is porous by nature, consequently it is brittle and exhibits a low actuation stress (0.3 - 0.4 MPa).

  12. Facile Synthesis of New Aromatic Polyamides Based on 1,2-Dihydro-2-(4-carboxylphenyl)-4-[4-(4-carboxyl- phenoxy)-3-methylphenyl]phthalazin-1-one

    Institute of Scientific and Technical Information of China (English)

    程琳; 应磊; 杨小玲; 蹇锡高

    2005-01-01

    A new monomer diacid, 1,2-dihydro-2-(4-carboxylphenyl)-4-[4-(4-carboxylphenoxy)-3-methylphenyl]phtha-lazin-1-one (3), was synthesized through the aromatic nucleophilic substitution reaction of a readily available unsymmetrical phthalazinone 1 bisphenol-like with p-chlorobenzonitrile in the presence of potassium carbonate in N,N-dimethylacetamide and alkaline hydrolysis. The diacid could be directly polymerized with various aromatic diamines 4a-4e using triphenyl phosphite and pyridine as condensing agents to give five new aromatic poly(ether amide)s 5a-5e containing the kink non-coplanar heterocyclic units with inherent viscosities of 1.30-1.54 dL/g.The polymers were readily soluble in a variety of solvents such as N,N-dimethylformamide (DMF), N,N-dimethyl-acetamide (DMA), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidinone (NMP), and even in m-cresol and pyridine (Py). The transparent, flexible and tough films could be formed by solution casting. The glass transition tem-peratures Tg were in the range of 286-317℃.

  13. {sup 252}Cf plasma desorption and laser desorption mass spectrometry for the determination of molecular weight distribution of coal derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, B.R.; Bartle, K.D.; Ross, A.B.; Herod, A.A.; Kandiyoti, R.; Larsen, J.W. [University of Leeds, Leeds (United Kingdom). School of Chemistry

    1999-11-01

    A detailed knowledge of the molecular mass (MM) distribution in coal and its derived products is essential for a fundamental understanding of coal structure, and of the processes occurring during coal conversion. Fractionation using size exclusion chromatography (s.e.c.) using N-methyl-2-pyrrolidinone as the mobile phase has been applied to such materials and has provided improved MM distributions. Absolute calibration has been provided using matrix assisted laser desorption ionisation mass spectrometry (MAl.d.I.-m.s.). An alternative method of volatilising and ionising large molecules for mass spectrometry (m.s.) is {sup 252}Cf plasma desorption ({sup 252}Cf p.d.-m.s.). This involves the use of energetic fission fragments from the decay of {sup 252}Cf and produces mass spectra consisting predominantly of molecular ions from a range of polymers and biomolecules. This has been used by other workers to determine the molecular weight distribution of heavy distillation residues obtained from coal liquefaction processes either unfractionated or fractionated into broad fractions. Generally, a good agreement was obtained between values of MM determined by {sup 252}Cf p.d.-m.s. and s.e.c. A comparison is reported of MM distribution determined by {sup 252}Cf p.d.-m.s. and laser desorption mass spectrometry (l.d.-m.s.) for narrower fractions separated by s.e.c. from a coal tar pitch. 19 refs., 4 figs., 1 tab.

  14. Identification of organically associated trace elements in wood and coal by inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Richaud, R.; Lazaro, M.J.; Lachas, H.; Miller, B.B.; Herod, A.A.; Dugwell, D.R.; Kandiyoti, R. [Imperial College of Science, Technology and Medicine, London (United Kingdom). Dept. of Chemical Engineering and Chemical Technology

    2000-07-01

    1-Methyl-2-pyrrolidinone (NMP) was used to extract samples of wood (forest residue) and coal; the extracts were analysed by inductively coupled plasma mass spectrometry (ICP-MS) using two different sample preparation methods, in order to identify trace elements associated with the organic part of the samples. A sample of fly ash was similarly extracted and analysed. Size exclusion chromatograms of the extracts indicated the presence of significant amounts of large molecular mass materials ({gt} 1000 {mu}) in the biomass and coal extracts but not in the ash extract. Trace element analyses were carried out using ICP-MS on the acid digests prepared by 'wet ashing' and microwave extraction. Sixteen elements (As, Ba, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, pH, Sb, Se, V and Zn) were quantified, in the samples before extraction, in the extracts and in the residues. Concentrations of trace elements in the original biomass samples were lower than in the coal sample while the concentrations in the ash sample were the highest. The major trace elements in the NMP extracts were Ba, Cu, Mn and Zn from the forest residue; Ba, Cu, Mn, Pb and Zn from the coal; Cu and Zn from the ash. These elements are believed to be associated with the organic extracts from the forest residue and coal, and also from the ash.

  15. Configuration control on the shape memory stiffness of molecularly imprinted polymer for specific uptake of creatinine

    Science.gov (United States)

    Ang, Qian Yee; Zolkeflay, Muhammad Helmi; Low, Siew Chun

    2016-04-01

    In this study, sol-gel processing was proposed to prepare a creatinine (Cre)-imprinted molecularly imprinted polymer (MIP). The intermolecular interaction constituted by the cross-linkers, i.e., 2-acrylamido-2-methylpropane-sulfonic acid (AMPS) and aluminium ion (Al3+), was studied and compared in order to form a confined matrix that promises the effectiveness of molecular imprinting. In view of the shape recognition, the hydrogen bonded Cre-AMPS did not demonstrate good recognition of Cre, with Cre binding found only at 5.70 ± 0.15 mg g-1 of MIP. Whilst, MIP cross-linked using Al3+ was able to attain an excellent Cre adsorption capacity of 19.48 ± 0.64 mg g-1 of MIP via the stronger ionic interaction of Cre-Al3+. Based on the Scatchard analysis, a higher Cre concentration in testing solution required greater driving force to resolve the binding resistance of Cre molecules, so as to have a precise Cre binding with shape factor. The molecular recognition ability of Cre-MIP in present work was shape-specific for Cre as compared to its structural analogue, 2-pyrrolidinone (2-pyr), by an ideal selectivity coefficient of 6.57 ± 0.10. In overall, this study has come up with a practical approach on the preparation of MIP for the detection of renal dysfunction by point-of-care Cre testing.

  16. Delay photoconductivity in polyaniline films from different solvents

    Energy Technology Data Exchange (ETDEWEB)

    Bondarenko, V.E. [Russian Acad. of Sci., Moscow (Russian Federation). Inst. of Biochem. Phys.; Zhuravleva, T.S. [Russian Acad. of Sci., Moscow (Russian Federation). Inst. of Biochem. Phys.; Efimov, O.N. [Rossijskaya Akademiya Nauk, Chernogolovka (Russian Federation). Inst. Khimicheskoj Fiziki; Nikolaeva, G.V. [Rossijskaya Akademiya Nauk, Chernogolovka (Russian Federation). Inst. Khimicheskoj Fiziki

    1997-01-01

    Decay kinetics of photoconductivity induced by the nanosecond laser pulses has been studied for films of polyaniline (PANI) in the emeraldine base form (EB) in the temperature range from 110 to 300 K. The films are prepared by casting solutions of EB in formic acid and N-methyl-2-pyrrolidinone (NMP) on glass plates covered by conducting layer of SnO{sub 2}. Photocurrent signals were registered up to 40 ms and 20 {mu}s in the films obtained from formic acid and from NMP, respectively. In both cases the kinetic curves are fitted well by the stretched-exponential function F{sub 1}(t) {proportional_to} exp[-(t/{tau}{sub str}){sup {beta}}] with the temperature dependent parameters {tau}{sub str} and {beta}. It was found that the quantum yield of photocharge was equal to 10{sup -4} for the films obtained from the formic acid solution and to 2.10{sup -6} for those obtained from the NMP solution. The possible mechanisms accounting for photocurrent characteristics are discussed. (orig.)

  17. Liquid-Phase Exfoliation of Graphite into Single- and Few-Layer Graphene with α-Functionalized Alkanes.

    Science.gov (United States)

    Haar, Sébastien; Bruna, Matteo; Lian, Jian Xiang; Tomarchio, Flavia; Olivier, Yoann; Mazzaro, Raffaello; Morandi, Vittorio; Moran, Joseph; Ferrari, Andrea C; Beljonne, David; Ciesielski, Artur; Samorì, Paolo

    2016-07-21

    Graphene has unique physical and chemical properties, making it appealing for a number of applications in optoelectronics, sensing, photonics, composites, and smart coatings, just to cite a few. These require the development of production processes that are inexpensive and up-scalable. These criteria are met in liquid-phase exfoliation (LPE), a technique that can be enhanced when specific organic molecules are used. Here we report the exfoliation of graphite in N-methyl-2-pyrrolidinone, in the presence of heneicosane linear alkanes terminated with different head groups. These molecules act as stabilizing agents during exfoliation. The efficiency of the exfoliation in terms of the concentration of exfoliated single- and few-layer graphene flakes depends on the functional head group determining the strength of the molecular dimerization through dipole-dipole interactions. A thermodynamic analysis is carried out to interpret the impact of the termination group of the alkyl chain on the exfoliation yield. This combines molecular dynamics and molecular mechanics to rationalize the role of functionalized alkanes in the dispersion and stabilization process, which is ultimately attributed to a synergistic effect of the interactions between the molecules, graphene, and the solvent.

  18. Novel Soluble Polyimide Containing 4-tert-Butyltoluene Moiety: Synthesis and Characterization

    Institute of Scientific and Technical Information of China (English)

    WANG, Chenyi; LI, Guang; JIANG, Jianming

    2009-01-01

    Based on the synthesis of a rigid aromatic diamine, α,α-bis(4-aminophenyl)-4-(t-butyl)toluene (1), a novel polyimide (PI) 3 was prepared from this diamine monomer and 4,4'-oxydiphthalic dianhydride via a one-step high-temperature polycondensation. FT-IR, ~1H NMR and elemental analysis were used to investigate the chemical structures of 1 and 3. The results confirmed that they agreed with the proposed structures for both 1 and 3 completely. The obtained PI 3 showed excellent solubility in most common solvents such as N-methyl-2-pyrrolidinone,N,N-dimethylacetamide, N,N-dimethylformamide, chloroform, dichloromethane and tetrahydrofuran. The resulting strong and flexible film exhibited high thermal stability with the glass transition temperature at 317 ℃ and the temperature at 10% weight loss beyond 519 ℃ in both air and nitrogen atmospheres. Moreover, the film also showed high optical transparency, low dielectric constant (3.13 at 1 MHz), low water absorption (0.40%) and hydrophobic character.

  19. Synthesis of a family of spirocyclic scaffolds: building blocks for the exploration of chemical space.

    Science.gov (United States)

    Kumar, Sarvesh; Thornton, Paul D; Painter, Thomas O; Jain, Prashi; Downard, Jared; Douglas, Justin T; Santini, Conrad

    2013-07-05

    This report describes the preparation of a series of 17 novel racemic spirocyclic scaffolds that are intended for the creation of compound libraries by parallel synthesis for biological screening. Each scaffold features two points of orthogonal diversification. The scaffolds are related to each other in four ways: (1) through stepwise changes in the size of the nitrogen-bearing ring; (2) through the oxidation state of the carbon-centered point of diversification; (3) through the relative stereochemical orientation of the two diversification sites in those members that are stereogenic; and (4) through the provision of both saturated and unsaturated versions of the furan ring in the scaffold series derived from 3-piperidone. The scaffolds provide incremental changes in the relative orientation of the diversity components that would be introduced onto them. The scaffolds feature high sp(3) carbon content which is essential for the three-dimensional exploration of chemical space. This characteristic is particularly evident in those members of this family that bear two stereocenters, i.e., the two series derived from 3-piperidone and 3-pyrrolidinone. In the series derived from 3-piperidone we were able to "split the difference" between the two diastereomers by preparation of their corresponding unsaturated version.

  20. Size-exclusion chromatography of large molecules from coal liquids, petroleum residues, soots, biomass tars and humic substances.

    Science.gov (United States)

    Herod, Alan A; Zhuo, Yuqun; Kandiyoti, Rafael

    2003-06-30

    Size-exclusion chromatography (SEC) using 1-methyl-2-pyrrolidinone (NMP) as eluent has been calibrated using various standard polymers and model compounds and applied to the analysis of extracts of coal, petroleum and kerogens, to petroleum vacuum residues, soots, biomass tars and humic substances. Three separate columns of different molecular mass (MM) ranges were used, with detection by UV absorption; an evaporative light scattering detector was used for samples with no UV absorption. Fractionation was useful to separate signal from the less abundant high-mass material, which was normally masked by the strong signal from the more abundant low-mass material in the absence of fractionation. Fractionation methods used to isolate high-mass materials before SEC analysis included planar chromatography, column chromatography and solvent solubility. The apparently large molecules were concentrated into the fractions not soluble in common solvents and were relatively immobile in planar chromatography. All samples and fractions contained some material excluded from the column porosity. Evidence from other techniques suggests that the excluded material is of different structures from that of the resolved material rather than consisting of aggregates of small molecules. We speculate that the excluded material may elute early because the structures of this material are three-dimensional rather than planar or near planar.

  1. Shear Rheology of Suspensions of Porous Zeolite Particles in Concentrated Polymer Solutions

    Science.gov (United States)

    Olanrewaju, Kayode O.; Breedveld, Victor

    2008-07-01

    We present experimental data on the shear rheology of Ultem (polyetherimide)/NMP(l-methyl-2-pyrrolidinone) solutions with and without suspended surface-modified porous/nonporous zeolite (ZSM-5) particles. We found that the porous zeolite suspensions have relative viscosities that significantly exceed the Krieger-Dougherty predictions for hard sphere suspensions. The major origin of this discrepancy is the selective absorption of NMP solvent into the zeolite pores, which raises both the polymer concentration and the particle volume fraction, thus enhancing both the viscosity of the continuous phase Ultem/NMP polymer solution and the particle contribution to the suspension viscosity. Other factors, such as zeolite non-sphericity and specific interactions with Ultem polymer, contribute to the suspension viscosity to a lesser extent. We propose a predictive model for the viscosity of porous zeolite suspensions by incorporating an absorption parameter, α, into the Krieger-Dougherty model. We also propose independent approaches to determine α. The first one is indirect and based on zeolite density/porosity data, assuming that all pores will be filled with solvent. The other method is based on our experimental data, by comparing the viscosity data of porous versus non-porous zeolite suspensions. The different approaches are compared.

  2. Ceftobiprole: a new broad spectrum cephalosporin.

    Science.gov (United States)

    El Solh, Ali

    2009-07-01

    Ceftobiprole, formerly designated BAL9141/Ro 63-9141, is a pyrrolidinone-3-ylidene-methyl cephalosporin with demonstrated in vitro activity against MRSA, Enterococcus faecalis, Enterobacteriaceae and Pseudomonas aeruginosa. Ceftobiprole has a low potential for inducing chromosomal AmpC beta-lactamases but it is hydrolyzed by most extended spectrum beta-lactamases and metallo-beta-lactamases. Glomerular filtration is predominantly responsible for removal of the free drug from the systemic circulation. The efficacy of ceftobiprole in the treatment of complicated skin and ski-structure infections has been recently demonstrated in two Phase III randomized clinical trials involving 1600 patients. Two other Phase III clinical trials to assess ceftobiprole's efficacy in community-acquired pneumonia and nosocomial pneumonia have also concluded. While the drug met the noninferiority criteria for community-acquired pneumonia and nosocomial pneumonia involving non-ventilator associated pneumonia, ceftobiprole was less effective than the comparator in ventilator associated pneumonia subjects. Ceftobiprole was well tolerated with a safety profile consistent with the cephalosporin class of antibiotic. The most frequent drug-related adverse event was dysgeusia. Ceftobiprole is intended for use in the hospital for the treatment of infections that frequently involve beta-lactam-resistant Gram-negative and Gram-positive organisms.

  3. Porous Polyimide Membranes Prepared by Wet Phase Inversion for Use in Low Dielectric Applications

    Directory of Open Access Journals (Sweden)

    Jung Ah Lim

    2013-04-01

    Full Text Available A wet phase inversion process of polyamic acid (PAA allowed fabrication of a porous membrane of polyimide (PI with the combination of a low dielectric constant (1.7 and reasonable mechanical properties (Tensile strain: 8.04%, toughness: 3.4 MJ/m3, tensile stress: 39.17 MPa, and young modulus: 1.13 GPa, with further thermal imidization process of PAA. PAA was simply synthesized from purified pyromellitic dianhydride (PMDA and 4,4-oxydianiline (ODA in two different reaction solvents such as γ-butyrolactone (GBL and N-methyl-2-pyrrolidinone (NMP, which produce Mw/PDI of 630,000/1.45 and 280,000/2.0, respectively. The porous PAA membrane was fabricated by the wet phase inversion process based on a solvent/non-solvent system via tailored composition between GBL and NMP. The porosity of PI, indicative of a low electric constant, decreased with increasing concentration of GBL, which was caused by sponge-like formation. However, due to interplay between the low electric constant (structural formation and the mechanical properties, GBL was employed for further exploration, using toluene and acetone vs. DI-water as a coagulation media. Non-solvents influenced determination of the PAA membrane size and porosity. With this approach, insight into the interplay between dielectric properties and mechanical properties will inform a wide range of potential low-k material applications.

  4. A thermodynamic study of ketoreductase-catalyzed reactions 5. Reduction of substituted ketones in n-hexane

    Energy Technology Data Exchange (ETDEWEB)

    Tewari, Yadu B. [Biochemical Science and Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States)], E-mail: yadu.tewari@nist.gov; Vanderah, David J. [Biochemical Science and Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States)], E-mail: david.vanderah@nist.gov; Schantz, Michele M. [Biochemical Science and Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States)], E-mail: michele.schantz@nist.gov; Goldberg, Robert N. [Biochemical Science and Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States)], E-mail: robert.goldberg@nist.gov; Rozzell, J. David [Codexis, Inc., 129 N. Hill Avenue, Pasadena, CA 91106 (United States)], E-mail: david.rozzell@codexis.com; Liebman, Joel F. [Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250 (United States)], E-mail: jliebman@umbc.edu; Hui, Raymond Wai-Man; Nissenbaum, Yitzy; Parniani, Ahmad Reza [Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250 (United States)

    2008-04-15

    The equilibrium constants K for the ketoreductase-catalyzed reduction reactions of 1-benzyl-3-pyrrolidinone, ethyl 2-oxo-4-phenylbutyrate, ethyl 4-chloroacetoacetate, 1-benzyl-4-piperidone, and 1-benzyl-3-piperidone were measured in n-hexane at T = 298.15 K by using gas chromatography. The equilibrium constants for the reaction involving 1-benzyl-4-piperidone were also measured as a function of temperature (288.15 to 308.05) K. The calculated thermodynamic quantities for the reaction (1-benzyl-4-piperidone + 2-propanol = 1-benzyl-4-hydroxypiperidine + acetone) reaction carried out in n-hexane at T = 298.15 K are: K = (26.2 {+-} 1.7); {delta}{sub r}G{sub m}{sup 0}=-(8.10{+-}0.16)kJ.mol{sup -1}; {delta}{sub r}H{sub m}{sup 0}=-(3.44{+-}0.42)kJ.mol{sup -1}; and {delta}{sub r}S{sub m}{sup 0}=(15.6{+-}1.4)J.K{sup -1}.mol{sup -1}. The chirality of the hydroxyl products of the reactions has also been investigated. The results showed that the stereoselectivity of the hydroxyl products formed can be controlled by the selection of the solvent and enzyme used in these reactions. The thermochemical results for these reactions are compared with the results for reactions that have analogous structural features as well as with the results of quantum chemical calculations.

  5. Limiting activity coefficients and gas-liquid partition coefficients of various solutes in piperidinium ionic liquids: measurements and LSER calculations.

    Science.gov (United States)

    Paduszyński, Kamil; Domańska, Urszula

    2011-06-30

    This paper is a continuation of our systematic investigations on piperidinium ionic liquids and presents new data on activity coefficients at infinite dilution for 43 solutes: linear and branched alkanes, cycloalkanes, alkenes, alkynes, benzene, alkylbenzenes, alcohols, water, thiophene, tetrahyrdofuran (THF), methyl tert-butyl ether (MTBE), linear ethers, acetone, and linear ketones in the ionic liquid 1-butyl-1-methyl-piperidinium bis(trifluoromethylsulfonyl)imide, [BMPIP][NTf2]. The data were determined by gas-liquid chromatography (GLC) at temperatures from 308.15 to 358.15 K. These values were compared to those previously published for the bis-(trifluoromethylsulfonyl)imide-based ionic liquids. The partial molar excess enthalpies ΔH1(E,∞) and entropies ΔS1(E,∞) at infinite dilution were calculated from the experimental γ13(∞) values obtained over the temperature range. The values of the selectivities for different separation problems were calculated from γ13(∞) and compared to literature values for N-methyl-2-pyrrolidinone (NMP), sulfolane, and additional ionic liquids. Experimental limiting activity coefficients were used to calculate gas-IL partition coefficients of solutes, K(L). The modeling with specific linear solvation energy relationship (LSER) equations was performed for data obtained in this work and those reported earlier for 1-butyl-1-methylpiperidinium thiocyanate, [BMPIP][SCN].

  6. SAXS and NMR analysis for the cast solvent effect on sPEEK membrane properties.

    Science.gov (United States)

    Luu, Dinh Xuan; Cho, Eun-Bum; Han, Oc Hee; Kim, Dukjoon

    2009-07-30

    The cast solvent effect on the structure and properties of sulfonated poly(ether ether ketone) (sPEEK) was studied. PEEK was sulfonated to have different sulfonation degrees of 65, 70, and 75%, and its membrane was prepared using the two types of solvents, N,N-dimethylacetamide (DMA) and 1-methyl-2-pyrrolidinone (NMP). Ionic cluster size was analyzed using small-angle X-ray scattering (SAXS), and it was correlated with a few essential membrane properties such as water uptake, methanol permeability, proton conductivity, and cell performance in direct methanol fuel cells (DMFCs). Synchrotron SAXS and solid state NMR data revealed the structural difference between the sPEEK membranes prepared using NMP and DMA, regarding the cluster dimensions of 3.22 and 2.70 nm, respectively. Although the water uptake, methanol permeability, and proton conductivity of the membranes prepared with NMP were higher than those with DMA, the overall cell performance was vice versa. The dimensional instability associated with high water swelling as well as high methanol permeability were the main causes for this inferior cell efficiency of NMP cast membranes. This report demonstrates the importance of selection of cast solvent in preparation of SPEEK electrolyte membranes for DMFC application.

  7. Studies of the fundamentals of solids state batteries

    Science.gov (United States)

    Abraham, K. M.; Alamgir, M.

    1990-11-01

    Several methods have been developed to dimensionally stabilize polymer electrolytes based on poly-(bis (methoxy ethoxy ethoxide) phosphazene), known as MEEP. In contrast to the poor dimensional stability exhibited by complexes of MEEP with most Li salts, those prepared with LiAlCl4 have been isolated as the first example of free-standing MEEP-(LiX)n films. The mechanical properties of dimensionally unstable MEEP-(LIX)n complexes can be significantly improved by forming composites with polymers such as poly(ethylene oxide), poly(propylene oxide), poly(ethylene glycol diacrylate) and poly(vinyl pyrrolidinone). The conductivity of 6.7 x 10(exp -5) ohm(exp -1) cm(exp -1) at 25 C exhibited by 55 w/o MEEP/45 w/o PEO-(LiN(CF3SO2)2)0.13 is among the highest values reported to date for a dimensionally stable electrolyte. The preparation, and conductivity, calorimetric and electrochemical studies of these electrolytes are described. Cyclic voltammetric data indicated that these electrolytes have anodic stability at least up to 4.5V versus Li(+)/Li. They have shown excellent compatibility with Li metal making them suitable for use as Li(+) conductive solid electrolytes in solid-state Li batteries. Li/TiS2 solid-state cells utilizing some of these electrolytes have exceeded 200 cycles.

  8. Sample contamination with NMP-oxidation products and byproduct-free NMP removal from sample solutions

    Energy Technology Data Exchange (ETDEWEB)

    Cesar Berrueco; Patricia Alvarez; Silvia Venditti; Trevor J. Morgan; Alan A. Herod; Marcos Millan; Rafael Kandiyoti [Imperial College London, London (United Kingdom). Department of Chemical Engineering

    2009-05-15

    1-Methyl-2-pyrrolidinone (NMP) is widely used as a solvent for coal-derived products and as eluent in size exclusion chromatography. It was observed that sample contamination may take place, through reactions of NMP, during extraction under refluxing conditions and during the process of NMP evaporation to concentrate or isolate samples. In this work, product distributions from experiments carried out in contact with air and under a blanket of oxygen-free nitrogen have been compared. Gas chromatography/mass spectrometry (GC-MS) clearly shows that oxidation products form when NMP is heated in the presence of air. Upon further heating, these oxidation products appear to polymerize, forming material with large molecular masses. Potentially severe levels of interference have been encountered in the size exclusion chromatography (SEC) of actual samples. Laser desorption mass spectrometry and SEC agree in showing an upper mass limit of nearly 7000 u for a residue left after distilling 'pure' NMP in contact with air. Furthermore, experiments have shown that these effects could be completely avoided by a strict exclusion of air during the refluxing and evaporation of NMP to dryness. 45 refs., 13 figs.

  9. An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass-derived carbohydrates

    Energy Technology Data Exchange (ETDEWEB)

    Chheda, Juben N.; Dumesic, James A. [University of Wisconsin-Madison, Department of Chemical and Biological Engineering, Madison, WI 53706 (United States)

    2007-05-30

    We present results for the conversion of carbohydrate feedstocks to liquid alkanes by the combination of dehydration, aldol-condensation/hydrogenation, and dehydration/hydrogenation processing. With respect to the first dehydration step, we demonstrate that HMF can be produced in good selectivity from abundantly available polysaccharides (such as inulin, sucrose) containing fructose monomer units using a biphasic batch reactor system. The reaction system can be optimized to achieve good yields to 5-hydroxymethylfurfural (HMF) from fructose by varying the contents of aqueous-phase modifiers such as dimethylsulfoxide (DMSO) and 1-methyl-2-pyrrolidinone (NMP). Regarding the aldol-condensation/hydrogenation step, we present the development of stable, solid base catalysts in aqueous environments. We address the effects of various reaction parameters such as the molar ratio of reactants and temperature on overall product yield for sequential aldol-condensation and hydrogenation steps. Overall, our results show that it is technically possible to convert carbohydrate feedstocks to produce liquid alkanes by the combination of dehydration, aldol-condensation/hydrogenation, and dehydration/hydrogenation processing; however, further optimization of these processes is required to decrease the overall number of separate steps (and reactors) required in this conversion. (author)

  10. 离子液体催化合成乙二醇丁醚醋酸酯%Synthesis of 2-butoxyethyl acetate in the presence of ionic liquid catalyst

    Institute of Scientific and Technical Information of China (English)

    滕俊江; 李春海; 马丽群; 钱键

    2011-01-01

    Ethylene glycol monobutyl ether and acetic acid were used as the starting materials to synthesize 2-butoxyethyl acetate in the presence of ionic liquid l-methyl-2-pyrrolidinone hydro-sulfate as a catalyst. The influence of synthetic conditions such as dosage of catalyst, ratio of acid to alcohol, reaction time and water stripping agent on yield were investigated. The purity of as-synthesized product was determined by gas chromatographic analysis; and its structure was characterized by means of nuclear magnetic resonance spectroscopy and mass spectrome-try. Results show that as-synthesized product has a purity of above 99. 0%. Ionic liquid 1-methyl-2-pyrrolidinone hydrosulfate exhibits excellent catalytic activity for the synthesis of 2-butoxyethyl acetate. Target product 2-butoxyethyl acetate is obtained at a yield of 94. 6% when the dosage of catalyst (vs. Total mass of reactants) , amount of ethylene glycol monobutyl ether, molar ratio of ethylene glycol monobutyl ether to acetic acid, refluxing time, and dosage of cyclohexane are kept as 6%, 11.8 g, 1 : 2, 3h, and 15 mL, respectively. Besides, the catalyst can be reused for five times without significant loss in yield.%以乙二醇单丁醚和冰醋酸为原料,在离子液体N-甲基吡咯烷酮硫酸氢盐([Hnmp] HSO4)催化下,合成了乙二醇丁醚醋酸酯.考察了催化剂用量、物料配比、反应时间、带水剂等因素对反应收率的影响.利用气相色谱仪分析了产物的纯度;利用核磁共振谱仪和质谱仪表征了产物的结构.结果表明,合成产物的纯度大于99.0%.[Hnmp]H SO4对合成乙二醇丁醚醋酸酯有良好的催化活性;在催化剂用量为反应物料总质量的6%,乙二醇单丁醚用量为11.8g,乙二醇单丁醚与冰醋酸的物质的量之比为1∶2,回流时间为3h,带水剂环己烷用量为15 mL的反应条件下,产物收率达94.6%;且催化剂重复使用5次仍保持较高活性.

  11. Synthesis and characterization of polymers for light waveguide applications

    Science.gov (United States)

    Li, Bo

    The overall goal of this research was to prepare organo- soluble polymers that display low birefringence, low optical loss, and high thermal stability for use in light waveguide devices. Thus, two series of thermally stable polymers, i.e., aromatic polyimides and perfluorocyclobutane-containing poly(aryl ethers), were synthesized and characterized. The approach to the aromatic polyimides involved the synthesis of a new series of 4,4'-(9- fluorenylidene)dianilines containing large polarizable substituents. The diamines were polymerized with 2,2'-bis[4-(3,4- dicarboxyphenoxy)phenyl]propane dianhydride (BisA-DA) and 2,2'-bis(3,4- dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) in refluxing m-cresol containing a catalytic amount of isoquinoline. The polyimides were soluble in common organic solvents such as N-methyl-2- pyrrolidinone (NMP), tetrahydrofuran (THF), chloroform (CHCl3), and cyclopentanone and could be solution cast into tough films. Thin films of the new cardo polyimides displayed birefringences that ranged from -0.0042 to 0.0074. In the second part of this work, a series of new difunctional and trifunctional trifluorovinylether-containing monomers was synthesized and polymerized via the thermal cyclodimerization of the vinyl groups. The number of carbon-hydrogen bonds was minimized in these systems in order to minimize the optical loss. A tough, transparent film was made from a polymer prepared from a trifunctional monomer, 1,1,1- trifluoro-2,2,2-tris(4-trifluorovinyloxyphenyl)ethane, which had a birefringence of 0.0008. The film showed negligible absorption at 1550 nm in the near-IR region. The polymer was also very thermally stable. Most of the linear polymers were soluble in common organic solvents such as NMP, THF, chloroform and cyclopentanone and could be solution cast into thin films, which displayed birefringences that ranged from -0.0005 to 0.0048.

  12. Characterization of tuyere-level core-drill coke samples from blast furnace operation

    Energy Technology Data Exchange (ETDEWEB)

    S. Dong; N. Paterson; S.G. Kazarian; D.R. Dugwell; R. Kandiyoti [Imperial College London, London (United Kingdom). Department of Chemical Engineering

    2007-12-15

    A suite of tuyere-level coke samples have been withdrawn from a working blast furnace during coal injection, using the core-drilling technique. The samples have been characterized by size exclusion chromatography (SEC), Fourier transform Raman spectroscopy (FT-RS), and X-ray powder diffraction (XRD) spectroscopy. The 1-methyl-2-pyrrolidinone (NMP) extracts of the cokes sampled from the 'bosh', the rear of the 'bird's nest', and the 'dead man' zones were found by SEC to contain heavy soot-like materials (ca. 10{sup 7}-10{sup 8} apparent mass units). In contrast, NMP extracts of cokes taken from the raceway and the front of the 'bird's nest' only contained a small amount of material of relatively lower apparent molecular mass (up to ca. 10{sup 5} u). Since the feed coke contained no materials extractable by the present method, the soot-like materials are thought to have formed during the reactions of volatile matter released from the injectant coal, probably via dehydrogenation and repolymerization of the tars. The Raman spectra of the NMP-extracted core-drilled coke samples showed variations reflecting their temperature histories. Area ratios of D-band to G-band decreased as the exposure temperature increased, while intensity ratios of D to G band and those of 2D to G bands increased with temperature. The graphitic (G), defect (D), and random (R) fractions of the carbon structure of the cokes were also derived from the Raman spectra. The R fractions decreased with increasing temperature, whereas G fractions increased, while the D fractions showed a more complex variation with temperature. These data appear to give clues regarding the graphitization mechanism of tuyere-level cokes in the blast furnace. 41 refs., 9 figs., 6 tabs.

  13. Predicted concentrations in new relocatable classrooms of volatile organic compounds emitted from standard and alternate interior finish materials

    Energy Technology Data Exchange (ETDEWEB)

    Hodgson, Alfred T.; Fisk, William J.; Shendell, Derek G.; Apte, Michael G.

    2001-07-01

    and 1-methyl-2-pyrrolidinone should be achieved as the result of the source reduction procedure.

  14. Extraction of lanthanides by polysulfone microcapsules containing EHPNA. I. Piercing method

    Institute of Scientific and Technical Information of China (English)

    靖宇; 王月; 侯海龙; 徐建鸿; 王运东

    2015-01-01

    Since the conventional liquid-liquid extraction method suffered from a series of problems such as inefficiency of one stage extraction, vast device occupation and severe emulsification, we adopted microcapsule (MC) technique to change the former liq-uid-liquid extraction to liquid-solid extraction. Firstly, the piercing method was performed to prepare the empty polysulfone (PSF) microcapsules, which was easy to implement and control. Secondly, the ultrasonic approach was utilized to prepare the functional microcapsules containing 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (EHPNA). We focused on a key factor of the molar ratio of PSF over 1-Methyl-2-pyrrolidinone (NMP), attaining a loading ratio as high as 7.21 g-EHPNA/g-PSF. Thirdly, we examined the kinetics and thermodynamics of extraction. Kinetic results demonstrated that equilibrium was reached within two hours, with an extraction rate of Sm3+≈Er3+>La3+; Thermodynamic results showed that the extraction of lanthanides complied with the Langmuir law, with an extraction capacity of 0.25–0.30 mmol/g-microcapsule. Fourthly, stripping experiment indicated that three hours were re-quired to accomplish equilibrium for La3+ and Sm3+ while longer hours for Er3+. Finally, seven extraction-stripping cyclic experiments were performed for three mixed elements, the results of which revealed that Sm3+ and Er3+ maintained constantly high extraction amount whilst La3+ leveled off at approximately 50%. This proposed polysulfone microcapsule containing EHPNA is suitable to be applied to extraction and concentration of rare earth metals.

  15. Effects of Composite Formulation on Mechanical Properties of Biodegradable Poly(Propylene Fumarate/Bone Fiber Scaffolds

    Directory of Open Access Journals (Sweden)

    Xun Zhu

    2010-01-01

    Full Text Available The objective of our paper was to determine the effects of composite formulation on the compressive modulus and ultimate strength of a biodegradable, in situ polymerizable poly(propylene fumarate (PPF and bone fiber scaffold. The following parameters were investigated: the incorporation of bone fibers (either mineralized or demineralized, PPF molecular weight, N-vinyl pyrrolidinone (NVP crosslinker amount, benzoyl peroxide (BP initiator amount, and sodium chloride porogen amount. Eight formulations were chosen based on a resolution III two-level fractional factorial design. The compressive modulus and ultimate strength of these formulations were measured on a materials testing machine. Absolute values for compressive modulus varied from 21.3 to 271 MPa and 2.8 to 358 MPa for dry and wet samples, respectively. The ultimate strength of the crosslinked composites varied from 2.1 to 20.3 MPa for dry samples and from 0.4 to 16.6 MPa for wet samples. Main effects of each parameter on the measured property were calculated. The incorporation of mineralized bone fibers and an increase in PPF molecular weight resulted in higher compressive modulus and ultimate strength. Both mechanical properties also increased as the amount of benzoyl peroxide increased or the NVP amount decreased in the formulation. Sodium chloride had a dominating effect on the increase of mechanical properties in dry samples but showed little effects in wet samples. Demineralization of bone fibers led to a decrease in the compressive modulus and ultimate strength. Our results suggest that bone fibers are appropriate as structural enforcement components in PPF scaffolds. The desired orthopaedic PPF scaffold might be obtained by changing a variety of composite formulation parameters.

  16. Effects of composite formulation on the mechanical properties of biodegradable poly(propylene fumarate)/bone fiber scaffolds.

    Science.gov (United States)

    Zhu, Xun; Liu, Nathan; Yaszemski, Michael J; Lu, Lichun

    2010-01-01

    The objective of our study was to determine the effects of composite formulation on the compressive modulus and ultimate strength of a biodegradable, in situ polymerizable poly(propylene fumarate) (PPF) and bone fiber scaffold. The following parameters were investigated: the incorporation of bone fibers (either mineralized or demineralized), PPF molecular weight, N-vinyl pyrrolidinone (NVP) crosslinker amount, benzoyl peroxide (BP) initiator amount, and sodium chloride porogen amount. Eight formulations were chosen based on a resolution III two level fractional factorial design. The compressive modulus and ultimate strength of these formulations were measured on a materials testing machine. Absolute values for compressive modulus varied from 21.3 to 271 MPa and 2.8 to 358 MPa for dry and wet samples, respectively. The ultimate strength of the crosslinked composites varied from 2.1 to 20.3 MPa for dry samples and from 0.4 to 16.6 MPa for wet samples. Main effects of each parameter on the measured property were calculated. The incorporation of mineralized bone fibers and an increase in PPF molecular weight resulted in higher compressive modulus and ultimate strength. Both mechanical properties also increased as the amount of benzoyl peroxide increased or the NVP amount decreased in the formulation. Sodium chloride had a dominating effect on the increase of mechanical properties in dry samples but showed little effects in wet samples. Demineralization of bone fibers led to a decrease in the compressive modulus and ultimate strength. Our results suggest that bone fibers are appropriate as structural enforcement components in PPF scaffolds. The desired orthopaedic PPF scaffold might be obtained by changing a variety of composite formulation parameters.

  17. Effect of ceftobiprole on the normal human intestinal microflora.

    Science.gov (United States)

    Bäckström, Tobias; Panagiotidis, Georgios; Beck, Olof; Asker-Hagelberg, Charlotte; Rashid, Mamun-Ur; Weintraub, Andrej; Nord, Carl Erik

    2010-12-01

    Ceftobiprole is a new broad-spectrum pyrrolidinone cephem active against meticillin-resistant Staphylococcus aureus, vancomycin-resistant Enterococcus faecalis and Gram-negative bacteria such as Enterobacteriaceae and Pseudomonas spp. The purpose of the present study was to investigate the effect of administration of ceftobiprole on the normal intestinal microflora. Twelve healthy subjects (six males and six females) aged 20-31 years received ceftobiprole 500 mg by intravenous infusion every 8h for 7 days. Plasma samples were collected on Days -1, 1, 4, 7, 10, 14 and 21 for determination of drug concentration by biological and chemical methods. Faecal samples were collected on Days -1, 2, 4, 7, 10, 14 and 21. For analysis of the microflora, faecal specimens were cultured on non-selective and selective media. Different colony types were counted, isolated in pure culture and identified to genus level. All new colonising aerobic and anaerobic bacteria were tested for susceptibility to ceftobiprole. Plasma concentrations of ceftobiprole 10 min after completion of infusion were as follows: Day 1, 14.7-23.6 mg/L; Day 4, 15.9-24.5 mg/L; and Day 7, 15.9-23.9 mg/L. No ceftobiprole was detected in plasma on Days -1, 10, 14 and 21. No measurable concentrations of ceftobiprole were found in faeces on Days -1, 2, 4, 7, 10, 14 and 21. There were minor changes in the numbers of enteric bacteria, enterococci and Candida albicans and there were moderate changes in the numbers of bifidobacteria, lactobacilli, clostridia and Bacteroides spp. during the same period. No Clostridium difficile strains or toxins were found. No new colonising aerobic and anaerobic bacteria with ceftobiprole minimum inhibitory concentrations of ≥ 4 mg/L were found. Ceftobiprole had no significant ecological impact on the human intestinal microflora.

  18. Activities of ceftobiprole, a novel broad-spectrum cephalosporin, against Haemophilus influenzae and Moraxella catarrhalis.

    Science.gov (United States)

    Bogdanovich, Tatiana; Clark, Catherine; Ednie, Lois; Lin, Gengrong; Smith, Kathy; Shapiro, Stuart; Appelbaum, Peter C

    2006-06-01

    Ceftobiprole, a broad-spectrum pyrrolidinone-3-ylidenemethyl cephem currently in phase III clinical trials, had MICs between 0.008 microg/ml and 8.0 microg/ml for 321 clinical isolates of Haemophilus influenzae and between Ceftobiprole MIC(50) and MIC(90) values for H. influenzae were 0.06 microg/ml and 0.25 microg/ml for beta-lactamase-positive strains (n = 262), 0.03 microg/ml and 0.25 microg/ml for beta-lactamase-negative strains (n = 40), and 0.5 microg/ml and 2.0 microg/ml for beta-lactamase-negative ampicillin-resistant strains (n = 19), respectively. Ceftobiprole MIC(50) and MIC(90) values for beta-lactamase-positive M. catarrhalis strains (n = 40) were 0.12 microg/ml and 0.5 microg/ml, respectively, whereas the ceftobiprole MIC range for beta-lactamase-negative M. catarrhalis strains (n = 9) was ceftobiprole, whereas amoxicillin-clavulanate MICs usually were higher than those of ceftobiprole. Azithromycin and telithromycin had unimodal MIC distributions against H. influenzae, with MIC(90) values of azithromycin and telithromycin of 2 microg/ml and 4 microg/ml, respectively. Except for selected quinolone-nonsusceptible H. influenzae strains, moxifloxacin proved highly active, with MIC(90) values of 0.12 microg/ml. Time-kill analyses showed that ceftobiprole, ceftriaxone, cefpodoxime, amoxicillin-clavulanate, azithromycin, telithromycin, and moxifloxacin were bactericidal at 2x MIC by 24 h against all 10 H. influenzae strains surveyed. Only modest increases in MICs were found for H. influenzae or M. catarrhalis clones after 50 serial passages in the presence of subinhibitory concentrations of ceftobiprole, and single-passage selection showed that the selection frequency of H. influenzae or M. catarrhalis clones with elevated ceftobiprole MICs is quite low.

  19. Photochemical modification of poly(ether sulfone) ultrafiltration membranes by UV-assisted graft polymerization for the prevention of biofouling

    Science.gov (United States)

    Pieracci, John Paul

    Membranes are widely used by the biotechnology industry in the separation and recovery of proteins from biological solutions. Fouling of membrane surfaces by irreversible protein adsorption during ultrafiltration causes loss of membrane permeability and can reduce membrane selectivity and lead to significant product loss through denaturation. In this work, low fouling poly(ether sulfone) (PES) ultrafiltration membranes were produced by ultraviolet (UV) assisted graft polymerization of hydrophilic vinyl monomers using a newly developed photochemical dip modification technique. This technique was developed to make the UV modification process more easily adaptable to continuous membrane manufacturing processes. A method was also developed to measure and track the degree of polymer grafting on the membrane surface using attenuated total reflection Fourier transform infrared spectroscopy (FTIR/ATR). Grafting the hydrophilic monomer N-vinyl-2-pyrrolidinone (NVP) onto the membrane surface increased surface wettability and produced membranes with the high wettability of regenerated cellulose membranes. The enhanced surface wettability significantly decreased irreversible adsorptive fouling during the filtration of the protein bovine serum albumin (BSA). In order to maintain the rejection of BSA after modification, PES chain scission was tightly controlled by regulating the UV wavelength range and the light intensity used. The UV reactor system was operated with 300 nm UV lamps and a benzene filter used to remove high energy wavelengths below 275 nm that were determined to cause severe loss of BSA rejection due to pore enlargement from extensive chain scission. Dip modification caused membrane permeability to decrease due to the grafted chains blocking the membrane pores. The use of a chain transfer agent during modification followed by ethanol cleaning increased modified membrane permeability, but BSA rejection was severely decreased. The resultant membranes produced by

  20. A robust and versatile photoinduced living polymerization of conjugated and unconjugated monomers and its oxygen tolerance.

    Science.gov (United States)

    Xu, Jiangtao; Jung, Kenward; Atme, Amir; Shanmugam, Sivaprakash; Boyer, Cyrille

    2014-04-09

    Controlled/living radical polymerization techniques have transformed polymer chemistry in the last few decades, affording the production of polymers with precise control over both molecular weights and architectures. It is now possible to synthesize almost an infinite variety of macromolecules using nonspecialized equipment, finding applications in high-tech industry. However, they have several shortcomings. Until recently, living radical polymerizations could not be controlled by an external stimulus, such as visible light, pH, mechanical, chemical, etc. Moreover, they are usually sensitive to trace amounts of oxygen in the system. In this Article, we report a photoinduced living polymerization technique, which is able to polymerize a large range of monomers, including conjugated and unconjugated monomers, using ultralow concentrations of an iridium-based photoredox catalyst (typically 1 ppm to monomers) and a low energy visible LED as the light source (1-4.8 W, λ(max) = 435 nm). The synthesis of homopolymers with molecular weights ranging from 1000 to 2,000,000 g/mol was successfully achieved with narrow molecular weight distributions (M(w)/M(n) < 1.3). In addition, chain extensions of poly(methacrylate)s, poly(styrene), poly(N-vinyl pyrrolidinone), poly(vinyl ester)s, and poly(acrylate)s were performed to prepare diblock copolymers. The reusability of the catalyst was demonstrated by the synthesis of a decablock polymer by multiple chain extensions. Most importantly, this process was employed to prepare well-defined polymers and multiblock copolymers in the presence of air.

  1. DMAC and NMP as Electrolyte Additives for Li-Ion Cells

    Science.gov (United States)

    Smart, Marshall; Bugga, Ratnakumar; Lucht, Brett

    2008-01-01

    Dimethyl acetamide (DMAC) and N-methyl pyrrolidinone (NMP) have been found to be useful as high-temperature-resilience-enhancing additives to a baseline electrolyte used in rechargeable lithium-ion electrochemical cells. The baseline electrolyte, which was previously formulated to improve low-temperature performance, comprises LiPF6 dissolved at a concentration of 1.0 M in a mixture comprising equal volume proportions of ethylene carbonate, diethyl carbonate, and dimethyl carbonate. This and other electrolytes comprising lithium salts dissolved in mixtures of esters (including alkyl carbonates) have been studied in continuing research directed toward extending the lower limits of operating temperatures and, more recently, enhancing the high-temperature resilience of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. Although these electrolytes provide excellent performance at low temperatures (typically as low as -40 C), when the affected Li-ion cells are subjected to high temperatures during storage and cycling, there occur irreversible losses of capacity accompanied by power fade and deterioration of low-temperature performance. The term "high-temperature resilience" signifies, loosely, the ability of a cell to resist such deterioration, retaining as much as possible of its initial charge/discharge capacity during operation or during storage in the fully charged condition at high temperature. For the purposes of the present development, a temperature is considered to be high if it equals or exceeds the upper limit (typically, 30 C) of the operating-temperature range for which the cells in question are generally designed.

  2. In vitro studies of composite bone filler based on poly(propylene fumarate) and biphasic α-tricalcium phosphate/hydroxyapatite ceramic powder.

    Science.gov (United States)

    Wu, Chang-Chin; Yang, Kai-Chiang; Yang, Shu-Hua; Lin, Min-Huei; Kuo, Tzong-Fu; Lin, Feng-Huei

    2012-04-01

    While many different filler materials have been applied in vertebral augmentation procedures, none is perfect in all biomechanical and biological characteristics. To minimize possible shortages, we synthesized a new biodegradable, injectable, and premixed composite made from poly(propylene fumarate) (PPF) and biphasic α-tricalcium phosphate (α-TCP)/hydroxyapatite (HAP) ceramics powder and evaluated the material properties of the compound in vitro. We mixed the PPF cross-linked by N-vinyl pyrrolidinone and biphasic α-TCP/HAP powder in different ratios with benzoyl peroxide as an initiator. The setting time and temperature were recorded, although they could be manipulated by modulating the concentrations of hydroquinone and N,N-dimethyl-p-toluidine. Degradation, cytocompatibility, mechanical properties, and radiopacity were analyzed after the composites were cured by a cylindrical shape. We also compared the study materials with poly(methyl methacrylate) (PMMA) and PPF with pure HAP particles. Results showed that lower temperature during curing process (38-44°C), sufficient initial mechanical compressive fracture strength (61.1±3.7MPa), and gradual degradation were observed in the newly developed bone filler. Radiopacity in Hounsfield units was similar to PMMA as determined by computed tomography scan. Both pH value variation and cytotoxicity were within biological tolerable limits based on the biocompatibility tests. Mixtures with 70% α-TCP/HAP powder were superior to other groups. This study indicated that a composite of PPF and biphasic α-TCP/HAP powder is a promising, premixed, injectable biodegradable filler and that a mixture containing 70% α-TCP/HAP exhibits the best properties.

  3. Exploring the selectivity of auto-inducer complex with LuxR using molecular docking, mutational studies and molecular dynamics simulations

    Science.gov (United States)

    Rajamanikandan, Sundaraj; Srinivasan, Pappu

    2017-03-01

    Bacteria communicate with one another using extracellular signaling molecules called auto-inducers (AHLs), a process termed as quorum sensing. The quorum sensing process allows bacteria to regulate various physiological activities. In this regard, quorum sensing master regulator LuxR from Vibrio harveyi represents an attractive therapeutic target for the development of novel anti-quorum sensing agents. Eventhough the binding of AHL complex with LuxR is evidenced in earlier reports, but their mode of binding is not clearly determined. Therefore, in the present work, molecular docking, in silico mutational studies, molecular dynamics simulations and free energy calculations were performed to understand the selectivity of AHL into the binding site of LuxR. The results revealed that Asn133 and Gln137 residues play a crucial role in recognizing AHL more effectively into the binding site of LuxR with good binding free energy. In addition to that, the carbonyl group presents in the lactone ring and amide group of AHL plays a vital role in the formation of hydrogen bond interactions with the protein. Further, structure based virtual screening was performed using ChemBridge database to screen potent lead molecules against LuxR. 4-benzyl-2-pyrrolidinone and N-[2(1-cyclohexen-1-yl) enthyl]-N'(2-ethoxyphenyl) were selected based on dock score, binding affinity and mode of interactions with the receptor. Furthermore, binding free energy, density functional theory and ADME prediction were performed to rank the lead molecules. Thus, the identified lead molecules can be used for the development of anti-quorum sensing drugs.

  4. 新型聚硼硅氮烷杂化树脂的制备研究%Study on Preparation of a Novel Hybrid Resin from Polyborosilazane

    Institute of Scientific and Technical Information of China (English)

    胡笛; 杨丽萍; 李永明; 张宗波; 徐彩虹

    2014-01-01

    以聚硼硅氮烷(PSNB)、N-乙烯基吡咯烷酮(NVP)为原料,由过氧化二异丙苯(DCP)引发自由基共聚合反应,制备了聚硼硅氮烷(PSNB/NVP)杂化树脂。采用差示扫描量热仪、热失重仪、红外光谱仪、平板流变仪等对杂化树脂的热性能、固化过程、流变行为等进行测试。结果表明,随着PSNB与NVP的质量比的提高,杂化树脂的热稳定性升高,PSNB与NVP质量比为20/80的杂化树脂在热质量损失率达到为5%时的温度较聚N-乙烯基吡咯烷酮提高近200℃;由杂化树脂高温裂解可得到硅硼碳氮多孔陶瓷,其孔尺寸及分布极不均匀。%A novel polyborosilazane (PSNB)and NVP hybrid resin was prepared by free radical copoly-merization of PSNB and 1-vinyl-2-pyrrolidinone with the initiation of dicumyl peroxide. The thermal proper-ties,curing behavior and rheological properties were characterized by DSC,TGA,FT IR and parallel plate rheometer. The thermal stability of the hybrid resin increased with increasing proportion of PSNB. The temper-ature of the 5% mass loss of the hybrid resin was increased about 200℃ with 20% weight percent of PSNB. SiBCN porous ceramics were prepared by pyrolysis of the hybrid resin under high temperature with the uneven pore size and distribution.

  5. An investigation of pore collapse in asymmetric polysulfone membranes

    Science.gov (United States)

    Subrahmanyan, Sumitra

    2003-06-01

    Porous polysulfone membranes prepared by phase inversion can be tailored to suit filtration requirements by the choice of solvent and coagulant. In the current research polysulfone membranes were prepared by inverting a solution in N-methyl pyrrolidinone (NMP) in isopropanol to form uniform sized pores. Phase inversion resulted in the formation of an asymmetric membrane. The membranes have a characteristic "skin" which is supported by a highly porous substructure. Water-wet membranes experience capillary force during water evaporation. Since the modulus of the membranes is lower than the capillary force, the membrane walls shrink and thicken giving rise to a condensed structure. The "skin" regulates permeation through the membranes which is essential for filtration. A change in the pore structure of the skin alters the permeability. The current research investigates the influence of amine plasma treatments on the surface pore structure of polysulfone membranes. The permeation of a rhodamine dye through the plasma treated membranes and through non-plasma treated membranes is used to examine the influence of the plasma treatment. Furthermore, the influence of plasma treatment on the loss of water from the membranes leading to pore collapse is also explored. The study revealed that a plasma ablates the skin, increasing the permeation. An ammonia plasma treatment produced more etching, and hence increased permeation compared to permeation for an aniline plasma-treated membrane. A one-minute aniline plasma treatment only caused a moderate increase in permeation. Plasma treatments introduced significant surface modification by the introduction of new functionalities. However, permeation was not influenced by the surface modification. Water trapped in the pores is essential to maintain the pore structure of the membrane. The surface treatment dictates the pore size and therefore, the convection allowing water evaporation, leading to pore collapse. Heat treating also

  6. Identification of organically associated trace elements in wood and coal by inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Richaud, R; Lazaro, M J; Lachas, H; Miller, B B; Herod, A A; Dugwell, D R; Kandiyoti, R

    2000-01-01

    1-Methyl-2-pyrrolidinone (NMP) was used to extract samples of wood (forest residue) and coal; the extracts were analysed by inductively coupled plasma mass spectrometry (ICP-MS) using two different sample preparation methods, in order to identify trace elements associated with the organic part of the samples. A sample of fly ash was similarly extracted and analysed in order to assess the behaviour of the mineral matter contained within the wood and coal samples. 32% of the biomass was extracted at the higher temperature and 12% at room temperature while only 12% of the coal was extracted at the higher temperature and 3% at room temperature. Less than 2% of the ash dissolved at the higher temperature. Size exclusion chromatograms of the extracts indicated the presence of significant amounts of large molecular mass materials (>1000 mu) in the biomass and coal extracts but not in the ash extract. Trace element analyses were carried out using ICP-MS on the acid digests prepared by 'wet ashing' and microwave extraction. Sixteen elements (As, Ba, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, Pb, Sb, Se, V and Zn) were quantified, in the samples before extraction, in the extracts and in the residues. Concentrations of trace elements in the original biomass sample were lower than in the coal sample while the concentrations in the ash sample were the highest. The major trace elements in the NMP extracts were Ba, Cu, Mn and Zn from the forest residue; Ba, Cu, Mn, Pb and Zn from the coal; Cu and Zn from the ash. These elements are believed to be associated with the organic extracts from the forest residue and coal, and also from the ash. Be and Sb were not quantified in the extracts because they were present at too low concentrations; up to 40% of Mn was extracted from the biomass sample at 202 degrees C, while Se was totally extracted from the ash sample. For the forest residue, approximately 7% (at room temperature) and 45% (at 202 degrees C) of the total trace elements studied were

  7. Noninvasive Characterization of the Effect of Varying PLGA Molecular Weight Blends on In Situ Forming Implant Behavior Using Ultrasound Imaging

    Directory of Open Access Journals (Sweden)

    Luis Solorio, Alexander M. Olear, Jesse I. Hamilton, Ravi B. Patel, Ashlei C. Beiswenger, Jon E. Wallace, Haoyan Zhou, Agata A. Exner

    2012-01-01

    Full Text Available In situ forming implants (ISFIs have shown promise in drug delivery applications due to their simple manufacturing and minimally invasive administration. Precise, reproducible control of drug release from ISFIs is essential to their successful clinical application. This study investigated the effect of varying the molar ratio of different molecular weight (Mw poly(D,L-lactic-co-glycolic acid (PLGA polymers within a single implant on the release of a small Mw mock drug (sodium fluorescein both in vitro and in vivo. Implants were formulated by dissolving three different PLGA Mw (15, 29, and 53kDa, as well as three 1:1 molar ratio combinations of each PLGA Mw in 1-methyl-2-pyrrolidinone (NMP with the mock drug fluorescein. Since implant morphology and microstructure during ISFI formation and degradation is a crucial determinant of implant performance, and the rate of phase inversion has been shown to have an effect on the implant microstructure, diagnostic ultrasound was used to noninvasively quantify the extent of phase inversion and swelling behavior in both environments. Implant erosion, degradation, as well as the in vitro and in vivo release profiles were also measured using standard techniques. A non-linear mathematical model was used to correlate the drug release behavior with polymer phase inversion, with all formulations yielding an R2 value greater than 0.95. Ultrasound was also used to create a 3D image reconstruction of an implant over a 12 day span. In this study, swelling and phase inversion were shown to be inversely related to the polymer Mw with 53kDa polymer implants increasing at an average rate of 9.4%/day compared with 18.6%/day in the case of the 15 kDa PLGA. Additionally the onset of erosion, complete phase inversion, and degradation facilitated release required 9 d for 53 kDa implants, while these same processes began 3 d after injection into PBS with the 15 kDa implants. It was also observed that PLGA blends generally had

  8. Noninvasive characterization of the effect of varying PLGA molecular weight blends on in situ forming implant behavior using ultrasound imaging.

    Science.gov (United States)

    Solorio, Luis; Olear, Alexander M; Hamilton, Jesse I; Patel, Ravi B; Beiswenger, Ashlei C; Wallace, Jon E; Zhou, Haoyan; Exner, Agata A

    2012-01-01

    In situ forming implants (ISFIs) have shown promise in drug delivery applications due to their simple manufacturing and minimally invasive administration. Precise, reproducible control of drug release from ISFIs is essential to their successful clinical application. This study investigated the effect of varying the molar ratio of different molecular weight (Mw) poly(D,L-lactic-co-glycolic acid) (PLGA) polymers within a single implant on the release of a small Mw mock drug (sodium fluorescein) both in vitro and in vivo. Implants were formulated by dissolving three different PLGA Mw (15, 29, and 53 kDa), as well as three 1:1 molar ratio combinations of each PLGA Mw in 1-methyl-2-pyrrolidinone (NMP) with the mock drug fluorescein. Since implant morphology and microstructure during ISFI formation and degradation is a crucial determinant of implant performance, and the rate of phase inversion has been shown to have an effect on the implant microstructure, diagnostic ultrasound was used to noninvasively quantify the extent of phase inversion and swelling behavior in both environments. Implant erosion, degradation, as well as the in vitro and in vivo release profiles were also measured using standard techniques. A non-linear mathematical model was used to correlate the drug release behavior with polymer phase inversion, with all formulations yielding an R(2) value greater than 0.95. Ultrasound was also used to create a 3D image reconstruction of an implant over a 12 day span. In this study, swelling and phase inversion were shown to be inversely related to the polymer Mw with 53 kDa polymer implants increasing at an average rate of 9.4%/day compared with 18.6%/day in the case of the 15 kDa PLGA. Additionally the onset of erosion, complete phase inversion, and degradation facilitated release required 9 d for 53 kDa implants, while these same processes began 3 d after injection into PBS with the 15 kDa implants. It was also observed that PLGA blends generally had

  9. In vivo pharmacodynamics of ceftobiprole against multiple bacterial pathogens in murine thigh and lung infection models.

    Science.gov (United States)

    Craig, W A; Andes, D R

    2008-10-01

    Ceftobiprole medocaril is the parenteral prodrug of ceftobiprole, a novel pyrrolidinone broad-spectrum cephalosporin with in vitro and in vivo bactericidal activities against methicillin-resistant Staphylococcus aureus (MRSA) and penicillin-resistant Streptococcus pneumoniae (PRSP). We have used murine thigh and lung infection models in neutropenic and normal mice to characterize the in vivo pharmacokinetic (PK)-pharmacodynamic (PD) activities of ceftobiprole against multiple strains of S. aureus (including MRSA), S. pneumoniae (including PRSP), and gram-negative bacilli. Serum levels of ceftobiprole following the administration of multiple doses were determined by a microbiological assay. In vivo bactericidal activities and postantibiotic effects (PAEs) of ceftobiprole against MRSA and PRSP strains were determined from serial CFU/thigh values following single doses of ceftobiprole (40 and 160 mg/kg of body weight). Dose fractionation studies were used to determine which PK-PD index correlated best with activity. Magnitudes of the PK-PD indices were calculated from MICs and PK parameters. A sigmoid dose-response model was used to estimate the dose (mg/kg/24 h) required to achieve a static and 2-log(10) kill effects over 24 h. PK results showed area under the concentration-time curve/dose values of 1.8 to 2.8 and half-lives of 0.29 to 0.51 h. MICs ranged from 0.015 to 2 microg/ml. Ceftobiprole demonstrated time-dependent killing; its in vivo PAEs varied from 3.8 h to 4.8 h for MRSA and from 0 to 0.8 h for PRSP. The time above MIC (T > MIC) correlated best with efficacy for both MRSA and PRSP. The T > MIC values required for the static doses were significantly longer (P ceftobiprole against S. pneumoniae but only slightly against Klebsiella pneumoniae. Based on its PD profile, ceftobiprole is a promising new beta-lactam agent with activity against gram-negative and gram-positive organisms including MRSA and PRSP.

  10. The efficacy and safety of ceftobiprole in the treatment of complicated skin and skin structure infections: evidence from 2 clinical trials.

    Science.gov (United States)

    Deresinski, Stanley C

    2008-05-01

    Complicated skin and skin structure infections (cSSSIs) are common and are associated with significant health and economic costs. These infections are predominantly characterized by infection with Staphylococcus aureus, and SENTRY Surveillance data indicate that the occurrence of this pathogen in cSSSIs has increased and that almost half of the isolated pathogens are methicillin-resistant S. aureus (MRSA). Surveillance data also indicate that Gram-negative isolates are not uncommon in cSSSIs. In the past, empiric antimicrobial coverage of both Gram-positive and Gram-negative infections has generally necessitated the use of at least 2 antimicrobial agents. Ceftobiprole, a novel advanced-generation pyrrolidinone cephalosporin, is currently under review by the Food and Drug Administration as therapy for cSSSIs. This article presents a summary of the results of 2 recently published multicenter noninferiority trials involving approximately 1600 patients with a variety of cSSSIs. In the 1st trial, which included patients with Gram-positive cSSSI, the clinical cure rate at the test-of-cure (TOC) visit (the primary end point) among patients receiving ceftobiprole was 93.3%. The 2nd trial included a broad range of cSSSIs of varying pathogenicity. In this trial, the clinical cure rate among patients receiving ceftobiprole for S. aureus and MRSA infection was 94.6% and 91.8%, respectively. Ceftobiprole's capacity as a broad-spectrum agent was demonstrated in the 2nd trial, in which the clinical cure rate at TOC was 90.5% against a variety of infections and pathogens (including Gram negatives). In addition, the cure rate among patients with moderate to severe diabetic foot infection who received ceftobiprole was 86.2%, and these patients experienced a shorter length of stay in the hospital than those who received a comparator. This article also addresses the results of these trials in the context of the current medical need for safe broad-spectrum antimicrobial agents with

  11. In vitro antibacterial activity of ceftobiprole against clinical isolates from French teaching hospitals: proposition of zone diameter breakpoints.

    Science.gov (United States)

    Lascols, C; Legrand, P; Mérens, A; Leclercq, R; Muller-Serieys, C; Drugeon, H B; Kitzis, M D; Reverdy, M E; Roussel-Delvallez, M; Moubareck, C; Brémont, S; Miara, A; Gjoklaj, M; Soussy, C-J

    2011-03-01

    The aims of this study were to determine the in vitro activity profile of ceftobiprole, a pyrrolidinone cephalosporin, against a large number of bacterial pathogens and to propose zone diameter breakpoints for clinical categorisation according to the European Committee on Antimicrobial Susceptibility Testing (EUCAST) minimum inhibitory concentration (MIC) breakpoints. MICs of ceftobiprole were determined by broth microdilution against 1548 clinical isolates collected in eight French hospitals. Disk diffusion testing was performed using 30 μg disks according to the method of the Comité de l'Antibiogramme de la Société Française de Microbiologie (CA-SFM). The in vitro activity of ceftobiprole, expressed by MIC(50/90) (MICs for 50% and 90% of the organisms, respectively) (mg/L), was as follows: meticillin-susceptible Staphylococcus aureus, 0.25/0.5; meticillin-resistant S. aureus (MRSA), 1/2; meticillin-susceptible coagulase-negative staphylococci (CoNS), 0.12/0.5; meticillin-resistant CoNS, 1/2; penicillin-susceptible Streptococcus pneumoniae, ≤ 0.008/0.03; penicillin-resistant S. pneumoniae, 0.12/0.5; viridans group streptococci, 0.03/0.12; β-haemolytic streptococci, ≤ 0.008/0.016; Enterococcus faecalis, 0.25/1; Enterococcus faecium, 64/128; Enterobacteriaceae, 0.06/32; Pseudomonas aeruginosa, 4/16; Acinetobacter baumannii, 0.5/64; Haemophilus influenzae, 0.03/0.12; and Moraxella catarrhalis, 0.25/0.5. According to the regression curve, zone diameter breakpoints could be 28, 26, 24 and 22 mm for MICs of 0.5, 1, 2 and 4 mg/L respectively. In conclusion, this study confirms the potent in vitro activity of ceftobiprole against many Gram-positive bacteria, including MRSA but not E. faecium, whilst maintaining a Gram-negative spectrum similar to the advanced-generation cephalosporins such as cefepime. Thus ceftobiprole appears to be well suited for the empirical treatment of a variety of healthcare-associated infections.

  12. 功能化离子液体催化合成甘油单月桂酸酯%Synthesis of glycerol monolaurate using functionalized ionic liquids catalysts

    Institute of Scientific and Technical Information of China (English)

    王松; 张争艳; 常欠欠; 李三喜; 张林楠

    2015-01-01

    合成了由吡啶、N-甲基咪唑、N-甲基-2-吡咯烷酮提供有机阳离子,磷钨酸、对甲苯磺酸提供阴离子的6种离子液体.使用NMR、FT-IR和TG对离子液体表征,并考察它们催化甘油与月桂酸酯化的催化效果.结果表明,这些离子液体都具有较好的热稳定性,以1-(丁基-4-磺酸基)-3-甲基咪唑磷钨酸盐离子液体的热稳定性最好.在最佳条件使用离子液体催化甘油与月桂酸反应时,阴离子的种类对月桂酸的转化率影响较大,以对甲苯磺酸为阴离子的离子液体催化反应时,月桂酸转化率较以磷钨酸为阴离子的离子液体的高;1-(丁基-4-磺酸基)-3-甲基咪唑对甲苯磺酸盐离子液体做催化剂时甘油单月桂酸酯的产率最高.催化剂重复使用性方面,离子液体重复使用5次催化活性没有明显变化.%Six ionic liquids based on pyridine (Py), 1-methylimidazole (MIM),N-methyl-2-pyrrolidinone(NMP) cations were prepared by coupling corresponding SO3H-functionalized zwitterion ionic complex with different counterpart anions including H3PW12O40 andp-toluenesulfonic acid (PTSA). The obtained ionic liquids were well characterized by FT-IR, TG,1H NMR,13C NMR methods and then these ionic liquids were deployed in the esterification reaction of glycerol with lauric acid under the condition without organic solvent. The effects of various key reaction parameters including reaction temperature, glycerol/lauric acid molar ratio, molar ratio of ionic liquid to lauric acid and the type of catalysts on the acid conversion and yield of glycerol monolaurate were discussed. The results indicated that all the ionic liquids exhibit good thermal stability and compared with other ionic liquids, [MIMBS]3PW12O40 ionic liquid has the best thermal stability. When [MIMBS][PTSA] ionic liquid was used to optimize esterification reaction parameters, the optimum reaction conditions were established as follows: glycerol/lauric acid ratio of 4, amount of

  13. Ceftobiprole Medocaril: BAL5788, JNJ 30982081, JNJ30982081, RO 65-5788, RO 655788.

    Science.gov (United States)

    2006-01-01

    Ceftobiprole medocaril [BAL 5788, RO 65-5788, JNJ 30982081] is a prodrug in phase III clinical development with Basilea Pharmaceutica and Cilag AG (Johnson & Johnson) for the potential treatment of serious bacterial infections, including methicillin-resistant Staphylococcus aureus (MRSA). Ceftobiprole medocaril is the water-soluble prodrug of the pyrrolidinone cephalosporin, ceftobiprole [BAL 9141, RO 63-9141]. Because of the low water solubility of ceftobiprole, its clinical application was limited and Basilea began its investigations into ceftobiprole medocaril for further development. Ceftobiprole medocaril is being developed for IV administration and is currently undergoing phase III trials for complicated skin and skin structure infections (including MRSA) and hospital-acquired (nosocomial) pneumonia. Ceftobiprole medocaril has a broad spectrum of activity against Gram-positive bacteria (including methicillin-resistant staphylococci, penicillin-resistant pneumococci and Enterococcus faecalis) and Gram-negative bacteria. Ceftobiprole medocaril inhibits all transpeptidases, including the penicillin-binding protein (PBP) 2a, by a unique combination of features. PBP 2a is the primary enzyme responsible for beta-lactam drug resistance in MRSA; PBP 2a also acts as a key defense mechanism by interacting with the bacterial cell wall to form a chemical barricade that is impervious to antibiotics. Ceftobiprole medocaril has been designed specifically to bind to this penicillin-resistant target. Ceftobiprole medocaril is bactericidal and has not shown resistance development in vitro or in stringent animal models. Studies conducted by Basilea have demonstrated that ceftobiprole medocaril is readily converted to ceftobiprole, and shows markedly improved water solubility. In February 2005, Basilea Pharmaceutica AG entered into an exclusive worldwide agreement with Cilag AG International (Johnson & Johnson) to develop, manufacture and market ceftobiprole medocaril. Ortho

  14. 毒死蜱/环糊精在锌铝类水滑石中插层的制备和性能%Preparation and Characterization of Chlorpyrifos/Cyclodextrin Complex Intercalation into ZnAl-Layered Double Hydroxide

    Institute of Scientific and Technical Information of China (English)

    刘洁翔; 任纪辉; 赵乔; 石婷静; 刘志芳; 罗诏; 张晓光

    2016-01-01

    Chlorpyrifos (CPF) was firstly included in sulfonated hydroxyethyl-β-cyclodextrin (SBECD) and carboxymethyl-β-cyclodextrin (CMCD) in an ethanol or 1-methyl-2-pyrrolidinone (NMP) solvent. Inclusion complexes (CPF/SBECD and CPF/CMCD) were then intercalated into the gal eries of ZnAl-layered double hydroxides (ZAL) to synthesize ZAL-SBECD-CPF and ZAL-CMCD-CPF intercalated materials. The structure and thermal stability of nanohybrids were characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and thermal gravimetric and differential thermal analysis (TG-DTA). The results showed that both CPF/SBECD and CPF/SBECD were successful y intercalated in the interlayer. The samples prepared in the NMP solvent had a stronger diffraction peak intensity than those prepared with ethanol. The intercalated CPF molecules had a high thermal stability. Furthermore, the release behaviors of CPF from ZAL-SBECD-CPF and ZAL-CMCD-CPF nanohybrids were investigated and analyzed at pH 5.0 and 6.8. ZAL-SBECD-CPF had almost no slow-release behavior, while ZAL-CMCD-CPF showed distinct slow-release, which was caused by the different arrangements of cyclodextrin (CD) in the interlayer. BC release from nanohybrids was faster and the amount released higher at pH 6.8 than at pH 5.0. This was closely correlated with the structural type of CD and the release media. The CPF release kinetic process can be fitted wel by pseudo-second-order and parabolic diffusion models. ZAL-CMCD-CPF remarkably exhibited control ed release behavior, suggesting that it can be potential y applied as a control ed release pesticide formulation.%以层状锌铝类水滑石(ZAL)为主体,分别以磺丁基醚-β-环糊精(SBECD)和羧甲基-β-环糊精(CMCD)包结毒死蜱(CPF)为客体分子,分别在乙醇和N-甲基吡咯烷酮(NMP)溶剂条件下制备ZAL-SBECD-CPF和ZAL-CMCD-CPF插层材料,采用X射线粉末衍射(XRD)、傅里叶变换红外(FT-IR)光谱和热重-差热