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Sample records for aryl ether inhibitors

  1. Design and synthesis of aryl ether and sulfone hydroxamic acids as potent histone deacetylase (HDAC) inhibitors.

    Science.gov (United States)

    Pabba, Chittari; Gregg, Brian T; Kitchen, Douglas B; Chen, Zhen Jia; Judkins, Angela

    2011-01-01

    A series of novel hydroxamic acid based histone deacetylases (HDAC) inhibitors with aryl ether and aryl sulfone residues at the terminus of a substituted, unsaturated 5-carbon spacer moiety have been synthesized for the first time and evaluated. Compounds with meta- and para-substitution on the aryl ring of ether hydroxamic acids 19c, 20c, 19e, 19f and 19g are potent HDAC inhibitors with activities at low nanomolar levels. Copyright © 2010 Elsevier Ltd. All rights reserved.

  2. Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Meng [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Gutiérrez, Oliver Y. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4 85748 Garching Germany

    2018-03-06

    Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

  3. A Convenient and Efficient Method for Demethylation of Aryl Methyl Ethers with Magnesium Iodide in Ionic Liquid

    International Nuclear Information System (INIS)

    Lee, Kwan Soo; Kim, Kee D.

    2010-01-01

    We have developed a new and efficient method for the demethylation of various types of aryl methyl ethers using readily available, stable, and easily handled magnesium iodide in [BMIM]BF 4 ionic liquid. Owing to its simplicity and mild reaction conditions the protocol reported herein may serve as a useful alternative to the existing methods for the deprotection of aryl methyl ethers to the corresponding phenolic derivatives. Demethylation of aryl methyl ethers to the corresponding phenols are very important reactions in organic synthesis. A number of methods have been reported for the cleavage of highly stable aryl methyl ethers utilizing strong acids or bases such as aluminum chloride, boron tribromide, cerium chloride, alkaline thiolate, methyl magnesium iodide, and L-Selectride. However, all of these methods invariably suffered from one or more drawbacks such as harsh reaction conditions, long reaction times, difficulty of manipulation, use of exotic reagents, and low reaction yields. Furthermore, in the most of known methods for demethylation of aryl methyl ethers, use of large excess amounts of demethylating agents have been generally required. Thus, it is highly desirable to develop an improved convenient and efficient procedure for demethylation reactions of aryl methyl ethers

  4. A Convenient and Efficient Method for Demethylation of Aryl Methyl Ethers with Magnesium Iodide in Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kwan Soo [KAIST, Daejeon (Korea, Republic of); Kim, Kee D. [Sangji University, Wonju (Korea, Republic of)

    2010-12-15

    We have developed a new and efficient method for the demethylation of various types of aryl methyl ethers using readily available, stable, and easily handled magnesium iodide in [BMIM]BF{sub 4} ionic liquid. Owing to its simplicity and mild reaction conditions the protocol reported herein may serve as a useful alternative to the existing methods for the deprotection of aryl methyl ethers to the corresponding phenolic derivatives. Demethylation of aryl methyl ethers to the corresponding phenols are very important reactions in organic synthesis. A number of methods have been reported for the cleavage of highly stable aryl methyl ethers utilizing strong acids or bases such as aluminum chloride, boron tribromide, cerium chloride, alkaline thiolate, methyl magnesium iodide, and L-Selectride. However, all of these methods invariably suffered from one or more drawbacks such as harsh reaction conditions, long reaction times, difficulty of manipulation, use of exotic reagents, and low reaction yields. Furthermore, in the most of known methods for demethylation of aryl methyl ethers, use of large excess amounts of demethylating agents have been generally required. Thus, it is highly desirable to develop an improved convenient and efficient procedure for demethylation reactions of aryl methyl ethers.

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

    DEFF Research Database (Denmark)

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

    2008-01-01

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

  6. A unified approach for the synthesis of symmetrical and unsymmetrical dibenzyl ethers from aryl aldehydes through reductive etherification

    Directory of Open Access Journals (Sweden)

    J. Sembian Ruso

    2016-05-01

    Full Text Available In this paper, we describe a simple and convenient conversion of aryl aldehydes to symmetrical dibenzyl ethers through reductive etherification. Similarly, unsymmetrical dibenzyl ether was obtained from aryl aldehyde and TES-protected benzyl alcohol. Triethyl silane with catalytic amount of InCl3 was found to be an efficient condition for the reductive etherification. Moreover, it exhibits remarkable functional group compatibility with yield ranging from good to excellent.

  7. Cascade synthesis of dihydrobenzofuran via Claisen rearrangement of allyl aryl ethers using FeCl3/MCM-41 catalyst

    Directory of Open Access Journals (Sweden)

    Sachin S. Sakate

    2018-05-01

    Full Text Available Dihydrobenzofuran as one of the active ingredients of the naturally occurring motif is synthesized by using in situ generation of ortho allyl phenols. Aryl allyl ethers on reacting with catalytic amounts of non noble metal iron (III chloride supported on MCM-41 under moderate reaction conditions yield dihydrobenzofuran. First step via Claisen rearrangement gives ortho allyl phenol followed by its in situ cyclization to yield dihydrobenzofuran in very good yields. Both Lewis as well as Brønsted acidity of the catalyst as evidenced by Py-FTIR studies was found to catalyze the cascade synthesis of dihydrobenzofuran. The scope of the present strategy was successfully demonstrated for several substrates with varying electronic effects for the synthesis of corresponding dihydrobenzofuran with high yields in a range of 71–86%. Keywords: Claisen rearrangement, Dihydrobenzofuran, Aryl allyl ether, MCM-41, Ferric chloride

  8. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

    KAUST Repository

    Liu, Xiangqian; Hsiao, Chien-Chi; Kalvet, Indrek; Leiendecker, Matthias; Guo, Lin; Schoenebeck, Franziska; Rueping, Magnus

    2016-01-01

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel

  9. 2-(Hetero(aryl)methylene)hydrazine-1-carbothioamides as potent urease inhibitors.

    Science.gov (United States)

    Saeed, Aamer; Imran, Aqeel; Channar, Pervaiz A; Shahid, Mohammad; Mahmood, Wajahat; Iqbal, Jamshed

    2015-02-01

    A small series of 2-(hetero(aryl)methylene) hydrazine-1-carbothioamides including two aryl derivatives was synthesized and tested for their inhibitory activity against urease. Compound (E)-2-(Furan-2-ylmethylene) hydrazine-1-carbothioamide (3f), having a furan ring, was the most potent inhibitor of urease with an IC50 value of 0.58 μM. Molecular modeling was carried out through docking the designed compounds into the urease binding site to predict whether these derivatives have analogous binding mode to the urease inhibitors. The study revealed that all of the tested compounds bind with both metal atoms at the active site of the enzyme. The aromatic ring of the compounds forms ionic interactions with the residues, Ala(440), Asp(494), Ala(636), and Met(637). © 2014 John Wiley & Sons A/S.

  10. Synthesis and Preliminary Properties of Novel Poly(aryl ethers Containing β-Naphthalene Pendant Group

    Directory of Open Access Journals (Sweden)

    L. Wang

    2014-01-01

    Full Text Available Two novel poly(aryl ethers containing β-naphthalene pendant group were synthesized and the structures of these polymers were confirmed by 1HNMR spectroscopy. The polymers exhibited good thermal stabilities with high Tg of 256°C and 274°C, respectively. The polymers are soluble in common organic solvents, such as DMAc, DMSO, CH2Cl2, and CHCl3, and can be electrospun into microfiber (1–5 µm with lots of nanopores (<100 nm from CHCl3 solution. These fibers showed high hydrophobicity, and the contact angle of fibers is above 120°.

  11. Molecular motions of non-crystalline poly(aryl ether-ether-ketone) PEEK and influence of electron beam irradiation

    International Nuclear Information System (INIS)

    Sasuga, T.; Hagiwara, M.

    1985-01-01

    The dynamic mechanical relaxation of non-crystalline poly(aryl ether-ether-ketone) PEEK and the one irradiated with electron beam were studied. The three distinct γ, β, α' relaxation maxima were observed in unirradiated PEEK from low to high temperature. It was revealed from the study on the irradiation effects that three different molecular processes are overlapped in γ relaxation peak, i.e., molecular motion of water bound to main chain, local motion of main chain, and local mode of the aligned and/or oriented moiety. The β relaxation connected with the glass transition occurred at 150 deg C and it shifted to higher temperature by irradiation. The α' relaxation which can be attributed to rearrangement of molecular chain due to crystallization was observed in unirradiated PEEK approx. 180 deg C and its magnitude decreased with the increase in irradiation dose. This effect indicates the formation of structures inhibiting crystallization such as crosslinking and/or short branching during irradiation. A new relaxation, β', appeared in the temperature range of 40 deg to 100 deg C by irradiation and its magnitude increased with dose. This relaxation was attributed to rearrangement of molecular chain from loosened packing around chain ends, which were introduced into the non-crystalline region by chain scission under irradiation, to more rigid molecular packing. (author)

  12. Thermal aromatic Claisen rearrangement and Strecker reaction of alkyl(allyl-aryl ethers under green reaction conditions: Efficient and clean preparation of ortho-allyl phenols (naphthols and alkyl(allyloxyarene-based γ-amino nitriles

    Directory of Open Access Journals (Sweden)

    Kheila N. Silgado-Gómez

    2017-11-01

    Full Text Available Chemical transformations of 13 diverse allyl(alkyl-aryl ethers, easily prepared using Williamson reaction of different hydroxyarenes and allyl bromide and alkyl (n-butyl, n-octyl bromides, were studied. Thermal aromatic Claisen rearrangement of allyl-aryl ethers to obtain ortho-allyl phenols (naphthols employing propylene carbonate as a nontoxic and biodegradable solvent was described for the first time. The use of this green solvent allowed to enhance notably product yields and reduce significantly the reaction time comparing with the use of 1,2-dichlorobenzene, toxic solvent, which is traditionally employed in this type of Claisen rearrangement. Three-component Strecker reaction of selected alkyl(allyl-aryl ethers with formyl function on aryl fragment and, piperidine and potassium cyanide in the presence of sulfuric acid supported on silica gel (SSA, SiO2-O-SO3H under mild reaction conditions was used in the preparation of new γ-amino nitriles, analogues of alkaloid girgensohnine [2-(4-hydroxyphenyl-2-(piperidin-1-ylacetonitrile], a perspective biological model in the search for new insecticidal agrochemicals against Aedes aegypti. The use of SSA, an inexpensive and reusable solid catalyst, allowed to obtain new series of 2-[4-alkyl(allyloxyphenyl]-2-(piperidin-1-ylacetonitriles in short time at room temperature with good yields.

  13. Synthesis and characterization of novel polyamide-ethers based on bis-imidazole containing bulky aryl pendant groups

    Directory of Open Access Journals (Sweden)

    Seyed Mahdi Saadati

    2013-01-01

    Full Text Available A series of novel polyamide-ethers (PAEs based on bis-imidazole containing bulky aryl pendant groups was prepared by direct polycondensation of a diamine, 4-(1-(4-(4-(2-(4-aminophenyl-4,5-diphenyl-1H-imidazol-1-ylphenoxyphenyl-4,5-diphenyl-1H-imidazol-2-ylbenzenamine (DABI, and various dicarboxylic acids. All the resulting polyamide-ethers were amorphous with inherent viscosities ranged from 0.52 to 0.61 dL/g and were readily soluble in many organic solvents which could be solution-cast into transparent and tough films. The glass transition temperatures (Tg of these polymers were affected considerably by their chemical structure and ranged from 230 to 310 ºC. They had useful levels of thermal stability associated with relatively high temperatures of 10% weight loss (T10 in the range of 329-399 ºC in air atmosphere.

  14. Rearrangements of Cycloalkenyl Aryl Ethers

    Directory of Open Access Journals (Sweden)

    Mercedesz Törincsi

    2016-04-01

    Full Text Available Rearrangement reactions of cycloalkenyl phenol and naphthyl ethers and the acid-catalyzed cyclization of the resulting product were investigated. Claisen rearrangement afforded 2-substituted phenol and naphthol derivatives. Combined Claisen and Cope rearrangement resulted in the formation of 4-substituted phenol and naphthol derivatives. In the case of cycloocthylphenyl ether the consecutive Claisen and Cope rearrangements were followed by an alkyl migration. The mechanism of this novel rearrangement reaction is also discussed.

  15. New aromatic activated dihalides and bisphenol monomers for the preparation of novel poly(arylene ethers)

    Science.gov (United States)

    Wolfe, James F.

    1993-01-01

    The goal of this research program was to synthesize a series of unique monomers of type I to be utilized at NASA-Langley in the preparation of new poly(arylene ether ketones), poly(arylene ether ketosulfones), and poly(arylene ether ketophosphine oxides). These A-A and A-B monomer systems, which possess activated aryl halide and/or phenolic end groups, are accessible via condensation reactions of appropriately substituted aryl acetonitrile carbanions with activated aryl dihalides followed by oxidative decyanation.

  16. Recent Developments of C-Aryl Glucoside SGLT2 Inhibitors.

    Science.gov (United States)

    Zhang, Yang; Liu, Zhao-Peng

    2016-01-01

    Sodium-glucose cotransporter 2 (SGLT2) is almost exclusively expressed in the proximal renal tubules. It is responsible for about 90% of the glucose reabsorption from tubular fluid. Selective inhibition of SGLT2 is expected to favor in the normalization of plasma glucose levels in T2DM patients through the prevention of renal glucose reabsorption and the promotion of glucose excretion from urine. Selective SGLT2 inhibitors have the merits to minimize the gastrointestinal side effects associated with SGLT1 inhibition, and selective SGLT2 inhibition may have a low risk of hypoglycemia. Since the C-aryl glucosides are metabolically more stable than the O-glucosides, numerous efforts have been made in the development of potent and selective C-aryl glucoside SGLT2 inhibitors, and a number of them are now used as anti-diabetes drugs in clinic or at various stages of clinical developments. Based on their structural features, in this review, these SGLT2 inhibitors are classified as three types: the phenyl/arylmethylphenyl C-glucosides, with an emphasis on the modifications on the proximal and/or the distal phenyl ring, and the spacer; the heteroarylmethylphenyl Cglucosides, with a replacement of the distal phenyl ring by a heterocycle like pyridazine, pyrimidine, thiophene and benzothiophene, thiazole, 1,3,4-thiadiazole, and triazolopyridinone; and the glucose-modified Caryl glucosides, including the glucose C-1 derived O-spiroketals, C-4 gem-difluoro analogues, C-5 and C-6 modified derivatives, dioxa-bicyclo[3.2.1]octane bridged ketals, the thioglucosides, and carbasugars. The structure-activity relationships (SARs) of each type along with their inhibitory potency against human SGLT2 and selectivity over human SGLT1 are discussed.

  17. Enhanced antifouling and antibacterial properties of poly (ether sulfone) membrane modified through blending with sulfonated poly (aryl ether sulfone) and copper nanoparticles

    Science.gov (United States)

    Zhang, Jingjing; Xu, Ya'nan; Chen, Shouwen; Li, Jiansheng; Han, Weiqing; Sun, Xiuyun; Wu, Dihua; Hu, Zhaoxia; Wang, Lianjun

    2018-03-01

    A series of novel blend ultrafiltration (UF) membranes have been successfully prepared from commercial poly (ether sulfone), lab-synthesized sulfonated poly (aryl ether sulfone) (SPAES, 1 wt%) and copper nanoparticles (0 ∼ 0.4 wt%) via immersion precipitation phase conversion. The micro-structure and separation performance of the membranes were characterized by field emission scanning electron microscopy (SEM) and cross-flow filtration experiments, respectively. Sodium alginate, bovine serum albumin and humic acid were chosen as model organic foulants to investigate the antifouling properties, while E. coil was used to evaluate the antibacterial property of the fabricated membranes. By the incorporation with SPAES and copper nanoparticles, the hydrophilicity, antifouling and antibacterial properties of the modified UF membranes have been profoundly improved. At a copper nanoparticles content of 0.4 wt%, the PES/SPAES/nCu(0.4) membrane exhibited a high pure water flux of 193.0 kg/m2 h, reaching the smallest contact angle of 52°, highest flux recovery ratio of 79% and largest antibacterial rate of 78.9%. Furthermore, the stability of copper nanoparticles inside the membrane matrix was also considerably enhanced, the copper nanoparticles were less than 0.08 mg/L in the effluent during the whole operation.

  18. Development of 1-aryl-3-furanyl/thienyl-imidazopyridine templates for inhibitors against hypoxia inducible factor (HIF)-1 transcriptional activity.

    Science.gov (United States)

    Fuse, Shinichiro; Ohuchi, Toshiaki; Asawa, Yasunobu; Sato, Shinichi; Nakamura, Hiroyuki

    2016-12-15

    1,3-Disubstituted-imidazopyridines were designed for developing inhibitors against HIF-1 transcriptional activity. Designed compounds were rapidly synthesized from a key aromatic scaffold via microwave-assisted Suzuki-Miyaura coupling/CH direct arylation sequence. Evaluation of ability to inhibit the hypoxia induced transcriptional activity of HIF-1 revealed that the compound 2i and 3a retained the same level of the inhibitory activity comparing with that of known inhibitor, YC-1 (1). Identified, readily accessible 1-aryl-3-furanyl/thienyl-imidazopyridine templates should be useful for future drug development. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. C2 Arylated Benzo[b]thiophene Derivatives as Staphylococcus aureus NorA Efflux Pump Inhibitors.

    Science.gov (United States)

    Liger, François; Bouhours, Pascale; Ganem-Elbaz, Carine; Jolivalt, Claude; Pellet-Rostaing, Stéphane; Popowycz, Florence; Paris, Jean-Marc; Lemaire, Marc

    2016-02-04

    An innovative and straightforward synthesis of second-generation 2-arylbenzo[b]thiophenes as structural analogues of INF55 and the first generation of our laboratory-made molecules was developed. The synthesis of C2-arylated benzo[b]thiophene derivatives was achieved through a method involving direct arylation, followed by simple structural modifications. Among the 34 compounds tested, two of them were potent NorA pump inhibitors, which led to a 16-fold decrease in the ciprofloxacin minimum inhibitory concentration (MIC) against the SA-1199B strain at concentrations of 0.25 and 0.5 μg mL(-1) (1 and 1.5 μm, respectively). This is a promising result relative to that obtained for reserpine (MIC=20 μg mL(-1)), a reference compound amongst NorA pump inhibitors. These molecules thus represent promising candidates to be used in combination with ciprofloxacin against fluoroquinolone-resistant strains. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Structural investigation of HIV-1 nonnucleoside reverse transcriptase inhibitors: 2-Aryl-substituted benzimidazoles

    Science.gov (United States)

    Ziółkowska, Natasza E.; Michejda, Christopher J.; Bujacz, Grzegorz D.

    2009-11-01

    Acquired immunodeficiency syndrome (AIDS) caused by the human immunodeficiency virus (HIV) is one of the most destructive epidemics in history. Inhibitors of HIV enzymes are the main targets to develop drugs against that disease. Nonnucleoside reverse transcriptase inhibitors of HIV-1 (NNRTIs) are potentially effective and nontoxic. Structural studies provide information necessary to design more active compounds. The crystal structures of four NNRTI derivatives of 2-aryl-substituted N-benzyl-benzimidazole are presented here. Analysis of the geometrical parameters shows that the structures of the investigated inhibitors are rigid. The important geometrical parameter is the dihedral angle between the planes of the π-electron systems of the benzymidazole and benzyl moieties. The values of these dihedral angles are in a narrow range for all investigated inhibitors. There is no significant difference between the structure of the free inhibitor and the inhibitor in the complex with RT HIV-1. X-ray structures of the investigated inhibitors are a good basis for modeling enzyme-inhibitor interactions in rational drug design.

  1. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

    KAUST Repository

    Liu, Xiangqian

    2016-04-10

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel-catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process.

  2. Antibacterial activity of berberine-NorA pump inhibitor hybrids with a methylene ether linking group.

    Science.gov (United States)

    Samosorn, Siritron; Tanwirat, Bongkot; Muhamad, Nussara; Casadei, Gabriele; Tomkiewicz, Danuta; Lewis, Kim; Suksamrarn, Apichart; Prammananan, Therdsak; Gornall, Karina C; Beck, Jennifer L; Bremner, John B

    2009-06-01

    Conjugation of the NorA substrate berberine and the NorA inhibitor 5-nitro-2-phenyl-1H-indole via a methylene ether linking group gave the 13-substituted berberine-NorA inhibitor hybrid, 3. A series of simpler arylmethyl ether hybrid structures were also synthesized. The hybrid 3 showed excellent antibacterial activity (MIC Staphylococcus aureus, 1.7 microM), which was over 382-fold more active than the parent antibacterial berberine, against this bacterium. This compound was also shown to block the NorA efflux pump in S. aureus.

  3. H2O2 recycling during oxidation of the arylglycerol beta-aryl ether lignin structure by lignin peroxidase and glyoxal oxidase.

    Science.gov (United States)

    Hammel, K E; Mozuch, M D; Jensen, K A; Kersten, P J

    1994-11-15

    Oxidative C alpha-C beta cleavage of the arylglycerol beta-aryl ether lignin model 1-(3,4-dimethoxy-phenyl)-2-phenoxypropane-1,3-diol (I) by Phanerochaete chrysosporium lignin peroxidase in the presence of limiting H2O2 was enhanced 4-5-fold by glyoxal oxidase from the same fungus. Further investigation showed that each C alpha-C beta cleavage reaction released 0.8-0.9 equiv of glycolaldehyde, a glyoxal oxidase substrate. The identification of glycolaldehyde was based on 13C NMR spectrometry of reaction product obtained from beta-, gamma-, and beta,gamma-13C-substituted I, and quantitation was based on an enzymatic NADH-linked assay. The oxidation of glycolaldehyde by glyoxal oxidase yielded 0.9 oxalate and 2.8 H2O2 per reaction, as shown by quantitation of oxalate as 2,3-dihydroxyquinoxaline after derivatization with 1,2-diaminobenzene and by quantitation of H2O2 in coupled spectrophotometric assays with veratryl alcohol and lignin peroxidase. These results suggest that the C alpha-C beta cleavage of I by lignin peroxidase in the presence of glyoxal oxidase should regenerate as many as 3 H2O2. Calculations based on the observed enhancement of LiP-catalyzed C alpha-C beta cleavage by glyoxal oxidase showed that approximately 2 H2O2 were actually regenerated per cleavage of I when both enzymes were present. The cleavage of arylglycerol beta-aryl ether structures by ligninolytic enzymes thus recycles H2O2 to support subsequent cleavage reactions.

  4. Synthesis and biological evaluation of novel dioxa-bicycle C-aryl glucosides as SGLT2 inhibitors.

    Science.gov (United States)

    Yan, Qi; Ding, Ning; Li, Yingxia

    2016-02-08

    A series of novel C-aryl glucosides containing dioxa-bicycle were synthesized and evaluated for inhibition activity against hSGLT2. Among the compounds tested, compound 6a showed moderate SGLT2 inhibition activities at 700 nM. The results could benefit the discovery of new SGLT2 inhibitors. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. 1,3-disubstituted ureas functionalized with ether groups are potent inhibitors of the soluble epoxide hydrolase with improved pharmacokinetic properties.

    Science.gov (United States)

    Kim, In-Hae; Tsai, Hsing-Ju; Nishi, Kosuke; Kasagami, Takeo; Morisseau, Christophe; Hammock, Bruce D

    2007-10-18

    Soluble epoxide hydrolase (sEH) is a therapeutic target for treating hypertension and inflammation. 1,3-Disubstituted ureas functionalized with an ether group are potent sEH inhibitors. However, their relatively low metabolic stability leads to poor pharmacokinetic properties. To improve their bioavailability, we investigated the effect of incorporating various polar groups on the ether function on the inhibition potencies, physical properties, in vitro metabolic stability, and pharmacokinetic properties. The structure-activity relationship studies showed that a hydrophobic linker between the urea group and the ether function is necessary to keep their potency. In addition, urea-ether inhibitors having a polar group such as diethylene glycol or morpholine significantly improved their physical properties and metabolic stability without any loss of inhibitory potency. Furthermore, improved pharmacokinetic properties in murine and canine models were obtained with the resulting inhibitors. These findings will facilitate the usage of sEH inhibitors in animal models of hypertension and inflammation.

  6. Degradation of lignin β-aryl ether units in Arabidopsis thaliana expressing LigD, LigF and LigG from Sphingomonas paucimobilis SYK-6

    DEFF Research Database (Denmark)

    Mnich, Ewelina; Vanholme, Ruben; Oyarce, Paula

    2017-01-01

    Lignin is a major polymer in the secondary plant cell wall and composed of hydrophobic interlinked hydroxyphenylpropanoid units. The presence of lignin hampers conversion of plant biomass into biofuels; plants with modified lignin are therefore being investigated for increased digestibility....... The bacterium Sphingomonas paucimobilis produces lignin-degrading enzymes including LigD, LigF and LigG involved in cleaving the most abundant lignin inter-unit linkage, the β-aryl ether bond. In this study, we expressed the LigD, LigF and LigG (LigDFG) genes in Arabidopsis thaliana to introduce post...

  7. Copper Promoted Synthesis of Diaryl Ethers

    OpenAIRE

    Ghosh, Rajshekhar; Samuelson, Ashoka G

    2004-01-01

    An efficient protocol using copper based reagents for the coupling of aryl halides with phenols to generate diaryl ethers is described. Acopper( I) complex, [ Cu( CH3CN) (4)] ClO4, or the readily available copper( II) source, CuCO3 . Cu( OH) (2) . H2O ( in combination with potassium phosphate), can be used. Aryl halides and phenols with different steric and electronic demands have been used to assess the efficiency of the procedure. The latter source of copper gives better yields under all co...

  8. Design and synthesis of N₁-aryl-benzimidazoles 2-substituted as novel HIV-1 non-nucleoside reverse transcriptase inhibitors.

    Science.gov (United States)

    Monforte, Anna-Maria; Ferro, Stefania; De Luca, Laura; Lo Surdo, Giuseppa; Morreale, Francesca; Pannecouque, Christophe; Balzarini, Jan; Chimirri, Alba

    2014-02-15

    A series of novel N1-aryl-2-arylthioacetamido-benzimidazoles were synthesized and evaluated as inhibitors of human immunodeficiency virus type-1 (HIV-1). Some of them proved to be effective in inhibiting HIV-1 replication at submicromolar and nanomolar concentration acting as HIV-1 non-nucleoside RT inhibitors (NNRTIs), with low cytotoxicity. The preliminary structure-activity relationship (SAR) of these new derivatives was discussed and rationalized by docking studies. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Well-Defined Copper(I) Fluoroalkoxide Complexes for Trifluoroethoxylation of Aryl and Heteroaryl Bromides

    KAUST Repository

    Huang, Ronglu

    2015-03-17

    © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Copper(I) fluoroalkoxide complexes bearing dinitrogen ligands were synthesized and the structure and reactivity of the complexes toward trifluoroethoxylation, pentafluoropropoxylation, and tetrafluoropropoxylation of aryl and heteroaryl bromides were investigated. Efficiency drive: A series of copper(I) fluoroalkoxide complexes bearing N,N ligands have been prepared and structurally characterized. These well-defined complexes serve as efficient reagents for the fluoroalkoxylation of aryl and heteroaryl bromides to produce a wide range of trifluoroethyl, pentafluoropropyl, and tetrafluoropropyl (hetero)aryl ethers in good to excellent yields.

  10. Geissoschizine methyl ether, a corynanthean-type indole alkaloid from Uncaria rhynchophylla as a potential acetylcholinesterase inhibitor.

    Science.gov (United States)

    Yang, Zhong-Duo; Duan, Dong-Zhu; Du, Juan; Yang, Ming-Jun; Li, Shuo; Yao, Xiao-Jun

    2012-01-01

    Geissoschizine methyl ether (1), a newly discovered strong acetylcholinesterase (AChE) inhibitor, along with six weakly active alkaloids, vallesiachotamine (2), hisuteine (3), hirsutine (4), isorhynchophylline (5), cisocorynoxeine (6) and corynoxeine (7) have been isolated from Uncaria rhynchophylla. Geissoschizine methyl ether (1) inhibited 50% of AChE activity at concentrations of 3.7 ± 0.3 µg mL(-1) while the IC(50) value of physostigmine as a standard was 0.013 ± 0.002 µg mL(-1). The mode of AChE inhibition by 1 was reversible and non-competitive. In addition, molecular modelling was performed to explore the binding mode of inhibitor 1 at the active site of AChE.

  11. Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes for vanadium redox flow battery applications

    Science.gov (United States)

    Zhang, Bengui; Zhang, Shouhai; Weng, Zhihuan; Wang, Guosheng; Zhang, Enlei; Yu, Ping; Chen, Xiaomeng; Wang, Xinwei

    2016-09-01

    Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes (QADMPEK) are prepared and investigated for vanadium redox flow batteries (VRFB) application. The bulky, rigid and highly hydrophobic adamantane segment incorporated into the backbone of membrane material makes QADMPEK membranes have low water uptake and swelling ratio, and the as-prepared membranes display significantly lower permeability of vanadium ions than that of Nafion117 membrane. As a consequence, the VRFB cell with QADMPEK-3 membrane shows higher coulombic efficiency (99.4%) and energy efficiency (84.0%) than those for Nafion117 membrane (95.2% and 80.5%, respectively) at the current density of 80 mA cm-2. Furthermore, at a much higher current density of 140 mA cm-2, QADMPEK membrane still exhibits better coulombic efficiency and energy efficiency than Nafion117 membrane (coulombic efficiency 99.2% vs 96.5% and energy efficiency 76.0% vs 74.0%). Moreover, QADMPEK membranes show high stability in in-situ VRFB cycle test and ex-situ oxidation stability test. These results indicate that QADMPEK membranes are good candidates for VRFB applications.

  12. Mechanism-based inactivation of benzo[a]pyrene hydroxylase by aryl acetylenes and aryl olefins

    International Nuclear Information System (INIS)

    Gan, L.S.; Lu, J.Y.L.; Alworth, W.L.

    1986-01-01

    A series of aryl acetylenes and aryl olefins have been examined as substrates and inhibitors of cytochrome P-450 dependent monooxgenases in liver microsomes from 5,6-benzoflavone or phenobarbital pretreated rats. 1-Ethynylpyrene, 3-ethynylperylene, 2-ethynylfluorene, methyl 1-pyrenyl acetylene, cis- and trans-1-(2-bromovinyl)pyrene, and 1-allylpyrene serve as mechanism-based irreversible inactivators (suicide inhibitors) of benzo[a]pyrene hydroxylase, while 1-vinylpyrene and phenyl 1-pyrenyl acetylene do not cause a detectable suicide inhibition of benzo[a]pyrene hydroxylase. The mechanism-based loss of benzo[a]pyrene hydroxylase caused by the aryl acetylenes is not accompanied by a corresponding loss of the P-450 content of the microsomes (suicide destruction). The suicide inhibition by these aryl acetylenes therefore does not involve covalent binding to the heme moiety of the monooxygenase. Nevertheless, in the presence of NADPH, 3 H-labeled 1-ethynylpyrene becomes covalently attached to the cytochrome P-450 protein; the measured stoichiometry of binding is one 1-ethynylpyrene per P-450 heme unit. The authors conclude that the inhibition of benzo[a]pyrene hydroxylase produced by 1-ethynylpyrene may be related to the mechanism of suicide inhibition of P-450 activity by chloramphenicol rather than the mechanism of suicide destruction of P-450 previously described for acetylene and propyne

  13. C-Aryl glucoside SGLT2 inhibitors containing a biphenyl motif as potential anti-diabetic agents.

    Science.gov (United States)

    Ding, Yuyang; Mao, Liufeng; Xu, Dengfeng; Xie, Hui; Yang, Ling; Xu, Hongjiang; Geng, Wenjun; Gao, Yong; Xia, Chunguang; Zhang, Xiquan; Meng, Qingyi; Wu, Donghai; Zhao, Junling; Hu, Wenhui

    2015-07-15

    A series of highly active C-aryl glucoside SGLT2 inhibitors containing a biphenyl motif were designed and synthesized for biological evaluation. Among the compounds tested, compound 16l demonstrated high inhibitory activity against SGLT2 (IC50=1.9 nM) with an excellent pharmacokinetic profile. Further study indicated that the in vivo efficacy of compound 16l was comparable to that of dapagliflozin, suggesting that further development would be worthwhile. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Indoleamine 2,3-dioxygenase 1 (IDO1) inhibitors activate the aryl hydrocarbon receptor

    Energy Technology Data Exchange (ETDEWEB)

    Moyer, Benjamin J. [Department of Molecular and Systems Biology, Geisel School of Medicine at Dartmouth, Dartmouth Hitchcock Medical Center, One Medical Center Drive, Lebanon, NH 03756 (United States); Rojas, Itzel Y. [Norris Cotton Cancer Center, Geisel School of Medicine at Dartmouth, Dartmouth Hitchcock Medical Center, One Medical Center Drive, Lebanon, NH 03756 (United States); Murray, Iain A. [Center for Molecular Toxicology and Carcinogenesis, The Pennsylvania State University, University Park, PA 16802 (United States); Department of Veterinary and Biomedical Sciences, The Pennsylvania State University, University Park, PA 16802 (United States); Lee, Seokwon; Hazlett, Haley F. [Norris Cotton Cancer Center, Geisel School of Medicine at Dartmouth, Dartmouth Hitchcock Medical Center, One Medical Center Drive, Lebanon, NH 03756 (United States); Perdew, Gary H. [Center for Molecular Toxicology and Carcinogenesis, The Pennsylvania State University, University Park, PA 16802 (United States); Department of Veterinary and Biomedical Sciences, The Pennsylvania State University, University Park, PA 16802 (United States); Tomlinson, Craig R., E-mail: Craig.R.Tomlinson@Dartmouth.edu [Department of Molecular and Systems Biology, Geisel School of Medicine at Dartmouth, Dartmouth Hitchcock Medical Center, One Medical Center Drive, Lebanon, NH 03756 (United States); Norris Cotton Cancer Center, Geisel School of Medicine at Dartmouth, Dartmouth Hitchcock Medical Center, One Medical Center Drive, Lebanon, NH 03756 (United States)

    2017-05-15

    Indoleamine 2,3-dioxygenase 1 (IDO1) plays a key role in the immune system by regulating tryptophan levels and T cell differentiation. Several tumor types overexpress IDO1 to avoid immune surveillance making IDO1 of interest as a target for therapeutic intervention. As a result, several IDO1 inhibitors are currently being tested in clinical trials for cancer treatment as well as several other diseases. Many of the IDO1 inhibitors in clinical trials naturally bear structural similarities to the IDO1 substrate tryptophan, as such, they fulfill many of the structural and functional criteria as potential AHR ligands. Using mouse and human cell-based luciferase gene reporter assays, qPCR confirmation experiments, and CYP1A1 enzyme activity assays, we report that some of the promising clinical IDO1 inhibitors also act as agonists for the aryl hydrocarbon receptor (AHR), best known for its roles in xenobiotic metabolism and as another key regulator of the immune response. The dual role as IDO antagonist and AHR agonist for many of these IDO target drugs should be considered for full interrogation of their biological mechanisms and clinical outcomes. - Highlights: • Indoleamine-2,3-dioxygenase 1 (IDO1) inhibitors are in cancer clinical trials. • Some IDO1 inhibitors also potently activate AHR signaling. • The dual role of the IDO1 inhibitors may explain some past paradoxical findings. • AHR induction studies must be included in assessing clinical suitability.

  15. Indoleamine 2,3-dioxygenase 1 (IDO1) inhibitors activate the aryl hydrocarbon receptor

    International Nuclear Information System (INIS)

    Moyer, Benjamin J.; Rojas, Itzel Y.; Murray, Iain A.; Lee, Seokwon; Hazlett, Haley F.; Perdew, Gary H.; Tomlinson, Craig R.

    2017-01-01

    Indoleamine 2,3-dioxygenase 1 (IDO1) plays a key role in the immune system by regulating tryptophan levels and T cell differentiation. Several tumor types overexpress IDO1 to avoid immune surveillance making IDO1 of interest as a target for therapeutic intervention. As a result, several IDO1 inhibitors are currently being tested in clinical trials for cancer treatment as well as several other diseases. Many of the IDO1 inhibitors in clinical trials naturally bear structural similarities to the IDO1 substrate tryptophan, as such, they fulfill many of the structural and functional criteria as potential AHR ligands. Using mouse and human cell-based luciferase gene reporter assays, qPCR confirmation experiments, and CYP1A1 enzyme activity assays, we report that some of the promising clinical IDO1 inhibitors also act as agonists for the aryl hydrocarbon receptor (AHR), best known for its roles in xenobiotic metabolism and as another key regulator of the immune response. The dual role as IDO antagonist and AHR agonist for many of these IDO target drugs should be considered for full interrogation of their biological mechanisms and clinical outcomes. - Highlights: • Indoleamine-2,3-dioxygenase 1 (IDO1) inhibitors are in cancer clinical trials. • Some IDO1 inhibitors also potently activate AHR signaling. • The dual role of the IDO1 inhibitors may explain some past paradoxical findings. • AHR induction studies must be included in assessing clinical suitability.

  16. A modified approach to 2-(N-aryl)-1,3-oxazoles: application to the synthesis of the IMPDH inhibitor BMS-337197 and analogues.

    Science.gov (United States)

    Dhar, T G Murali; Guo, Junqing; Shen, Zhongqi; Pitts, William J; Gu, Henry H; Chen, Bang-Chi; Zhao, Rulin; Bednarz, Mark S; Iwanowicz, Edwin J

    2002-06-13

    [structure: see text] A modified approach to the synthesis of 2-(N-aryl)-1,3-oxazoles, employing an optimized iminophosphorane/heterocumulene-mediated methodology, and its application to the synthesis of BMS-337197, a potent inhibitor of IMPDH, are described.

  17. A mild and efficient procedure for the synthesis of ethers from various alkyl halides

    Directory of Open Access Journals (Sweden)

    Mosstafa Kazemi

    2013-10-01

    Full Text Available A simple, mild and practical procedure has been developed for the synthesis of symmetrical and unsymmetrical ethers by using DMSO, TBAI in the presence of K2CO3. We extended the utility of Potassium carbonate as an efficient base for the preparation of ethers. A wide range of alkyl aryl and dialkyl ethers are synthezied from treatment of aliphatic alcohols and phenols with various alkyl halides in the prescence of efficient base Potassium carbonate. Secondary alkyl halides were easily converted to corresponding ethers in releatively good yields . This is a mild, simple and practical procedure for the preparation of ethers in high yields and suitable times under mild condition.

  18. Simple and Efficient Generation of Aryl Radicals from Aryl Triflates: Synthesis of Aryl Boronates and Aryl Iodides at Room Temperature.

    Science.gov (United States)

    Liu, Wenbo; Yang, Xiaobo; Gao, Yang; Li, Chao-Jun

    2017-06-28

    Despite the wide use of aryl radicals in organic synthesis, current methods to prepare them from aryl halides, carboxylic acids, boronic acids, and diazonium salts suffer from limitations. Aryl triflates, easily obtained from phenols, are promising aryl radical progenitors but remain elusive in this regard. Inspired by the single electron transfer process for aryl halides to access aryl radicals, we developed a simple and efficient protocol to convert aryl triflates to aryl radicals. Our success lies in exploiting sodium iodide as the soft electron donor assisted by light. This strategy enables the scalable synthesis of two types of important organic molecules, i.e., aryl boronates and aryl iodides, in good to high yields, with broad functional group compatibility in a transition-metal-free manner at room temperature. This protocol is anticipated to find potential applications in other aryl-radical-involved reactions by using aryl triflates as aryl radical precursors.

  19. Asymmetric synthesis of quaternary aryl amino acid derivatives via a three-component aryne coupling reaction

    Directory of Open Access Journals (Sweden)

    Elizabeth P. Jones

    2011-11-01

    Full Text Available A method was developed for the synthesis of α-alkyl, α-aryl-bislactim ethers in good to excellent yields and high diastereoselectivities, consisting of a facile one-pot procedure in which the aryl group is introduced by means of a nucleophilic addition to benzyne and the alkyl group by alkylation of a resultant benzylic anion. Hydrolysis of the sterically less hindered adducts gave the corresponding quaternary amino acids with no racemization, whereas hydrolytic ring opening gave the corresponding valine dipeptides from bulkier bislactims.

  20. 1,3-Disubstituted Ureas Functionalized with Ether Groups are Potent Inhibitors of the Soluble Epoxide Hydrolase with Improved Pharmacokinetic Properties

    OpenAIRE

    Kim, In-Hae; Tsai, Hsing-Ju; Nishi, Kosuke; Kasagami, Takeo; Morisseau, Christophe; Hammock, Bruce D.

    2007-01-01

    Soluble epoxide hydrolase (sEH) is a therapeutic target for treating hypertension and inflammation. 1,3-Disubstituted ureas functionalized with an ether group are potent sEH inhibitors. However, their relatively low metabolic stability leads to poor pharmacokinetic properties. To improve their bioavailability, we investigated the effect of incorporating various polar groups on the ether function on the inhibition potencies, physical properties, in vitro metabolic stability, and pharmacokineti...

  1. Identification of metabolites of the tryptase inhibitor CRA-9249: observation of a metabolite derived from an unexpected hydroxylation pathway.

    Science.gov (United States)

    Yu, Walter; Dener, Jeffrey M; Dickman, Daniel A; Grothaus, Paul; Ling, Yun; Liu, Liang; Havel, Chris; Malesky, Kimberly; Mahajan, Tania; O'Brian, Colin; Shelton, Emma J; Sperandio, David; Tong, Zhiwei; Yee, Robert; Mordenti, Joyce J

    2006-08-01

    The metabolites of the tryptase inhibitor CRA-9249 were identified after exposure to liver microsomes. CRA-9249 was found to be degraded rapidly in liver microsomes from rabbit, dog, cynomolgus monkey, and human, and less rapidly in microsomes from rat. The key metabolites included cleavage of an aryl ether, in addition to an unexpected hydroxylation of the amide side chain adjacent to the amide nitrogen. The chemical structures of both metabolites were confirmed by synthesis and comparison to material isolated from the liver microsomes. Several suspected hydroxylated metabolites were also synthesized and analyzed as part of the structure identification process.

  2. Structural optimization of N1-aryl-benzimidazoles for the discovery of new non-nucleoside reverse transcriptase inhibitors active against wild-type and mutant HIV-1 strains.

    Science.gov (United States)

    Monforte, Anna Maria; De Luca, Laura; Buemi, Maria Rosa; Agharbaoui, Fatima E; Pannecouque, Christophe; Ferro, Stefania

    2018-02-01

    Non-nucleoside reverse transcriptase inhibitors (NNRTIs) are recommended components of preferred combination antiretroviral therapies used for the treatment of human immunodeficiency virus (HIV) infection. These regimens are extremely effective in suppressing virus replication. Recently, our research group identified some N 1 -aryl-2-arylthioacetamido-benzimidazoles as a novel class of NNRTIs. In this research work we report the design, the synthesis and the structure-activity relationship studies of new compounds (20-34) in which some structural modifications have been introduced in order to investigate their effects on reverse transcriptase (RT) inhibition and to better define the features needed to increase the antiviral activity. Most of the new compounds proved to be highly effective in inhibiting both RT enzyme at nanomolar concentrations and HIV-1 replication in MT4 cells with minimal cytotoxicity. Among them, the most promising N 1 -aryl-2-arylthioacetamido-benzimidazoles and N 1 -aryl-2-aryloxyacetamido-benzimidazoles were also tested toward a panel of single- and double-mutants strain responsible for resistance to NNRTIs, showing in vitro antiviral activity toward single mutants L100I, K103N, Y181C, Y188L and E138K. The best results were observed for derivatives 29 and 33 active also against the double mutants F227L and V106A. Computational approaches were applied in order to rationalize the potency of the new synthesized inhibitors. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Screening of ligands for the Ullmann synthesis of electron-rich diaryl ethers.

    Science.gov (United States)

    Otto, Nicola; Opatz, Till

    2012-01-01

    In the search for new ligands for the Ullmann diaryl ether synthesis, permitting the coupling of electron-rich aryl bromides at relatively low temperatures, 56 structurally diverse multidentate ligands were screened in a model system that uses copper iodide in acetonitrile with potassium phosphate as the base. The ligands differed largely in their performance, but no privileged structural class could be identified.

  4. Identification of [4-[4-(methylsulfonyl)phenyl]-6-(trifluoromethyl)-2-pyrimidinyl] amines and ethers as potent and selective cyclooxygenase-2 inhibitors.

    Science.gov (United States)

    Swarbrick, Martin E; Beswick, Paul J; Gleave, Robert J; Green, Richard H; Bingham, Sharon; Bountra, Chas; Carter, Malcolm C; Chambers, Laura J; Chessell, Iain P; Clayton, Nick M; Collins, Sue D; Corfield, John A; Hartley, C David; Kleanthous, Savvas; Lambeth, Paul F; Lucas, Fiona S; Mathews, Neil; Naylor, Alan; Page, Lee W; Payne, Jeremy J; Pegg, Neil A; Price, Helen S; Skidmore, John; Stevens, Alexander J; Stocker, Richard; Stratton, Sharon C; Stuart, Alastair J; Wiseman, Joanne O

    2009-08-01

    A novel series of [4-[4-(methylsulfonyl)phenyl]-6-(trifluoromethyl)-2-pyrimidine-based cyclooxygenase-2 (COX-2) inhibitors, which have a different arrangement of substituents compared to the more common 1,2-diarylheterocycle based molecules, have been discovered. For example, 2-(butyloxy)-4-[4-(methylsulfonyl)phenyl]-6-(trifluoromethyl)pyrimidine (47), a member of the 2-pyrimidinyl ether series, has been shown to be a potent and selective inhibitor with a favourable pharmacokinetic profile, high brain penetration and good efficacy in rat models of hypersensitivity.

  5. Screening of ligands for the Ullmann synthesis of electron-rich diaryl ethers

    Directory of Open Access Journals (Sweden)

    Nicola Otto

    2012-07-01

    Full Text Available In the search for new ligands for the Ullmann diaryl ether synthesis, permitting the coupling of electron-rich aryl bromides at relatively low temperatures, 56 structurally diverse multidentate ligands were screened in a model system that uses copper iodide in acetonitrile with potassium phosphate as the base. The ligands differed largely in their performance, but no privileged structural class could be identified.

  6. Reactivity of Aryl Halides for Reductive Dehalogenation in (Seawater Using Polymer-Supported Terpyridine Palladium Catalyst

    Directory of Open Access Journals (Sweden)

    Toshimasa Suzuka

    2015-05-01

    Full Text Available A polymer-supported terpyridine palladium complex was prepared. The complex was found to promote hydrodechlorination of aryl chlorides with potassium formate in seawater. Generally, reductive cleavage of aryl chlorides using transition metal catalysts is more difficult than that of aryl bromides and iodides (reactivity: I > Br > Cl; however, the results obtained did not follow the general trend. Therefore, we investigated the reaction inhibition agents and found a method to remove these inhibitors. The polymeric catalysts showed high catalytic activity and high reusability for transfer reduction in seawater.

  7. Direct N9-arylation of purines with aryl halides

    DEFF Research Database (Denmark)

    Larsen, Anders Foller; Ulven, Trond

    2014-01-01

    An efficient method for N-arylation of purines is reported. The N-arylation is catalysed by Cu(i) and 4,7-bis(2-hydroxyethylamino)-1,10-phenanthroline (BHPhen) in aqueous DMF or ethanol. The reaction generally proceeds with high selectivity for the N(9)-position.......An efficient method for N-arylation of purines is reported. The N-arylation is catalysed by Cu(i) and 4,7-bis(2-hydroxyethylamino)-1,10-phenanthroline (BHPhen) in aqueous DMF or ethanol. The reaction generally proceeds with high selectivity for the N(9)-position....

  8. Effects of a Squalene Epoxidase Inhibitor, Terbinafine, on Ether Lipid Biosyntheses in a Thermoacidophilic Archaeon, Thermoplasma acidophilum

    Science.gov (United States)

    Kon, Takahide; Nemoto, Naoki; Oshima, Tairo; Yamagishi, Akihiko

    2002-01-01

    The archaeal plasma membrane consists mainly of diether lipids and tetraether lipids instead of the usual ester lipids found in other organisms. Although a molecule of tetraether lipid is thought to be synthesized from two molecules of diether lipids, there is no direct information about the biosynthetic pathway(s) or intermediates of tetraether lipid biosynthesis. In this study, we examined the effects of the fungal squalene epoxidase inhibitor terbinafine on the growth and ether lipid biosyntheses in the thermoacidophilic archaeon Thermoplasma acidophilum. Terbinafine was found to inhibit the growth of T. acidophilum in a concentration-dependent manner. When growing T. acidophilum cells were pulse-labeled with [2-14C]mevalonic acid in the presence of terbinafine, incorporation of radioactivity into the tetraether lipid fraction was strongly suppressed, while accumulation of radioactivity was noted at the position corresponding to diether lipids, depending on the concentration of terbinafine. After the cells were washed with fresh medium and incubated further without the radiolabeled substrate and the inhibitor, the accumulated radioactivity in the diether lipid fraction decreased quickly while that in the tetraether lipids increased simultaneously, without significant changes in the total radioactivity of ether lipids. These results strongly suggest that terbinafine inhibits the biosynthesis of tetraether lipids from a diether-type precursor lipid(s). The terbinafine treatment will be a tool for dissecting tetraether lipid biosynthesis in T. acidophilum. PMID:11844769

  9. Direct Synthesis of 5-Aryl Barbituric Acids by Rhodium(II)-Catalyzed Reactions of Arenes with Diazo Compounds**

    Science.gov (United States)

    Best, Daniel; Burns, David J; Lam, Hon Wai

    2015-01-01

    A commercially available rhodium(II) complex catalyzes the direct arylation of 5-diazobarbituric acids with arenes, allowing straightforward access to 5-aryl barbituric acids. Free N—H groups are tolerated on the barbituric acid, with no complications arising from N—H insertion processes. This method was applied to the concise synthesis of a potent matrix metalloproteinase (MMP) inhibitor. PMID:25959544

  10. Preparation and DMFC performance of a sulfophenylated poly(arylene ether ketone) polymer electrolyte membrane

    Energy Technology Data Exchange (ETDEWEB)

    Liu Baijun, E-mail: liubj@jlu.edu.c [College of Chemistry, Jilin University, Changchun 130012 (China); Hu Wei [College of Chemistry, Jilin University, Changchun 130012 (China); Kim, Yu Seung [Los Alamos National Laboratory, Electronic and Electrochemical Materials and Devices, Los Alamos, NM 87545 (United States); Zou Haifeng [College of Chemistry, Jilin University, Changchun 130012 (China); Robertson, Gilles P. [Institute for Chemical Process and Environmental Technology, National Research Council, Ottawa, Ontario K1A 0R6 (Canada); Jiang Zhenhua [College of Chemistry, Jilin University, Changchun 130012 (China); Guiver, Michael D. [Institute for Chemical Process and Environmental Technology, National Research Council, Ottawa, Ontario K1A 0R6 (Canada); Department of Energy Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of)

    2010-04-15

    A sulfonated poly(aryl ether ether ketone ketone) (PEEKK) having a well-defined rigid homopolymer-like chemical structure was synthesized from a readily prepared PEEKK by post-sulfonation with concentrated sulfuric acid at room temperature within several hours. The polymer electrolyte membrane (PEM) cast from the resulting polymer exhibited an excellent combination of thermal resistance, oxidative and dimensional stability, low methanol fuel permeability and high proton conductivity. Furthermore, membrane electrode assemblies (MEAs) were successfully fabricated and good direct methanol fuel cell (DMFC) performance was observed. At 2 M MeOH feed, the current density at 0.5 V reached 165 mA/cm, which outperformed our reported similarly structured analogues and MEAs derived from comparative Nafion membranes.

  11. Studies on Synthesis and Structure-Activity Relationship (SAR of Derivatives of a New Natural Product from Marine Fungi as Inhibitors of Influenza Virus Neuraminidase

    Directory of Open Access Journals (Sweden)

    Yongcheng Lin

    2011-10-01

    Full Text Available Based on the natural isoprenyl phenyl ether from a mangrove-derived fungus, 32 analogues were synthesized and evaluated for inhibitory activity against influenza H1N1 neuraminidase. Compound 15 (3-(allyloxy-4-hydroxybenzaldehyde exhibited the most potent inhibitory activity, with IC50 values of 26.96 μM for A/GuangdongSB/01/2009 (H1N1, 27.73 μM for A/Guangdong/03/2009 (H1N1, and 25.13 μM for A/Guangdong/05/2009 (H1N1, respectively, which is stronger than the benzoic acid derivatives (~mM level. These are a new kind of non-nitrogenous aromatic ether Neuraminidase (NA inhibitors. Their structures are simple and the synthesis routes are not complex. The structure-activity relationship (SAR analysis revealed that the aryl aldehyde and unsubstituted hydroxyl were important to NA inhibitory activities. Molecular docking studies were carried out to explain the SAR of the compounds, and provided valuable information for further structure modification.

  12. CoMFA and CoMSIA studies on C-aryl glucoside SGLT2 inhibitors as potential anti-diabetic agents.

    Science.gov (United States)

    Vyas, V K; Bhatt, H G; Patel, P K; Jalu, J; Chintha, C; Gupta, N; Ghate, M

    2013-01-01

    SGLT2 has become a target of therapeutic interest in diabetes research. CoMFA and CoMSIA studies were performed on C-aryl glucoside SGLT2 inhibitors (180 analogues) as potential anti-diabetic agents. Three different alignment strategies were used for the compounds. The best CoMFA and CoMSIA models were obtained by means of Distill rigid body alignment of training and test sets, and found statistically significant with cross-validated coefficients (q²) of 0.602 and 0.618, respectively, and conventional coefficients (r²) of 0.905 and 0.902, respectively. Both models were validated by a test set of 36 compounds giving satisfactory predicted correlation coefficients (r² pred) of 0.622 and 0.584 for CoMFA and CoMSIA models, respectively. A comparison was made with earlier 3D QSAR study on SGLT2 inhibitors, which shows that our 3D QSAR models are better than earlier models to predict good inhibitory activity. CoMFA and CoMSIA models generated in this work can provide useful information to design new compounds and helped in prediction of activity prior to synthesis.

  13. Chemical degradation mechanisms of membranes for alkaline membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Choe, Yoong-Kee [National Institute of Advanced Industrial Science and Technology, Umezono 1-1-1, Tsukuba (Japan); Henson, Neil J.; Kim, Yu Seung [Los Alamos National Laboratory, Los Alamos, NM (United States)

    2015-12-31

    Chemical degradation mechanisms of membranes for alkaline membrane fuel cells have been investigated using density functional theory (DFT). We have elucidated that the aryl-ether moiety of membranes is one of the weakest site against attack of hydroxide ions. The results of DFT calculations for hydroxide initiated aryl-ether cleavage indicated that the aryl-ether cleavage occurred prior to degradation of cationic functional group. Such a weak nature of the aryl-ether group arises from the electron deficiency of the aryl group as well as the low bond dissociation energy. The DFT results suggests that removal of the aryl-ether group in the membrane should enhance the stability of membranes under alkaline conditions. In fact, an ether fee poly(phenylene) membrane exhibits excellent stability against the attack from hydroxide ions.

  14. Simple preparation of new N-aryl-N-(3-indolmethyl acetamides and their spectroscopic analysis

    Directory of Open Access Journals (Sweden)

    José A. Henao

    2009-12-01

    Full Text Available To prepare new indolic molecules and characterize them by spectroscopic methods. Materials and methods: All reagentswere purchased from Aldrich, commercial grade. The purity of the products and the composition of the reaction mixtures were monitoredby thin layer chromatography over Silufol UV254 0.25 mm-thick chromatoplates. Product isolation and purification were performed bycolumn chromatography (SiO2, using ethyl acetate-petroleum ether mixtures as eluents. Results. The synthesis of new N-aryl-N-(3-indolmethyl acetamides based on first step iminization reaction of indol-3-carbaldehyde is accomplished. The structures of the C-3substituted indoles were confirmed by 1H-NMR and 13C-NMR studies supported by inverse-detected 2D NMR experiments and alsothrough monocrystal X-ray diffraction. Conclusions. An efficient, economic, and fast synthetic route was designed to the construction ofthe N-aryl-N-(3-indolmethyl acetamides, structural analogues of some alkaloids.

  15. Degradation of β-Aryl Ether Bonds in Transgenic Plants

    DEFF Research Database (Denmark)

    Mnich, Ewelina

    Lignin is one of the main building blocks of the plant cell wall. It tethers the cell wall by cross-linking with polysaccharides conferring mechanical strength to plants, aiding water transport and providing a mechanical barrier against pathogens. It is generated by the polymerization....... Compared to other plants grass cell walls contain elevated amount of ferulates which play a crucial role in cross-linking of polysaccharides and lignin. In addition ferulates are believed to be nucleation cites for the lignification. The bacterium Sphingomonas paucimobilis SYK6 has developed an enzyme...... of the cell wall. The aim of the study was to alter lignin structure by expression in plants of the enzymes from S. paucimobilis involved in ether bond degradation (LigDFG). Arabidopsis thaliana and Brachypodium distachyon transgenic lines were generated and characterized with respect to lignin structure...

  16. Biology-oriented drug synthesis (BIODS) of 2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethyl aryl ether derivatives, in vitro α-amylase inhibitory activity and in silico studies.

    Science.gov (United States)

    Taha, Muhammad; Imran, Syahrul; Ismail, Nor Hadiani; Selvaraj, Manikandan; Rahim, Fazal; Chigurupati, Sridevi; Ullah, Hayat; Khan, Fahad; Salar, Uzma; Javid, Muhammad Tariq; Vijayabalan, Shantini; Zaman, Khalid; Khan, Khalid Mohammed

    2017-10-01

    A new library of 2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethyl aryl ether derivatives (1-23) were synthesized and characterized by EI-MS and 1 H NMR, and screened for their α-amylase inhibitory activity. Out of twenty-three derivatives, two molecules 19 (IC 50 =0.38±0.82µM) and 23 (IC 50 =1.66±0.14µM), showed excellent activity whereas the remaining compounds, except 10 and 17, showed good to moderate inhibition in the range of IC 50 =1.77-2.98µM when compared with the standard acarbose (IC 50 =1.66±0.1µM). A plausible structure-activity relationship has also been presented. In addition, in silico studies was carried out in order to rationalize the binding interaction of compounds with the active site of enzyme. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. The HSP90 inhibitor 17-AAG potentiates the antileishmanial activity of the ether lipid edelfosine.

    Science.gov (United States)

    Varela-M, Rubén E; Mollinedo-Gajate, Cristina; Muro, Antonio; Mollinedo, Faustino

    2014-03-01

    HSP90 is an abundant protein in Leishmania parasites that plays a major role in the parasite survival under stress conditions. Here we found that the HSP90 inhibitor 17-AAG (≥100nM 17-AAG) induced cell cycle arrest at G0/G1 in Leishmania infantum and Leishmania panamensis promastigotes, and highly potentiated the induction of cell death by an apoptotic-like process mediated by the ether phospholipid edelfosine (5-20μM). These data suggest that the combined treatment of 17-AAG and edelfosine might be a novel and effective approach of combination therapy in the treatment of leishmaniasis. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Evaluation of crystallization kinetics of poly (ether-ketone-ketone and poly (ether-ether-ketone by DSC

    Directory of Open Access Journals (Sweden)

    Gibran da Cunha Vasconcelos

    2010-08-01

    Full Text Available The poly (aryl ether ketones are used as matrices in advanced composites with high performance due to its high thermal stability, excellent environmental performance and superior mechanical properties. Most of the physical, mechanical and thermodynamic properties of semi-crystalline polymers depend on the degree of crystallinity and morphology of the crystalline regions. Thus, a study on the crystallization process promotes a good prediction of how the manufacturing parameters affect the developed structure, and the properties of the final product. The objective of this work was to evaluate the thermoplastics polymers PEKK e PEEK by DSC, aiming to obtain the relationship between kinetics, content, nucleation and geometry of the crystalline phases, according to the parameters of the Avrami and Kissinger models. The analysis of the Avrami exponents obtained for the studied polymers indicates that both showed the formation of crystalline phases with heterogeneous nucleation and growth geometry of the type sticks or discs, depending on the cooling conditions. It was also found that the PEEK has a higher crystallinity than PEKK.

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

    DEFF Research Database (Denmark)

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

    2009-01-01

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

  20. Synthesis of quaternary aryl phosphonium salts: photoredox-mediated phosphine arylation.

    Science.gov (United States)

    Fearnley, A F; An, J; Jackson, M; Lindovska, P; Denton, R M

    2016-04-11

    We report a synthesis method for the construction of quaternary aryl phoshonium salts at ambient temperature. The regiospecific reaction involves the coupling of phosphines with aryl radicals derived from diaryliodonium salts under photoredox conditions.

  1. Metal-free, visible-light-mediated direct C-H arylation of heteroarenes with aryl diazonium salts.

    Science.gov (United States)

    Hari, Durga Prasad; Schroll, Peter; König, Burkhard

    2012-02-15

    Visible light along with 1 mol % eosin Y catalyzes the direct C-H bond arylation of heteroarenes with aryl diazonium salts by a photoredox process. We have investigated the scope of the reaction for several aryl diazonium salts and heteroarenes. The general and easy procedure provides a transition-metal-free alternative for the formation of aryl-heteroaryl bonds.

  2. Effect of p-amino-diphenyl ethers on hepatic microsomal cytochrome P450.

    Science.gov (United States)

    Jiang, Huidi; Xuan, Guida

    2003-09-01

    The present paper aims to investigate whether p-amino-2',4'-dichlorodiphenyl ether and p-amino-4'-methyldiphenyl ether are inhibitors as well as inducers of P450. Mice were given daily intraperitoneal (ip) injections of p-amino-2',4'-dichlorodiphenyl ether (0.25 mmol/kg) or p-amino-4'-methyldiphenyl ether (0.25 mmol/kg) for 4 days and tested at 24 h and 48 h after the last dose injection. The results showed the mice pentobarbital sleeping time was shorter and the P450 content of hepatic microsome increased significantly in the group pretreated with p-amino-4'-methyldiphenyl ether when compared with the control group, while in mice pretreated with p-amino-2',4'-dichlorodiphenyl ether the hepatic microsome P450 content increased but the pentobarbital sleeping time was extended in clear contrast to the control group. The sleeping time of the phenobarbital group (80 mg/kg daily ip injection for 4 days) was shortened at 24 h after the last injection with increased P450 content of hepatic microsome, but it showed no difference at 48 h. The zoxazolamine-paralysis times of mice treated with p-amino-2',4'-dichlorodiphenyl ether were longer than those of the control mice, while the same dose of zoxazolamine did not lead to paralysis in mice pretreated with BNF. p-Amino-2',4'-dichlorodiphenyl ether and p-amino-4'-methyldiphenyl ether inhibited the activity of 7-ethoxyresorufin O-deethylase from rat hepatic microsome induced by BNF in vitro by 70.0% and 50.1% respectively. These results suggest that p-amino-2',4'-dichlorodiphenyl ether and p-amino-4'-methyldiphenyl ether are inhibitors as well as inducers of P450.

  3. A direct method to visualise the aryl acylamidase activity on cholinesterases in polyacrylamide gels

    Directory of Open Access Journals (Sweden)

    Boopathy Rathanam

    2000-12-01

    Full Text Available Abstract Background In vertebrates, two types of cholinesterases exist, acetylcholinesterase and butyrylcholinesterase. The function of acetylcholinesterase is to hydrolyse acetylcholine, thereby terminating the neurotransmission at cholinergic synapse, while the precise physiological function of butyrylcholinesterase has not been identified. The presence of cholinesterases in tissues that are not cholinergically innervated indicate that cholinesterases may have functions unrelated to neurotransmission. Furthermore, cholinesterases display a genuine aryl acylamidase activity apart from their predominant acylcholine hydrolase activity. The physiological significance of this aryl acylamidase activity is also not known. The study on the aryl acylamidase has been, in part hampered by the lack of a specific method to visualise this activity. We have developed a method to visualise the aryl acylamidase activity on cholinesterase in polyacrylamide gels. Results The o-nitroaniline liberated from o-nitroacetanilide by the action of aryl acylamidase activity on cholinesterases, in the presence of nitrous acid formed a diazonium compound. This compound gave an azo dye complex with N-(1-napthyl-ethylenediamine, which appeared as purple bands in polyacrylamide gels. Treating the stained gels with trichloroacetic acid followed by Tris-HCl buffer helped in fixation of the stain in the gels. By using specific inhibitors for acetylcholinesterase and butyrylcholinesterase, respectively, differential staining for the aryl acylamidase activities on butyrylcholinesterase and acetylcholinesterase in a sample containing both these enzymes has been demonstrated. A linear relationship between the intensity of colour developed and activity of the enzyme was obtained. Conclusions A novel method to visualise the aryl acylamidase activity on cholinesterases in polyacrylamide gels has been developed.

  4. The Guareschi Pyridine Scaffold as a Valuable Platform for the Identification of Selective PI3K Inhibitors

    Directory of Open Access Journals (Sweden)

    Ubaldina Galli

    2015-09-01

    Full Text Available A novel series of 4-aryl-3-cyano-2-(3-hydroxyphenyl-6-morpholino-pyridines have been designed as potential phosphatidylinositol-3-kinase (PI3K inhibitors. The compounds have been synthesized using the Guareschi reaction to prepare the key 4-aryl-3-cyano-2,6-dihydroxypyridine intermediate. A different selectivity according to the nature of the aryl group has been observed. Compound 9b is a selective inhibitor against the PI3Kα isoform, maintaining a good inhibitory activity. Docking studies were also performed in order to rationalize its profile of selectivity.

  5. The Guareschi Pyridine Scaffold as a Valuable Platform for the Identification of Selective PI3K Inhibitors.

    Science.gov (United States)

    Galli, Ubaldina; Ciraolo, Elisa; Massarotti, Alberto; Margaria, Jean Piero; Sorba, Giovanni; Hirsch, Emilio; Tron, Gian Cesare

    2015-09-18

    A novel series of 4-aryl-3-cyano-2-(3-hydroxyphenyl)-6-morpholino-pyridines have been designed as potential phosphatidylinositol-3-kinase (PI3K) inhibitors. The compounds have been synthesized using the Guareschi reaction to prepare the key 4-aryl-3-cyano-2,6-dihydroxypyridine intermediate. A different selectivity according to the nature of the aryl group has been observed. Compound 9b is a selective inhibitor against the PI3Kα isoform, maintaining a good inhibitory activity. Docking studies were also performed in order to rationalize its profile of selectivity.

  6. Tandem trifluoromethylthiolation/aryl migration of aryl alkynoates to trifluoromethylthiolated alkenes.

    Science.gov (United States)

    Li, Huan; Liu, Shuai; Huang, Yangen; Xu, Xiu-Hua; Qing, Feng-Ling

    2017-09-12

    A trifluoromethylthiolation initiated aryl migration of aryl alkynoates was disclosed. This protocol employs AgSCF 3 as the SCF 3 source and MeCN as both the solvent and the hydrogen source. This provides a new access to trifluoromethylthiolated alkenes from readily available substrates and reagents.

  7. Multimetallic catalysed cross-coupling of aryl bromides with aryl triflates

    Science.gov (United States)

    Ackerman, Laura K. G.; Lovell, Matthew M.; Weix, Daniel J.

    2015-08-01

    The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts--multimetallic catalysis--can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts--(bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium--enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this

  8. Studies on non-steroidal inhibitors of aromatase enzyme; 4-(aryl/heteroaryl)-2-(pyrimidin-2-yl)thiazole derivatives.

    Science.gov (United States)

    Sahin, Zafer; Ertas, Merve; Berk, Barkın; Biltekin, Sevde Nur; Yurttas, Leyla; Demirayak, Seref

    2018-05-01

    Steroidal and non-steroidal aromatase inhibitors target the suppression of estrogen biosynthesis in the treatment of breast cancer. Researchers have increasingly focused on developing non-steroidal derivatives for their potential clinical use avoiding steroidal side-effects. Non-steroidal derivatives generally have planar aromatic structures attached to the azole ring system. One part of this ring system comprises functional groups that inhibit aromatization through the coordination of the haem group of the aromatase enzyme. Replacement of the triazole ring system and development of aromatic/cyclic structures of the side chain can increase selectivity over aromatase enzyme inhibition. In this study, 4-(aryl/heteroaryl)-2-(pyrimidin-2-yl)thiazole derivatives were synthesized and physical analyses and structural determination studies were performed. The IC 50 values were determined by a fluorescence-based aromatase inhibition assay and compound 1 (4-(2-hydroxyphenyl)-2-(pyrimidine-2-yl)thiazole) were found potent inhibitor of enzyme (IC 50 :0.42 nM). Then, their antiproliferative activity over MCF-7 and HEK-293 cell lines was evaluated using a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Compounds 1, 7, 8, 13, 15, 18, 21 were active against MCF-7 breast cancer cells. Lastly, a series of docking experiments were undertaken to analyze the crystal structure of human placental aromatase and identify the possible interactions between the most active structure and the active site. Copyright © 2018 Elsevier Ltd. All rights reserved.

  9. Inert and stable erbium(III)-cored complexes based on metalloporphyrins bearing aryl-ether dendron for optical amplification: synthesis and emission enhancement

    International Nuclear Information System (INIS)

    Oh, Jae Buem; Kim, Yong Hee; Nah, Min Kook; Kim, Hwan Kyu

    2005-01-01

    We have developed novel inert and stable erbium (Er)(III)-cored complexes based on metalloporphyrins for optical amplification. The functionalized metalloporphyrin ligands have been designed and synthesized to provide enough coordination sites for the formation of inert and stable 9-coordinated Er(III)-cored complexes. Er 3+ ions were encapsulated by the metalloporphyrin ligands, such as Zn(II)- and Pt(II)-porphyrins. The near-infrared (IR) emission intensity of Er 3+ ion is much stronger in the Er(III)-cored complex based on Pt(II)-porphyrin than Er(III)-cored complex based on Zn(II)-porphyrin. Furthermore, we have incorporated a G2-aryl-ether functionalized dendron into the Er(III)-cored complex, yielding an Er(III)-cored dendrimer complex bearing the Pt(II)-porphyrin. The Er(III)-cored dendrimer complex shows the stronger near-IR emission intensity than the corresponding complex based on Pt(II)-porphyrin by seven times in solid state. The lifetimes of the emission band of Pt(II)-porphyrin ligands in the visible region were found to be 30 and 40 μs for the Er(III)-cored complex and the Er(III)-cored dendrimer complex based on Pt(II)-porphyrin in deoxygenated THF solution samples, respectively. Also, in both cases, the sensitized luminescence intensity is increased in deoxygenated solution. Therefore, it indicates that the energy transfer from the metalloporphyrins to Er 3+ ions takes places through the triplet state. In this paper, the synthesis and photophysical properties of novel Er(III)-cored complexes based on metalloporphyrins and Er(III)-cored dendrimer complex based on metalloporphyrin will be discussed

  10. Docking of oxalyl aryl amino benzoic acid derivatives into PTP1B

    Science.gov (United States)

    Verma, Neelam; Mittal, Minakshi; Verma, Raman kumar

    2008-01-01

    Protein Tyrosine Phosphatases (PTPs) that function as negative regulators of the insulin signaling cascade have been identified as novel targets for the therapeutic enhancement of insulin action in insulin resistant disease states. Reducing Protein Tyrosine Phosphatase1B (PTP1B) abundance not only enhances insulin sensitivity and improves glucose metabolism but also protects against obesity induced by high fat feeding. PTP1B inhibitors such as Formylchromone derivatives, 1, 2-Naphthoquinone derivatives and Oxalyl aryl amino benzoic derivatives may eventually find an important clinical role as insulin sensitizers in the management of Type-II Diabetes and metabolic syndrome. We have carried out docking of modified oxalyl aryl amino benzoic acid derivatives into three dimensional structure of PTP1B using BioMed CAChe 6.1. These compounds exhibit good selectivity for PTP1B over most of phosphatases in selectivity panel such as SHP-2, LAR, CD45 and TCPTP found in literature. This series of compounds identified the amino acid residues such as Gly220 and Arg221 are important for achieving specificity via H-bonding interactions. Lipophilic side chain of methionine in modified oxalyl aryl amino benzoic acid derivative [1b (a2, b2, c1, d)] lies in closer vicinity of hydrophobic region of protein consisted of Meth258 and Phe52 in comparison to active ligand. Docking Score in [1b (a2, b2, c1, d)] is -131.740Kcal/mol much better than active ligand score -98.584Kcal/mol. This information can be exploited to design PTP1B specific inhibitors. PMID:19238234

  11. Heteroaryl ethers by oxidative palladium catalysis of pyridotriazol-1-yloxy pyrimidines with arylboronic acids.

    Science.gov (United States)

    Bardhan, Sujata; Wacharasindhu, Sumrit; Wan, Zhao-Kui; Mansour, Tarek S

    2009-06-18

    The oxidative palladium-catalyzed cross-coupling of pyrimidines containing pyridotriazol-1-yloxy (OPt) as either a urea or an amide functional group with arylboronic acids in the presence of Cs(2)CO(3) in DME containing 0.6-1.0% H(2)O is described for the preparation of heteroaryl ethers. The bromo substitution in the case of 3-(5-bromo-pyrimidin-2-yloxy)-3H-[1,2,3]triazolo[4,5-b]pyridine 1 could serve as a handle for further elaborations such as Suzuki coupling for attaching varied aryl groups.

  12. Indolyl aryl sulfones as HIV-1 non-nucleoside reverse transcriptase inhibitors: role of two halogen atoms at the indole ring in developing new analogues with improved antiviral activity.

    Science.gov (United States)

    Regina, Giuseppe La; Coluccia, Antonio; Piscitelli, Francesco; Bergamini, Alberto; Sinistro, Anna; Cavazza, Antonella; Maga, Giovanni; Samuele, Alberta; Zanoli, Samantha; Novellino, Ettore; Artico, Marino; Silvestri, Romano

    2007-10-04

    Indolyl aryl sulfones bearing the 4,5-difluoro (10) or 5-chloro-4-fluoro (16) substitution pattern at the indole ring were potent inhibitors of HIV-1 WT and the NNRTI-resistant strains Y181C and K103N-Y181C. These compounds were highly effective against the 112 and the AB1 strains in lymphocytes and inhibited at nanomolar concentration the multiplication of the IIIBBa-L strain in macrophages. Compound 16 was exceptionally potent against RT WT and RTs carrying the K103N, Y181I, and L100I mutations.

  13. 5-Bromo-2-aryl benzimidazole derivatives as non-cytotoxic potential dual inhibitors of α-glucosidase and urease enzymes.

    Science.gov (United States)

    Arshad, Tanzila; Khan, Khalid Mohammed; Rasool, Najma; Salar, Uzma; Hussain, Shafqat; Asghar, Humna; Ashraf, Mohammed; Wadood, Abdul; Riaz, Muhammad; Perveen, Shahnaz; Taha, Muhammad; Ismail, Nor Hadiani

    2017-06-01

    On the basis of previous report on promising α-glucosidase inhibitory activity of 5-bromo-2-aryl benzimidazole derivatives, these derivatives were further screened for urease inhibitory and cytotoxicity activity in order to get more potent and non-cytotoxic potential dual inhibitor for the patients suffering from diabetes as well as peptic ulcer. In this study, all compounds showed varying degree of potency in the range of (IC 50 =8.15±0.03-354.67±0.19μM) as compared to standard thiourea (IC 50 =21.25±0.15μM). It is worth mentioning that derivatives 7 (IC 50 =12.07±0.05μM), 8 (IC 50 =10.57±0.12μM), 11 (IC 50 =13.76±0.02μM), 14 (IC 50 =15.70±0.12μM) and 22 (IC 50 =8.15±0.03μM) were found to be more potent inhibitors than standard. All compounds were also evaluated for cytotoxicity towards 3T3 mouse fibroblast cell line and found to be completely non-toxic. Previously benzimidazole 1-25 were also showed α-glucosidase inhibitory potential. In silico studies were performed on the lead molecules i.e.2, 7, 8, 11, 14, and 22, in order to rationalize the binding interaction of compounds with the active site of urease enzyme. Copyright © 2017 Elsevier Inc. All rights reserved.

  14. The photocatalyzed Meerwein arylation: classic reaction of aryl diazonium salts in a new light.

    Science.gov (United States)

    Hari, Durga Prasad; König, Burkhard

    2013-04-26

    The use of diazonium salts for aryl radical generation and C-H arylation processes has been known since 1896 when Pschorr first used the reaction for intramolecular cyclizations. Meerwein developed it further in the early 1900s into a general arylation method. However, this reaction could not compete with the transition-metal-mediated formation of C(sp(2))-C(sp(2)) bonds. The replacement of the copper catalyst with iron and titanium compounds improved the situation, but the use of photocatalysis to induce the one-electron reduction and activation of the diazonium salts is even more advantageous. The first photocatalyzed Pschorr cyclization was published in 1984, and just last year a series of papers described applications of photocatalytic Meerwein arylations leading to aryl-alkene coupling products. In this Minireview we summarize the origins of this reaction and its scope and applications. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Direct Synthesis of 5-Aryl Barbituric Acids by Rhodium(II)-Catalyzed Reactions of Arenes with Diazo Compounds.

    Science.gov (United States)

    Best, Daniel; Burns, David J; Lam, Hon Wai

    2015-06-15

    A commercially available rhodium(II) complex catalyzes the direct arylation of 5-diazobarbituric acids with arenes, allowing straightforward access to 5-aryl barbituric acids. Free N-H groups are tolerated on the barbituric acid, with no complications arising from N-H insertion processes. This method was applied to the concise synthesis of a potent matrix metalloproteinase (MMP) inhibitor. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  16. Green Hydroselenation of Aryl Alkynes: Divinyl Selenides as a Precursor of Resveratrol

    Directory of Open Access Journals (Sweden)

    Gelson Perin

    2017-02-01

    Full Text Available A simple and efficient protocol to prepare divinyl selenides has been developed by the regio- and stereoselective addition of sodium selenide species to aryl alkynes. The nucleophilic species was generates in situ, from the reaction of elemental selenium with NaBH4, utilizing PEG-400 as the solvent. Several divinyl selenides were obtained in moderate to excellent yields with selectivity for the (Z,Z-isomer by a one-step procedure that was carried out at 60 °C in short reaction times. The methodology was extended to tellurium, giving the desired divinyl tellurides in good yields. Furthermore, the Fe-catalyzed cross-coupling reaction of bis(3,5-dimethoxystyryl selenide 3f with (4-methoxyphenylmagnesium bromide 5 afforded resveratrol trimethyl ether 6 in 57% yield.

  17. Green Hydroselenation of Aryl Alkynes: Divinyl Selenides as a Precursor of Resveratrol.

    Science.gov (United States)

    Perin, Gelson; Barcellos, Angelita M; Luz, Eduardo Q; Borges, Elton L; Jacob, Raquel G; Lenardão, Eder J; Sancineto, Luca; Santi, Claudio

    2017-02-20

    A simple and efficient protocol to prepare divinyl selenides has been developed by the regio- and stereoselective addition of sodium selenide species to aryl alkynes. The nucleophilic species was generates in situ , from the reaction of elemental selenium with NaBH₄, utilizing PEG-400 as the solvent. Several divinyl selenides were obtained in moderate to excellent yields with selectivity for the ( Z , Z )-isomer by a one-step procedure that was carried out at 60 °C in short reaction times. The methodology was extended to tellurium, giving the desired divinyl tellurides in good yields. Furthermore, the Fe-catalyzed cross-coupling reaction of bis(3,5-dimethoxystyryl) selenide 3f with (4-methoxyphenyl)magnesium bromide 5 afforded resveratrol trimethyl ether 6 in 57% yield.

  18. BDE-99, but not BDE-47, is a transient aryl hydrocarbon receptor agonist in zebrafish liver cells

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jie; Zhu, Jinyong; Chan, King Ming, E-mail: kingchan@cuhk.edu.hk

    2016-08-15

    Polybrominated diphenyl ethers (PBDEs) are endocrine-disrupting chemicals that affect the environment and the health of humans and wildlife. In this study, the zebrafish liver (ZFL) cell line was used in vitro to investigate two major PBDE contaminants: 2, 2′, 4, 4′, 5-pentabromodiphenyl ether (BDE-99) and 2, 2′, 4, 4′-tetrabromodiphenyl ether (BDE-47). BDE-99 was found to significantly induce cytochrome P450 (CYP1A), uridine diphosphate glucuronosyl transferase 1 family a, b (ugt1ab), 7-ethoxyresorufin-O-deethylase activity and an aryl hydrocarbon receptor (Ahr) dependent xenobiotic response element luciferase reporter system, confirming the Ahr-mediated activation of CYP1A by BDE-99. The time-course effect indicated that the role of BDE-99 in Ahr-mediated signaling is likely to be transient and highly dependent on the ability of BDE-99 to induce CYP1A and ugt1ab, and presumably its metabolism. BDE-99 also exhibited a significant dose-response effect on a developed zebrafish pregnane X receptor luciferase reporter gene system. However, the other abundant contaminant under study, BDE-47, did not exhibit the above effects. Together, these results indicated that the molecular mechanism of PBDEs induced in ZFL cells is a chemically specific process that differs between members of the PBDE family. CYP1A induction derived by BDE-99 warrants further risk assessment as the humans, wildlife and environment are exposed to a complex mixture including dioxin-like compounds and carcinogenic compounds. - Highlights: • BDE-99 is an aryl hydrocarbon receptor (Ahr) agonist in zebrafish liver cell-line ZFL. • BDE-99 induced EROD activity, CYP1A and ugt1ab gene expression, in ZFL. • BDE-99 induced the pregnane X receptor (Pxr) luciferase reporter gene system in ZFL. • BDE-47 did not show any effects in ZFL to induce CYP1A, ugt1ab, and EROD. • BDE-47 and -99 showed no induction of Rxr and Pxr pathways in ZFL cells.

  19. Nickel-Catalyzed Alkoxy-Alkyl Interconversion with Alkylborane Reagents through C−O Bond Activation of Aryl and Enol Ethers

    KAUST Repository

    Guo, Lin

    2016-11-07

    A nickel-catalyzed alkylation of polycyclic aromatic methyl ethers as well as methyl enol ethers with B-alkyl 9-BBN and trialkylborane reagents that involves the cleavage of stable C(sp2)−OMe bonds is described. The transformation has a wide substrate scope and good chemoselectivity profile while proceeding under mild reaction conditions; it provides a versatile way to form C(sp2)−C(sp3) bonds that does not suffer from β-hydride elimination. Furthermore, a selective and sequential alkylation process by cleavage of inert C−O bonds is presented to demonstrate the advantage of this method.

  20. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    DEFF Research Database (Denmark)

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.

    2009-01-01

    A mild, racemization-free, palladium-Catalyzed alpha-arylation of tetramic acids (2,4-pyrrolidinediones) has been developed. Various amino acid-derived tetramic acids were cleanly arylated by treatment with 2 mol % of Pd(OAc)(2), 4 mol % of a sterically demanding biaryl phosphine, 2.3 equiv of K2CO...... no effect on their reactivity: both electron-rich and electron-poor aryl chlorides and bromides or triflates led to good yields. Ortho-substituted aryl halides and heteroaryl halides, however, did not undergo the title reaction....

  1. Aminoarenethiolato-copper(I) as (pre-)catalyst for the synthesis of diaryl ethers from aryl bromides and sequential C-O/C-S and C-N/C-S cross coupling reactions

    NARCIS (Netherlands)

    Sperotto, Elena; Klink, Gerard P.M. van; Vries, Johannes G. de; Koten, Gerard van

    2010-01-01

    A small library of 2-aminoarenethiolato-copper(I) (CuSAr) complexes was tested as (pre-)catalysts in the arylation reaction of phenols with aryl bromides. These copper(I) (pre-)catalysts are thermally stable, soluble in common organic solvents, and allow reactions of 6 h at 160 °C with low catalyst

  2. Electrochemical Grafting of Graphene Nano Platelets with Aryl Diazonium Salts.

    Science.gov (United States)

    Qiu, Zhipeng; Yu, Jun; Yan, Peng; Wang, Zhijie; Wan, Qijin; Yang, Nianjun

    2016-10-26

    To vary interfacial properties, electrochemical grafting of graphene nano platelets (GNP) with 3,5-dichlorophenyl diazonium tetrafluoroborate (aryl-Cl) and 4-nitrobenzene diazonium tetrafluoroborate (aryl-NO 2 ) was realized in a potentiodynamic mode. The covalently bonded aryl layers on GNP were characterized using atomic force microscopy and X-ray photoelectron spectroscopy. Electrochemical conversion of aryl-NO 2 into aryl-NH 2 was conducted. The voltammetric and impedance behavior of negatively and positively charged redox probes (Fe(CN) 6 3-/4- and Ru(NH 3 ) 6 2+/3+ ) on three kinds of aryl layers grafted on GNP reveal that their interfacial properties are determined by the charge states of redox probes and reactive terminal groups (-Cl, -NO 2 , -NH 2 ) in aryl layers. On aryl-Cl and aryl-NH 2 garted GNP, selective and sensitive monitoring of positively charged lead ions as well as negatively charged nitrite and sulfite ions was achieved, respectively. Such a grafting procedure is thus a perfect way to design and control interfacial properties of graphene.

  3. Structure-based design, synthesis, and biological evaluation of novel pyrrolyl aryl sulfones: HIV-1 non-nucleoside reverse transcriptase inhibitors active at nanomolar concentrations.

    Science.gov (United States)

    Artico, M; Silvestri, R; Pagnozzi, E; Bruno, B; Novellino, E; Greco, G; Massa, S; Ettorre, A; Loi, A G; Scintu, F; La Colla, P

    2000-05-04

    Pyrrolyl aryl sulfones (PASs) have been recently reported as a new class of human immunodeficiency virus type 1 (HIV-1) reverse transcriptase (RT) inhibitors acting at the non-nucleoside binding site of this enzyme (Artico, M.; et al. J. Med. Chem. 1996, 39, 522-530). Compound 3, the most potent inhibitor within the series (EC(50) = 0.14 microM, IC(50) = 0.4 microM, and SI > 1429), was then selected as a lead compound for a synthetic project based on molecular modeling studies. Using the three-dimensional structure of RT cocrystallized with the alpha-APA derivative R95845, we derived a model of the RT/3 complex by taking into account previously developed structure-activity relationships. Inspection of this model and docking calculations on virtual compounds prompted the design of novel PAS derivatives and related analogues. Our computational approach proved to be effective in making qualitative predictions, that is in discriminating active versus inactive compounds. Among the compounds synthesized and tested, 20 was the most active one, with EC(50) = 0.045 microM, IC(50) = 0.05 microM, and SI = 5333. Compared with the lead 3, these values represent a 3- and 8-fold improvement in the cell-based and enzyme assays, respectively, together with the highest selectivity achieved so far in the PAS series.

  4. Biological processes for the production of aryl sulfates

    DEFF Research Database (Denmark)

    2016-01-01

    The present invention generally relates to the field of biotechnology as it applies to the production of aryl sulfates using polypeptides or recombinant cells comprising said polypeptides. More particularly, the present invention pertains to polypeptides having aryl sulfotransferase activity......, recombinant host cells expressing same and processes for the production of aryl sulfates employing these polypeptides or recombinant host cells....

  5. High Potency of Indolyl Aryl Sulfone Nonnucleoside Inhibitors towards Drug-Resistant Human Immunodeficiency Virus Type 1 Reverse Transcriptase Mutants Is Due to Selective Targeting of Different Mechanistic Forms of the Enzyme

    Science.gov (United States)

    Cancio, Reynel; Silvestri, Romano; Ragno, Rino; Artico, Marino; De Martino, Gabriella; La Regina, Giuseppe; Crespan, Emmanuele; Zanoli, Samantha; Hübscher, Ulrich; Spadari, Silvio; Maga, Giovanni

    2005-01-01

    Indolyl aryl sulfone (IAS) nonnucleoside inhibitors have been shown to potently inhibit the growth of wild-type and drug-resistant human immunodeficiency virus type 1 (HIV-1), but their exact mechanism of action has not been elucidated yet. Here, we describe the mechanism of inhibition of HIV-1 reverse transcriptase (RT) by selected IAS derivatives. Our results showed that, depending on the substitutions introduced in the IAS common pharmacophore, these compounds can be made selective for different enzyme-substrate complexes. Moreover, we showed that the molecular basis for this selectivity was a different association rate of the drug to a particular enzymatic form along the reaction pathway. By comparing the activities of the different compounds against wild-type RT and the nonnucleoside reverse transcriptase inhibitor-resistant mutant Lys103Asn, it was possible to hypothesize, on the basis of their mechanism of action, a rationale for the design of drugs which could overcome the steric barrier imposed by the Lys103Asn mutation. PMID:16251294

  6. Comparison of Properties among Dendritic and Hyperbranched Poly(ether ether ketones and Linear Poly(ether ketones

    Directory of Open Access Journals (Sweden)

    Atsushi Morikawa

    2016-02-01

    Full Text Available Poly(ether ether ketone dendrimers and hyperbranched polymers were prepared from 3,5-dimethoxy-4′-(4-fluorobenzoyldiphenyl ether and 3,5-dihydroxy-4′-(4-fluorobenzoyldiphenyl ether through aromatic nucleophilic substitution reactions. 1-(tert-Butyldimethylsiloxy-3,5-bis(4-fluorobenzoylbenzene was polycondensed with bisphenols, followed by cleavage of the protective group to form linear poly(ether ketones having the same hydroxyl groups in the side chains as the chain ends of the dendrimer and hyperbranched polymers. Their properties, such as solubilities, reduced viscosities, and thermal properties, were compared with one another. Similar comparisons were also carried out among the corresponding methoxy group polymers, and the size of the molecules was shown to affect the properties.

  7. Switch in Site of Inhibition: A Strategy for Structure-Based Discovery of Human Topoisomerase IIα Catalytic Inhibitors

    Science.gov (United States)

    2015-01-01

    A study of structure-based modulation of known ligands of hTopoIIα, an important enzyme involved in DNA processes, coupled with synthesis and in vitro assays led to the establishment of a strategy of rational switch in mode of inhibition of the enzyme’s catalytic cycle. 6-Arylated derivatives of known imidazopyridine ligands were found to be selective inhibitors of hTopoIIα, while not showing TopoI inhibition and DNA binding. Interestingly, while the parent imidazopyridines acted as ATP-competitive inhibitors, arylated derivatives inhibited DNA cleavage similar to merbarone, indicating a switch in mode of inhibition from ATP-hydrolysis to the DNA-cleavage stage of catalytic cycle of the enzyme. The 6-aryl-imidazopyridines were relatively more cytotoxic than etoposide in cancer cells and less toxic to normal cells. Such unprecedented strategy will encourage research on “choice-based change” in target-specific mode of action for rapid drug discovery. PMID:25941559

  8. Discovery and Development of the Aryl O-Sulfamate Pharmacophore for Oncology and Women's Health.

    Science.gov (United States)

    Thomas, Mark P; Potter, Barry V L

    2015-10-08

    In 1994, following work from this laboratory, it was reported that estrone-3-O-sulfamate irreversibly inhibits a new potential hormone-dependent cancer target steroid sulfatase (STS). Subsequent drug discovery projects were initiated to develop the core aryl O-sulfamate pharmacophore that, over some 20 years, have led to steroidal and nonsteroidal drugs in numerous preclinical and clinical trials, with promising results in oncology and women's health, including endometriosis. Drugs have been designed to inhibit STS, e.g., Irosustat, as innovative dual-targeting aromatase-steroid sulfatase inhibitors (DASIs) and as multitargeting agents for hormone-independent tumors, such as the steroidal STX140 and nonsteroidal counterparts, acting inter alia through microtubule disruption. The aryl sulfamate pharmacophore is highly versatile, operating via three distinct mechanisms of action, and imbues attractive pharmaceutical properties. This Perspective gives a personal view of the work leading both to the therapeutic concepts and these drugs, their current status, and how they might develop in the future.

  9. Numerical analysis of spray characteristics of dimethyl ether and diethyl ether fuel

    International Nuclear Information System (INIS)

    Mohan, Balaji; Yang, Wenming; Yu, Wenbin; Tay, Kun Lin

    2017-01-01

    Highlights: • Thermo-physical properties of liquid DME and DEE are reported. • Ether fuels tend to cavitate higher compared to that of diesel fuel. • Spray tip penetration and SMD are found to be lesser for ether fuels. • Ether fuels shows excellent atomization behavior. - Abstract: In this work, the spray characteristics of ether fuels such as dimethyl ether (DME) and diethyl ether (DEE) have been numerically investigated using KIVA-4 CFD code. A new hybrid spray model developed by coupling the standard KHRT model to cavitation sub model was used. The detailed thermo-physical properties of ether fuels have been predicted and validated with experimental results available from literature. The cavitation inception inside the injector nozzle hole has been studied for ether fuels in comparison with diesel fuel. It was found that ether fuels cavitates higher compared to that of conventional diesel fuel because of its low viscosity. The spray tip penetration of diesel fuel was longer than that of ether fuels due to high viscosity and density of diesel fuel. Ether fuels characterized by low Ohnesorge number and high Reynolds number showed better atomization behavior compared to that of the diesel fuel.

  10. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides

    Science.gov (United States)

    Strieter, Eric R.; Bhayana, Brijesh; Buchwald, Stephen L.

    2009-01-01

    The copper-catalyzed N-arylation of amides, i.e., the Goldberg reaction, is an efficient method for the construction of products relevant to both industry and academic settings. Herein, we present mechanistic details concerning the catalytic and stoichiometric N-arylation of amides. In the context of the catalytic reaction, our findings reveal the importance of chelating diamine ligands in controlling the concentration of the active catalytic species. The consistency between the catalytic and stoichiometric results suggest that the activation of aryl halides occurs through a 1,2-diamine-ligated copper(I) amidate complex. Kinetic studies on the stoichiometric N-arylation of aryl iodides using 1,2-diamine ligated Cu(I) amidates also provide insights into the mechanism of aryl halide activation. PMID:19072233

  11. Practical synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides via conventional and decarboxylative copper-free Sonogashira coupling reactions

    Directory of Open Access Journals (Sweden)

    Andrea Caporale

    2014-02-01

    Full Text Available Two efficient protocols for the palladium-catalyzed synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides in the absence of copper were developed. A simple catalytic system consisting of Pd(OAc2 and P(p-tol3 using DBU as the base and THF as the solvent was found to be highly effective for the coupling reaction of 2-methyl-3-butyn-2-ol (4 with a wide range of aryl bromides in good to excellent yields. Analogously, the synthesis of aryl-2-methyl-3-butyn-2-ols was performed also through the decarboxylative coupling reaction of 4-hydroxy-4-methyl-2-pentynoic acid with aryl bromides, using a catalyst containing Pd(OAc2 in combination with SPhos or XPhos in the presence of tetra-n-butylammonium fluoride (TBAF as the base and THF as the solvent. Therefore, new efficient approaches to the synthesis of terminal acetylenes from widely available aryl bromides rather than expensive iodides and using 4 or propiolic acid rather than TMS-acetylene as inexpensive alkyne sources are described.

  12. The hydrolysis of geminal ethers: a kinetic appraisal of orthoesters and ketals

    Directory of Open Access Journals (Sweden)

    Sonia L. Repetto

    2016-07-01

    Full Text Available A novel approach to protecting jet fuel against the effects of water contamination is predicated upon the coupling of the rapid hydrolysis reactions of lipophilic cyclic geminal ethers, with the concomitant production of a hydrophilic acyclic hydroxyester with de-icing properties (Fuel Dehydrating Icing Inhibitors - FDII. To this end, a kinetic appraisal of the hydrolysis reactions of representative geminal ethers was undertaken using a convenient surrogate for the fuel–water interface (D2O/CD3CN 1:4. We present here a library of acyclic and five/six-membered cyclic geminal ethers arranged according to their hydroxonium catalytic coefficients for hydrolysis, providing for the first time a framework for the development of FDII. A combination of 1H NMR, labelling and computational studies was used to assess the effects that may govern the observed relative rates of hydrolyses.

  13. Evaluation of atmospheric solid analysis probe ionization coupled to ion mobility mass spectrometry for characterization of poly(ether ether ketone) polymers

    Energy Technology Data Exchange (ETDEWEB)

    Cossoul, Emilie; Hubert-Roux, Marie; Sebban, Muriel [Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex (France); Churlaud, Florence [Arkema, Centre d’Etude de Recherche et Développement, 27470 Serquigny (France); Oulyadi, Hassan [Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex (France); Afonso, Carlos, E-mail: carlos.afonso@univ-rouen.fr [Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex (France)

    2015-01-26

    Highlights: • Solvent free approach. • Production of intact small oligomers of PEEK with ASAP ionization. • Comparison of the MS/MS spectra from M{sup +}· and [M + H]{sup +} precursor ions. • Identification of end-groups using tandem mass spectrometry. - Abstract: Recently, the interest of the coupling between atmospheric solid analysis probe (ASAP) and ion mobility–mass spectrometry has been revealed in the field of polymers. This method associates a direct ionization technique with a bi-dimensional separation method. Poly(ether ether ketones) (PEEK) belong to the family of the poly(aryl ether ketones) (PAEK) which are high performance aromatic polymers usually used in aerospace, electronics and nuclear industries. PEEK are important commercial thermoplastics with excellent chemical resistance and good mechanical properties. Because of their low solubility, few structural characterization studies of PEEK have been reported. In mass spectrometry, only MALDI-TOF analyses for polymer synthesis monitoring have been described with the use of strong acids such as sulfuric acid. This work demonstrates that ASAP is particularly efficient for analysis of PEEK in a solvent free approach with the production of intact small oligomers (n ≤ 2). Five types of PEEK oligomers with different end-groups were evidenced. With MALDI-TOF, the same end-groups with almost the same relative abundance were obtained which support the hypothesis that the oligomers detected in ASAP are intact small oligomers and not fragments or pyrolysis products. This is particularly interesting as generally the ASAP analysis of polymers yields pyrolysis products with the loss of end-group information. The end-groups assignments have been confirmed by tandem mass spectrometry (MS/MS) experiments on the M{sup +}· molecular ions, which allowed highlighting some specific neutral or radical losses as well as two diagnostic product ions. Thus, ASAP-IM/MS/MS proves to be a fast and efficient

  14. Penta- and octa-bromodiphenyl ethers promote proinflammatory protein expression in human bronchial epithelial cells in vitro.

    Science.gov (United States)

    Koike, Eiko; Yanagisawa, Rie; Takigami, Hidetaka; Takano, Hirohisa

    2014-03-01

    Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants in consumer products. Humans can be exposed to PBDEs mainly through the inhalation of air or dust. Thus, PBDEs can affect respiratory and immune systems. In the present study, we investigated whether PBDEs stimulate bronchial epithelial cells. We examined commercial penta-BDE (DE-71), octa-BDE (DE-79), and deca-BDE (DE-83R). Human bronchial epithelial cells (BEAS-2B) were exposed to each PBDE for 24h. Subsequently, the expression of intercellular adhesion molecule-1 (ICAM-1) and proinflammatory cytokines were investigated. DE-71 and DE-79, but not DE-83R, significantly increased the expression of ICAM-1, interleukin-6 (IL-6), and IL-8 in BEAS-2B. Because these remarkable effects were observed with DE-71, we further investigated the underlying intracellular mechanisms. DE-71 promoted epidermal growth factor receptor (EGFR) phosphorylation. Inhibitors of EGFR-selective tyrosine kinase and p38 mitogen-activated protein kinase effectively blocked the increase of IL-6 and IL-8. Furthermore, antagonists of thyroid hormone receptor and aryl hydrocarbon receptor significantly suppressed the increase in IL-6 and/or IL-8 production. In conclusion, penta- and octa-BDE, but not deca-BDE, might promote the expression of proinflammatory proteins in bronchial epithelial cells possibly by activating protein kinases and/or stimulating nuclear receptors related to subsequent activation of transcriptional factors. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Gas chromatography-mass spectrometric determination of traces of ether-type icing inhibitors in free-floating fuels

    Energy Technology Data Exchange (ETDEWEB)

    Shin, H.S. [Dept. of Environmental Education, Kongju National Univ., Kongju (Korea); Abuse Drug Research Center, Kongju National Univ., Kongju (Korea); Ahn, H.S. [Dept. of Environmental Science, Kongju National Univ., Kongju (Korea)

    2004-08-01

    A gas chromatographic-mass spectrometric (GC-MS) assay method has been developed for simultaneous determination of ethylene glycol monomethyl ether (EGME) and diethylene glycol monomethly ether (DEGME) in spilled aviation fuels. Ethylene glycol monobutyl ether (EGBE) and ethylene glycol monoethyl ether (EGEE) were used as internal standard and surrogate, respectively. Sample preparation consisted of back-extraction with 7 mL dichloromethane after extraction of 50 mL of fuel with 2 mL of water. The extract was concentrated to dryness, dissolved in 100 {mu}L methanol, and analyzed by GC-MS with selected-ion monitoring (SIM). The peaks had good chromatographic properties on a semi-polar column. EGME and DEGME were extracted from fuel with high recovery of 75 and 85%, with small variations, respectively. Method detection limits were 1.3 and 1.0 ng mL{sup -1} for EGME and DEGME, respectively, in spilled fuel. DEGME was detected at concentrations of 22.6 and 19.7 ng mL{sup -1} in two samples from among five free-floating samples collected in a tunnel of a subway station located in the vicinity of an army base in Korea. The method might be useful for differentiation between the fuel-types kerosene and JP-8, which might originate from a storage tank. (orig.)

  16. Cosmic Ether

    CERN Document Server

    Tomaschitz, R

    1998-01-01

    A prerelativistic approach to particle dynamics is explored in an expanding Robertson-Walker cosmology. The receding galactic background provides a distinguished frame of reference and a unique cosmic time. In this context the relativistic, purely geometric space-time concept is criticized. Physical space is regarded as a permeable medium, the cosmic ether, which effects the world-lines of particles and rays. We study in detail a Robertson-Walker universe with linear expansion factor and negatively curved, open three-space; we choose the permeability tensor of the ether in such a way that the semiclassical approximation is exact. Galactic red-shifts depend on the refractive index of the ether. In the local Minkowskian limit the ether causes a time variation of mass, which scales inversely proportional to cosmic time. In the globally geodesic rest frames of galactic observers the ether manifests itself in an unbounded speed of signal transfer, in bifurcations of world-lines, and in time inversion effects.

  17. The unexpected influence of aryl substituents in N-aryl-3-oxobutanamides on the behavior of their multicomponent reactions with 5-amino-3-methylisoxazole and salicylaldehyde

    Directory of Open Access Journals (Sweden)

    Volodymyr V. Tkachenko

    2014-12-01

    Full Text Available The switchable three-component reactions of 5-amino-3-methylisoxazole, salicylaldehyde and N-aryl-3-oxobutanamides under different conditions were studied and discussed. The unexpected influence of the aryl substituent in N-aryl-3-oxobutanamides on the behavior of the reaction was discovered. The key influence of ultrasonication and Lewis acid catalysts led to an established protocol to selectively obtain two or three types of heterocyclic scaffolds depending on the substituent in the N-aryl moiety.

  18. Fabrication and properties of poly(polyethylene glycol n-alkyl ether vinyl ether)s as polymeric phase change materials

    International Nuclear Information System (INIS)

    Pei, Dong-fang; Chen, Sai; Li, Shu-qin; Shi, Hai-feng; Li, Wei; Li, Xuan; Zhang, Xing-xiang

    2016-01-01

    A series of poly(polyethylene glycol n-alkyl ether vinyl ether)s (PC m E n VEs) with various lengths of alkyl chains and polyethylene glycol spacers as side chain (m = 16,18; n = 1,2) were synthesized via two steps. First, monomers-ethylene glycol hexadecyl ether vinyl ether (C 16 E 1 VE), ethylene glycol octadecyl ether vinyl ether (C 18 E 1 VE), diethylene glycol hexadecyl ether vinyl ether (C 16 E 2 VE) and diethylene glycol octadecyl ether vinyl ether (C 18 E 2 VE) were synthesized by a modified Williamson etherification. Then, four new types of phase change materials were successfully fabricated by a living cationic polymerization. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to characterize their composition, thermal properties and crystallization behavior. The results show that, the side chains of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are in a hexagonal lattice, and the onset temperatures for melting of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are 39.8 °C, 37.4 °C, 51.0 °C and 48.9 °C, the onset temperatures for crystallization are 36.7 °C, 35.2 °C, 47.4 °C and 46.3 °C, respectively. The enthalpy changes of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 100 J/g; on the contrary, it is 96 J/g for PC 16 E 1 VE. The enthalpy decrease is no more than 11% after 10 heating and cooling cycles. The 5 wt% mass loss temperatures of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 300 °C; on the contrary, it’s 283 °C for PC 16 E 1 VE. Using a weak polarity, flexible alkyl ether chain (-OCH 2 CH 2 O-) as a spacer to link the main chain and side chain is conducive to the crystallization of the alkyl side chain. These new phase change materials can be applied in heat storage, energy conservation, and environmental protection.

  19. C- versus O-Arylation of an Enol-Lactone Using Potassium tert-butoxide

    Directory of Open Access Journals (Sweden)

    El Moktar Essassi

    2003-05-01

    Full Text Available Abstract: The use of potassium tert-butoxide as the base in arylation reactions of an enollactone with a series of benzyl halides was explored. Our work demonstrates that the ratio of C-arylation to O-arylation varies with the substitution pattern of the aryl halide.

  20. Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase.

    Science.gov (United States)

    Kim, In-Hae; Park, Yong-Kyu; Nishiwaki, Hisashi; Hammock, Bruce D; Nishi, Kosuke

    2015-11-15

    Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase (sEH) were investigated. First, a series of alkyl or aryl groups were substituted on the carbon alpha to the phosphonate function in amide compounds to see whether substituted phosphonates can act as a secondary pharmacophore. A tert-butyl group (16) on the alpha carbon was found to yield most potent inhibition on the target enzyme. A 4-50-fold drop in inhibition was induced by other substituents such as aryls, substituted aryls, cycloalkyls, and alkyls. Then, the modification of the O-substituents on the phosphonate function revealed that diethyl groups (16 and 23) were preferable for inhibition to other longer alkyls or substituted alkyls. In amide compounds with the optimized diethylphosphonate moiety and an alkyl substitution such as adamantane (16), tetrahydronaphthalene (31), or adamantanemethane (36), highly potent inhibitions were gained. In addition, the resulting potent amide-phosphonate compounds had reasonable water solubility, suggesting that substituted phosphonates in amide inhibitors are effective for both inhibition potency on the human sEH and water solubility as a secondary pharmacophore. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Misconceptions about the ether

    International Nuclear Information System (INIS)

    Duffy, M.C.

    1980-01-01

    Several misconceptions concerning the ether concept and ether models are reviewed and clarified so that the relationship between modern ether theory and orthodox relativity may be better understood. The question of the ether's supposed superfluidity as a concept, and its status in modern physics remains to be answered. (author)

  2. Discovery of 4-aryl-N-arylcarbonyl-2-aminothiazoles as Hec1/Nek2 inhibitors. Part I: optimization of in vitro potencies and pharmacokinetic properties.

    Science.gov (United States)

    Lee, Ying-Shuan E; Chuang, Shih-Hsien; Huang, Lynn Y L; Lai, Chun-Liang; Lin, Yu-Hsiang; Yang, Ju-Ying; Liu, Chia-Wei; Yang, Sheng-chuan; Lin, Her-Sheng; Chang, Chia-chi; Lai, Jun-Yu; Jian, Pei-Shiou; Lam, King; Chang, Jia-Ming; Lau, Johnson Y N; Huang, Jiann-Jyh

    2014-05-22

    A series of 4-aryl-N-arylcarbonyl-2-aminothiazoles of scaffold 4 was designed and synthesized as Hec1/Nek2 inhibitors. Structural optimization of 4 led to compound 32 bearing C-4' 4-methoxyphenoxy and 4-(o-fluoropyridyl)carbonyl groups that showed low nanomolar in vitro antiproliferative activity (IC50: 16.3-42.7 nM), high intravenous AUC (64.9 μM·h, 2.0 mg/kg) in SD rats, and significant in vivo antitumor activity (T/C = 32%, 20 mg/kg, IV) in mice bearing human MDA-MB-231 xenografts. Cell responses resulting from Hec1/Nek2 inhibition were observed in cells treated with 32, including a reduced level of Hec1 coimmunoprecipitated with Nek2, degradation of Nek2, mitotic abnormalities, and apoptosis. Compound 32 showed selectivity toward cancer cells over normal phenotype cells and was inactive in a [(3)H]astemizole competitive binding assay for hERG liability screening. Therefore, 32 is as a good lead toward the discovery of a preclinical candidate targeting Hec1/Nek2 interaction.

  3. Selective copper catalysed aromatic N-arylation in water

    DEFF Research Database (Denmark)

    Engel-Andreasen, Jens; Shimpukade, Bharat; Ulven, Trond.

    2013-01-01

    4,7-Dipyrrolidinyl-1,10-phenanthroline (DPPhen) was identified as an efficient ligand for copper catalyzed selective arom. N-arylation in water. N-Arylation of indoles, imidazoles and purines proceeds with moderate to excellent yields and complete selectivity over aliph. amines. Aq. medium...

  4. Rhodium Catalyzed Intramolecular C-H Insertion of α-Aryl-α-diazo Ketones

    Science.gov (United States)

    Taber, Douglass F.; Tian, Weiwei

    2011-01-01

    Direct diazo transfer proceeds smoothly with α-aryl ketones. The derived α-aryl-α-diazo ketones cyclize efficiently with Rh catalysis to give the corresponding α-aryl cyclopentanones. PMID:17385917

  5. Electronic states of aryl radical functionalized graphenes: Density functional theory study

    Science.gov (United States)

    Tachikawa, Hiroto; Kawabata, Hiroshi

    2016-06-01

    Functionalized graphenes are known as a high-performance molecular device. In the present study, the structures and electronic states of the aryl radical functionalized graphene have been investigated by the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of graphene (GR). Also, the mechanism of aryl radical reaction with GR was investigated. The benzene, biphenyl, p-terphenyl, and p-quaterphenyl radicals [denoted by (Bz) n (n = 1-4), where n means numbers of benzene rings in aryl radical] were examined as aryl radicals. The DFT calculation of GR-(Bz) n (n = 1-4) showed that the aryl radical binds to the carbon atom of GR, and a C-C single bond was formed. The binding energies of aryl radicals to GR were calculated to be ca. 6.0 kcal mol-1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists in the aryl radical addition: the barrier heights were calculated to be 10.0 kcal mol-1. The electronic states of GR-(Bz) n were examined on the basis of theoretical results.

  6. Cu(I)/Diamine-catalyzed Aryl-alkyne Coupling Reactions

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    CuI/ethylene diamine/K2CO3/dioxane is shown to be a useful system for the cross coupling reactions of various aryl iodides and bromides with aryl and alkyl alkynes. Compared to the conventional Sonogashira reactions, the new procedure is free of palladium and phosphines.

  7. Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates.

    Science.gov (United States)

    Chary, Bathoju Chandra; Kim, Sunggak

    2013-09-25

    Rhodium(iii)-catalyzed C-H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

  8. Synthesis of isoprenoid bisphosphonate ethers through C–P bond formations: Potential inhibitors of geranylgeranyl diphosphate synthase

    Directory of Open Access Journals (Sweden)

    Xiang Zhou

    2014-07-01

    Full Text Available A set of bisphosphonate ethers has been prepared through sequential phosphonylation and alkylation of monophosphonate ethers. After formation of the corresponding phosphonic acid salts, these compounds were tested for their ability to inhibit the enzyme geranylgeranyl diphosphate synthase (GGDPS. Five of the new compounds show IC50 values of less than 1 μM against GGDPS with little to no activity against the related enzyme farnesyl diphosphate synthase (FDPS. The most active compound displayed an IC50 value of 82 nM when assayed with GGDPS, and no activity against FDPS even at a 10 μM concentration.

  9. Reproductive toxicity of the glycol ethers.

    Science.gov (United States)

    Hardin, B D

    1983-06-01

    The glycol ethers are an important and widely used class of solvents. Recent studies have demonstrated that ethylene glycol monomethyl ether (EGME), ethylene glycol dimethyl ether (EGdiME), ethylene glycol monoethyl ether (EGEE), and ethylene glycol monoethyl ether acetate (EGEEA) are teratogenic. Other studies have demonstrated that testicular atrophy or infertility follow treatment of males with EGME, ethylene glycol monomethyl ether acetate (EGMEA), EGEE, EGEEA, diethylene glycol dimethyl ether (diEGdiME), and diethylene glycol monoethyl ether (diEGEE). Experimental data are reviewed and structure-activity relationships are speculated upon.

  10. Improved biological processes for the production of aryl sulfates

    DEFF Research Database (Denmark)

    2017-01-01

    The present invention generally relates to the field of biotechnology as it applies to the production of aryl sulfates using recombinant host cells. More particularly, the present invention pertains to recombinant host cells comprising (e.g., expressing) a polypeptide having aryl sulfotransferase...... activity, wherein said recombinant host cells have been modified to have an increased uptake of sulfate compared to identical host cells that does not carry said modification. Further provided are processes for the production of aryl sulfates, such as zosteric acid, employing such recombinant host cells....

  11. A multidisciplinary study of 3-(β-d-glucopyranosyl)-5-substituted-1,2,4-triazole derivatives as glycogen phosphorylase inhibitors: Computation, synthesis, crystallography and kinetics reveal new potent inhibitors.

    Science.gov (United States)

    Kun, Sándor; Begum, Jaida; Kyriakis, Efthimios; Stamati, Evgenia C V; Barkas, Thomas A; Szennyes, Eszter; Bokor, Éva; Szabó, Katalin E; Stravodimos, George A; Sipos, Ádám; Docsa, Tibor; Gergely, Pál; Moffatt, Colin; Patraskaki, Myrto S; Kokolaki, Maria C; Gkerdi, Alkistis; Skamnaki, Vassiliki T; Leonidas, Demetres D; Somsák, László; Hayes, Joseph M

    2018-03-10

    3-(β-d-Glucopyranosyl)-5-substituted-1,2,4-triazoles have been revealed as an effective scaffold for the development of potent glycogen phosphorylase (GP) inhibitors but with the potency very sensitive to the nature of the alkyl/aryl 5-substituent (Kun et al., Eur. J. Med. Chem. 2014, 76, 567). For a training set of these ligands, quantum mechanics-polarized ligand docking (QM-PLD) demonstrated good potential to identify larger differences in potencies (predictive index PI = 0.82) and potent inhibitors with K i 's synthesis. The compounds were prepared in O-perbenzoylated forms by either ring transformation of 5-β-d-glucopyranosyl tetrazole by N-benzyl-arenecarboximidoyl chlorides, ring closure of C-(β-d-glucopyranosyl)formamidrazone with aroyl chlorides, or that of N-(β-d-glucopyranosylcarbonyl)arenethiocarboxamides by hydrazine, followed by deprotections. Kinetics experiments against rabbit muscle GPb (rmGPb) and human liver GPa (hlGPa) revealed five compounds as potent low μM inhibitors with three of these on the submicromolar range for rmGPa. X-ray crystallographic analysis sourced the potency to a combination of favorable interactions from the 1,2,4-triazole and suitable aryl substituents in the GP catalytic site. The compounds also revealed promising calculated pharmacokinetic profiles. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

  12. Visible light catalyzed methylsulfoxidation of (het)aryl diazonium salts using DMSO.

    Science.gov (United States)

    Pramanik, Mukund M D; Rastogi, Namrata

    2016-06-30

    The visible light catalyzed methylsulfoxidation of (het)aryl diazonium salts using DMSO is illustrated. This is the first example of DMSO being used as the source of the methylsulfinyl group. The procedure tolerates a wide range of functional groups on (het)aryl diazonium salts and provides aryl methyl sulfoxides in excellent yields under mild reaction conditions.

  13. Application of a Heterogeneous Chiral Titanium Catalyst Derived from Silica-Supported 3-Aryl H8-BINOL to Enantioselective Alkylation and Arylation of Aldehydes.

    Science.gov (United States)

    Akai, Junichiro; Watanabe, Satoshi; Michikawa, Kumiko; Harada, Toshiro

    2017-07-07

    A 3-aryl H 8 -BINOL was grafted on the surface of silica gel using a hydrosilane derivative as a precursor, and the resulting silica-supported ligand (6 mol %) was employed in the enantioselective alkylation and arylation of aldehydes in the presence of Ti(O i Pr) 4 . The reactions using Et 2 Zn, Et 3 B, and aryl Grignard reagents all afforded the corresponding adducts in high enantioselectivities and yields. The silica-immobilized titanium catalyst could be reused up to 14 times without appreciable deterioration of the activity.

  14. Photocatalytic Arylation of Alkenes, Alkynes and Enones with Diazonium Salts

    OpenAIRE

    Schroll, Peter; Hari, Durga Prasad; König, Burkhard

    2012-01-01

    Teaching old dogs new tricks: Visible light photoredox catalysis improves the classic Meerwein arylation protocol significantly and allows the light-controlled arylation of alkenes, alkynes and enones by diazonium salts.

  15. Synthesis and biological evaluation of aryl-oxadiazoles as inhibitors of Mycobacterium tuberculosis.

    Science.gov (United States)

    Martinez-Grau, Maria Angeles; Valcarcel, Isabel C Gonzalez; Early, Julie V; Gessner, Richard Klaus; de Melo, Candice Soares; de la Nava, Eva Maria Martin; Korkegian, Aaron; Ovechkina, Yulia; Flint, Lindsay; Gravelle, Anisa; Cramer, Jeff W; Desai, Prashant V; Street, Leslie J; Odingo, Joshua; Masquelin, Thierry; Chibale, Kelly; Parish, Tanya

    2018-04-13

    Despite increased research efforts to find new treatments for tuberculosis in recent decades, compounds with novel mechanisms of action are still required. We previously identified a series of novel aryl-oxadiazoles with anti-tubercular activity specific for bacteria using butyrate as a carbon source. We explored the structure activity relationship of this series. Structural modifications were performed in all domains to improve potency and physico-chemical properties. A number of compounds displayed sub-micromolar activity against M. tuberculosis utilizing butyrate, but not glucose as the carbon source. Compounds showed no or low cytotoxicity against eukaryotic cells. Three compounds were profiled in mouse pharmacokinetic studies. Plasma clearance was low to moderate but oral exposure suggested solubility-limited drug absorption in addition to first pass metabolism. The presence of a basic nitrogen in the linker slightly increased solubility, and salt formation optimized aqueous solubility. Our findings suggest that the 1,3,4-oxadiazoles are useful tools and warrant further investigation. Copyright © 2018 The Author(s). Published by Elsevier Ltd.. All rights reserved.

  16. New halogenated phenylcoumarins as tyrosinase inhibitors.

    Science.gov (United States)

    Matos, Maria João; Santana, Lourdes; Uriarte, Eugenio; Delogu, Giovanna; Corda, Marcella; Fadda, Maria Benedetta; Era, Benedetta; Fais, Antonella

    2011-06-01

    With the aim to find out structural features for the tyrosinase inhibitory activity, in the present communication we report the synthesis and pharmacological evaluation of a new series of phenylcoumarin derivatives with different number of hydroxyl or ether groups and bromo substituent in the scaffold. The synthesized compounds 5-12 were evaluated as mushroom tyrosinase inhibitors showing, two of them, lower IC(50) than the umbelliferone. Compound 12 (IC(50)=215 μM) is the best tyrosinase inhibitor of this series. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. Nickel-catalyzed synthesis of aryl trifluoromethyl sulfides at room temperature.

    Science.gov (United States)

    Zhang, Cheng-Pan; Vicic, David A

    2012-01-11

    Inexpensive nickel-bipyridine complexes were found to be active for the trifluoromethylthiolation of aryl iodides and aryl bromides at room temperature using the convenient [NMe(4)][SCF(3)] reagent. © 2011 American Chemical Society

  18. Divergent unprotected peptide macrocyclisation by palladium-mediated cysteine arylation.

    Science.gov (United States)

    Rojas, Anthony J; Zhang, Chi; Vinogradova, Ekaterina V; Buchwald, Nathan H; Reilly, John; Pentelute, Bradley L; Buchwald, Stephen L

    2017-06-01

    Macrocyclic peptides are important therapeutic candidates due to their improved physicochemical properties in comparison to their linear counterparts. Here we detail a method for a divergent macrocyclisation of unprotected peptides by crosslinking two cysteine residues with bis-palladium organometallic reagents. These synthetic intermediates are prepared in a single step from commercially available aryl bis-halides. Two bioactive linear peptides with cysteine residues at i , i + 4 and i , i + 7 positions, respectively, were cyclised to introduce a diverse array of aryl and bi-aryl linkers. These two series of macrocyclic peptides displayed similar linker-dependent lipophilicity, phospholipid affinity, and unique volume of distributions. Additionally, one of the bioactive peptides showed target binding affinity that was predominantly affected by the length of the linker. Collectively, this divergent strategy allowed rapid and convenient access to various aryl linkers, enabling the systematic evaluation of the effect of appending unit on the medicinal properties of macrocyclic peptides.

  19. Radiation deterioration of several aromatic polymers under oxidative conditions

    International Nuclear Information System (INIS)

    Sasuga, Tsuneo; Hagiwara, Miyuki

    1987-01-01

    Radiation-induced oxidative irradiation effects (with γ-rays under oxygen pressure) or poly(aryl sulphones) (U-PS and PES), poly(aryl ester) (U-Polymer), poly(aryl amide) (A-Film) and poly(aryl ether ether ketone) (PEEK) have been studied based on changes in tensile properties. The deterioration dose estimated from the decrease in the elongation at break was as low as one-fifth to one-tenth of that in high-dose-rate electron-beam irradiation, but the order of radiation resistance of the polymers did not differ from that in electron-beam irradiation, i.e. PEEK > A-Film > U-Polymer > U-PS > PES. The radiation stability of aromatic units under oxidative conditions was estimated from a comparison of the radiation resistance of the polymers themselves and their chemical structures. The following order was obtained: diphenyl ether, diphenyl ketone > aromatic amide>> bisphenol A > diphenyl sulphone. The deterioration mechanism of PEEK under oxidative irradiation was studied by measuring dynamic viscoelastic properties. It was concluded that deterioration in mechanical properties under oxidative irradiation was brought about by chain scission only. (author)

  20. 3D-QSAR (CoMFA, CoMSIA), molecular docking and molecular dynamics simulations study of 6-aryl-5-cyano-pyrimidine derivatives to explore the structure requirements of LSD1 inhibitors.

    Science.gov (United States)

    Ding, Lina; Wang, Zhi-Zheng; Sun, Xu-Dong; Yang, Jing; Ma, Chao-Ya; Li, Wen; Liu, Hong-Min

    2017-08-01

    Recently, Histone Lysine Specific Demethylase 1 (LSD1) was regarded as a promising anticancer target for the novel drug discovery. And several small molecules as LSD1 inhibitors in different structures have been reported. In this work, we carried out a molecular modeling study on the 6-aryl-5-cyano-pyrimidine fragment LSD1 inhibitors using three-dimensional quantitative structure-activity relationship (3D-QSAR), molecular docking and molecular dynamics simulations. Comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) were used to generate 3D-QSAR models. The results show that the best CoMFA model has q 2 =0.802, r 2 ncv =0.979, and the best CoMSIA model has q 2 =0.799, r 2 ncv =0.982. The electrostatic, hydrophobic and H-bond donor fields play important roles in the models. Molecular docking studies predict the binding mode and the interactions between the ligand and the receptor protein. Molecular dynamics simulations results reveal that the complex of the ligand and the receptor protein are stable at 300K. All the results can provide us more useful information for our further drug design. Copyright © 2017. Published by Elsevier Ltd.

  1. An efficient synthesis of S-[gamma]-[(4-trifluoromethyl)phenoxy] benzenepropanamine-[1-[sup 14]C]maleate, an important metabolite of fluoxetine hydrochloride. [Antidepressant, serotonin uptake inhibitor

    Energy Technology Data Exchange (ETDEWEB)

    Wheeler, W.J. (Lilly (Eli) and Co., Indianapolis, IN (United States). Lilly Research Labs.)

    1992-02-01

    S-[gamma]-[(4-Trifluoromethyl)phenoxy]benzenepropanamine-[1-[sup 14]C] maleate has been prepared in six steps from R-(-)1-phenyl-1,2-ethanediol. The isotope was incorporated by the reaction of NaCN-[[sup 14]C] with the tert. butyldimethylsilyl ether of R-(-)1-phenyl-1,2-ethane-diol 2-tosylate. Borane reduction and arylation, followed by salt formation yielded S-[gamma]-[(4-trifluoromethyl)phenoxy]benzenepropanamine-[1-[sup 14]C] maleate. (Author).

  2. Exogenous ether lipids predominantly target mitochondria.

    Directory of Open Access Journals (Sweden)

    Lars Kuerschner

    Full Text Available Ether lipids are ubiquitous constituents of cellular membranes with no discrete cell biological function assigned yet. Using fluorescent polyene-ether lipids we analyzed their intracellular distribution in living cells by microscopy. Mitochondria and the endoplasmic reticulum accumulated high amounts of ether-phosphatidylcholine and ether-phosphatidylethanolamine. Both lipids were specifically labeled using the corresponding lyso-ether lipids, which we established as supreme precursors for lipid tagging. Polyfosine, a fluorescent analogue of the anti-neoplastic ether lipid edelfosine, accumulated to mitochondria and induced morphological changes and cellular apoptosis. These data indicate that edelfosine could exert its pro-apoptotic power by targeting and damaging mitochondria and thereby inducing cellular apoptosis. In general, this study implies an important role of mitochondria in ether lipid metabolism and intracellular ether lipid trafficking.

  3. Ether formulations of relativity

    International Nuclear Information System (INIS)

    Duffy, M.C.

    1980-01-01

    Contemporary ether theories are surveyed and criticised, especially those formally identical to orthodox Relativity. The historical development of Relativity, Special and General, in terms of an ether, is briefly indicated. Classical interpretations of Generalized Relativity using ether are compared to Euclidean formulations using a background space. The history of a sub-group of theories, formulating a 'new' Relativity involving modified transforms, is outlined. According to the theory with which they agree, recent supposed detections of drift are classified and criticised. Cosmological evidence suggesting an ether is mentioned. Only ether theories formally identical to Relativity have been published in depth. They stand criticised as being contrary to the positivist spirit. The history of mechanical analogues is traced, from Hartley's representing gravitating matter as spherical standing waves, to recent suggestions that vortex-sponge might model electromagnetic, quantum, uncertainty and faster-than-light phenomena. Contemporary theories are particular physical theories, themselves 'second interpretations' of a primary mathematical model. Mechanical analogues are auxiliary, not necessary, to other theory, disclosing relationships between classical and non-classical descriptions of assemblies charging state. The ether-relativity polemic, part of a broader dispute about relativity, is founded on mistaken conceptions of the roles of mathematical and physical models, mechanical analogues; and a distored view of history, which indicates that ether theories have become relativistic. (author)

  4. Chemoselective N-arylation of aminobenzamides via copper catalysed Chan-Evans-Lam reactions.

    Science.gov (United States)

    Liu, Shuai; Zu, Weisai; Zhang, Jinli; Xu, Liang

    2017-11-15

    Chemoselective N-arylation of unprotected aminobenzamides was achieved via Cu-catalysed Chan-Evans-Lam cross-coupling with aryl boronic acids for the first time. Simple copper catalysts enable the selective arylation of amino groups in ortho/meta/para-aminobenzamides under open-flask conditions. The reactions were scalable and compatible with a wide range of functional groups.

  5. Optimization of Aryl Amides that Extend Survival in Prion-Infected Mice.

    Science.gov (United States)

    Giles, Kurt; Berry, David B; Condello, Carlo; Dugger, Brittany N; Li, Zhe; Oehler, Abby; Bhardwaj, Sumita; Elepano, Manuel; Guan, Shenheng; Silber, B Michael; Olson, Steven H; Prusiner, Stanley B

    2016-09-01

    Developing therapeutics for neurodegenerative diseases (NDs) prevalent in the aging population remains a daunting challenge. With the growing understanding that many NDs progress by conformational self-templating of specific proteins, the prototypical prion diseases offer a platform for ND drug discovery. We evaluated high-throughput screening hits with the aryl amide scaffold and explored the structure-activity relationships around three series differing in their N-aryl core: benzoxazole, benzothiazole, and cyano. Potent anti-prion compounds were advanced to pharmacokinetic studies, and the resulting brain-penetrant leads from each series, together with a related N-aryl piperazine lead, were escalated to long-term dosing and efficacy studies. Compounds from each of the four series doubled the survival of mice infected with a mouse-passaged prion strain. Treatment with aryl amides altered prion strain properties, as evidenced by the distinct patterns of neuropathological deposition of prion protein and associated astrocytic gliosis in the brain; however, none of the aryl amide compounds resulted in drug-resistant prion strains, in contrast to previous studies on compounds with the 2-aminothiazole (2-AMT) scaffold. As seen with 2-AMTs and other effective anti-prion compounds reported to date, the novel aryl amides reported here were ineffective in prolonging the survival of transgenic mice infected with human prions. Most encouraging is our discovery that aryl amides show that the development of drug resistance is not an inevitable consequence of efficacious anti-prion therapeutics. Copyright © 2016 by The American Society for Pharmacology and Experimental Therapeutics.

  6. The synthesis of α-aryl-α-aminophosphonates and α-aryl-α-aminophosphine oxides by the microwave-assisted Pudovik reaction

    Directory of Open Access Journals (Sweden)

    Erika Bálint

    2017-01-01

    Full Text Available A family of α-aryl-α-aminophosphonates and α-aryl-α-aminophosphine oxides was synthesized by the microwave-assisted solvent-free addition of dialkyl phosphites and diphenylphosphine oxide, respectively, to imines formed from benzaldehyde derivatives and primary amines. After optimization, the reactivity was mapped, and the fine mechanism was evaluated by DFT calculations. Two α-aminophosphonates were subjected to an X-ray study revealing a racemic dimer formation made through a N–H···O=P intermolecular hydrogen bridges pair.

  7. Influence of Functionality on Direct Arylation of Model Systems as a Route Toward Fluorinated Copolymers via Direct Arylation Polymerization (DArP)

    DEFF Research Database (Denmark)

    Livi, Francesco; Gobalasingham, Nemal S.; Bundgaard, Eva

    2015-01-01

    A screening of direct arylation conditions on amodel small molecule system is carried out to develop suitableconditions for the direct arylation polymerization (DArP) of fluorinatedcopolymers, which are incompatible with conditionspreviously utilized successfully for nonfluorinated systems. Themo......,4-phenylene)dithiophene. Polymers arefree of β-defects and significant homocoupling. This work furtherunderscores the attractive simplicity, relevance, and easeof DArP while reconfirming its broad compatibility withincreasingly popular fluorinated copolymers....

  8. Metal-Free N-Arylation of Secondary Amides at Room Temperature

    OpenAIRE

    Tinnis, Fredrik; Stridfeldt, Elin; Lundberg, Helena; Adolfsson, Hans; Olofsson, Berit

    2015-01-01

    The arylation of secondary acyclic amides has been achieved with diaryliodonium salts under mild and metal-free conditions. The methodology has a wide scope, allows synthesis of tertiary amides with highly congested aryl moieties, and avoids the regioselectivity problems observed in reactions with (diacetoxyiodo)benzene.

  9. Electronic structure and tautomerism of aryl ketones

    International Nuclear Information System (INIS)

    Novak, Igor; Klasinc, Leo; Šket, Boris; McGlynn, S.P.

    2015-01-01

    Graphical abstract: Photoelectron spectroscopy, tautomerism. - Highlights: • UV photoelectron spectroscopy of aryl ketones. • The relative stability of tautomers and their electronic structures. • The factors influencing tautomerism. - Abstract: The electronic structures of several aryl ketones (AK) and their α-halo derivatives have been studied by UV photoelectron spectroscopy (UPS). The relative stabilities of keto–enol tautomers have been determined using high-level ab initio calculations and the results were used in the analysis of UPS spectra. The main features of electronic structure and tautomerism of the AK derivatives are discussed

  10. Electronic structure and tautomerism of aryl ketones

    Energy Technology Data Exchange (ETDEWEB)

    Novak, Igor, E-mail: inovak@csu.edu.au [Charles Sturt University, POB 883, Orange, NSW 2800 (Australia); Klasinc, Leo, E-mail: klasinc@irb.hr [Physical Chemistry Department, Ruđer Bošković Institute, HR-10002 Zagreb (Croatia); Šket, Boris, E-mail: Boris.Sket@fkkt.uni-lj.si [Faculty of Chemistry and Chemical Technology, University of Ljubljana, SI-1000 (Slovenia); McGlynn, S.P., E-mail: sean.mcglynn@chemgate.chem.lsu.edu [Louisiana State University, Baton Rouge, LA 70803 (United States)

    2015-07-15

    Graphical abstract: Photoelectron spectroscopy, tautomerism. - Highlights: • UV photoelectron spectroscopy of aryl ketones. • The relative stability of tautomers and their electronic structures. • The factors influencing tautomerism. - Abstract: The electronic structures of several aryl ketones (AK) and their α-halo derivatives have been studied by UV photoelectron spectroscopy (UPS). The relative stabilities of keto–enol tautomers have been determined using high-level ab initio calculations and the results were used in the analysis of UPS spectra. The main features of electronic structure and tautomerism of the AK derivatives are discussed.

  11. Diversification of indoles via microwave-assisted ligand-free copper-catalyzed N-arylation

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Jae Kwan; Lee, Jin Hee; Kim, Tae Sung; Yum, Eul Kgun [Dept. of Chemistry, Chu ngnam National University, Daejon (Korea, Republic of); Park, Jee Jung [Western Seoul Center Korea Basic Science Institute, Seoul (Korea, Republic of)

    2016-12-15

    A simple, efficient Cu{sub 2}O catalyst system under microwave irradiation was developed for N-arylation of various indoles without ligands and additives. Diverse N-heteroarylated indoles were prepared by coupling indoles with various heteroaryl halides within 1 h. The selective reactivity of bromoindole with aryl iodide provided N-aryl bromoindoles, which could be useful intermediates for palladium-catalyzed Heck and Suzuki coupling reactions.

  12. Microwave-assisted synthesis of α-aryl malonates: Key intermediates for the

    Directory of Open Access Journals (Sweden)

    Mohamed A. Ibrahim

    2016-11-01

    Full Text Available We disclose a new microwave-assisted protocol for the effective α-arylation of diethyl malonate. The coupling of aryl halides with diethyl malonate proceeds smoothly in short reaction time in the presence of a catalytic amount of Cu(OTf2, 2-picolinic acid and Cs2CO3 in toluene using microwave irradiation. The resulting α-aryl malonates are then used as key intermediates for synthesis of variety of heterocyclic compounds, including benzodiazepines, isoquinolines and pyrrolopyridine scaffolds.

  13. Pd-Catalyzed Cross-Coupling Reactions of Amides and Aryl Mesylates

    Science.gov (United States)

    Dooleweerdt, Karin; Fors, Brett P.; Buchwald, Stephen L.

    2010-01-01

    A catalyst, based on a biarylphosphine ligand, for the Pd-catalyzed cross-coupling reactions of amides and aryl mesylates is described. This system allows an array of aryl and heteroaryl mesylates to be transformed into the corresponding N-arylamides in moderate to excellent yields. PMID:20420379

  14. N-Benzylhydroxylamine addition to beta-aryl enoates. Enantioselective synthesis of beta-aryl-beta-amino acid precursors

    Science.gov (United States)

    Sibi; Liu

    2000-10-19

    Chiral Lewis acid catalyzed N-benzylhydroxylamine addition to pyrrolidinone-derived enoates afforded beta-aryl-beta-amino acid derivatives in high enantiomeric purity with moderate to very good chemical efficiency.

  15. Initial Reactivity of Linkages and Monomer Rings in Lignin Pyrolysis Revealed by ReaxFF Molecular Dynamics.

    Science.gov (United States)

    Zhang, Tingting; Li, Xiaoxia; Guo, Li

    2017-10-24

    The initial conversion pathways of linkages and their linked monomer units in lignin pyrolysis were investigated comprehensively by ReaxFF MD simulations facilitated by the unique VARxMD for reaction analysis. The simulated molecular model contains 15 920 atoms and was constructed on the basis of Adler's softwood lignin model. The simulations uncover the initial conversion ratio of various linkages and their linked aryl monomers. For linkages and their linked monomer aryl rings of α-O-4, β-O-4 and α-O-4 & β-5, the C α /C β ether bond cracking dominates the initial pathway accounting for at least up to 80% of their consumption. For the linkage of β-β & γ-O-α, both the C α -O ether bond cracking and its linked monomer aryl ring opening are equally important. Ring-opening reactions dominate the initial consumption of other 4-O-5, 5-5, β-1, β-2, and β-5 linkages and their linked monomers. The ether bond cracking of C α -O and C β -O occurs at low temperature, and the aryl ring-opening reactions take place at relatively high temperature. The important intermediates leading to the stable aryl ring opening are the phenoxy radicals, the bridged five-membered and three-membered rings and the bridged six-membered and three-membered rings. In addition, the reactivity of a linkage and its monomer aryl ring may be affected by other linkages. The ether bond cracking of α-O-4 and β-O-4 linkages can activate its neighboring linkage or monomer ring through the formed phenoxy radicals as intermediates. The important intermediates revealed in this article should be of help in deepening the understanding of the controlling mechanism for producing aromatic chemicals from lignin pyrolysis.

  16. Maternal-infant transfer of polybrominated diphenyl ethers

    Energy Technology Data Exchange (ETDEWEB)

    Hirai, T.; Fujimine, Y.; Watanabe, S. [Otsuka Pharmaceutical Co., Ltd., Tokushima (Japan); Nakamura, Y. [SRL Nishinihon, Fukuoka (Japan); Shimomura, H. [Shimomura OBGY Clinic, Fukuoka (Japan); Nagayama, J. [Kyushu Univ., Fukuoka (Japan)

    2004-09-15

    Polybrominated diphenyl ethers (PBDEs) are widely used brominated flame retardants (BFRs) in plastics of automobiles, textile industry, television, personal computer, electronic appliances etc. The amount of production world-wide has reached 40,000 tons in 1992. In 1992 world-wide production of PBDEs reached 40,000 tons raising serious concern over the dangers of environmental pollution by BFRs. The toxicity of PBDEs was reported to be an antagonist of thyroid-hormone (T4) and inhibition to aryl hydrocarbon (Ah) receptor. Since PBDEs are structurally similar to PCBs and therefore they work as an antagonist. Polychlorinated biphenyl (PCBs) demonstrate biological stability and high lipophilicity. As a result, PCBs used in the past and released into the environment, have been transmitted through the food chain and accumlated in the human body over time. In Japan, approximately 58,000 tons of PCBs were produced with the grade name of Kanechlor in between 1954 and 1971. In this study, all PCB congeners and 25 PBDE congeners (17, 25, 28, 30, 32, 33, 35, 37, 47, 49, 66, 71, 75, 77, 85, 99, 100, 116, 119, 126, 138, 153, 154, 155, 166) were analyzed by the method that combines high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). The purpose of this study was to investigate whether congener-specific PCBs and PBDEs were transferred from pregnant women to their infants.

  17. Ether the nothing that connects everything

    CERN Document Server

    Milutis, Joe

    2006-01-01

    In Ether, the histories of the unseen merge with discussions of the technology of electromagnetism. Navigating more than three hundred years of the ether''s cultural and artistic history, Joe Milutis reveals its continuous reinvention and tangible impact without ever losing sight of its ephemeral, elusive nature. The true meaning of ether, Milutis suggests, may be that it can never be fully grasped.

  18. Usage of the word 'ether'

    International Nuclear Information System (INIS)

    Duffy, M.C.

    1980-01-01

    Confusion has been caused by scientists using the one word 'ether' to classify models differing from each other in important respects. Major roles assigned to the word are examined, and the nature of modern ether theories surveyed. The part played by the several meanings attached to the word, in the ether concept, is outlined. (author)

  19. Synthesis of sulfadiazinyl acyl/aryl thiourea derivatives as calf intestinal alkaline phosphatase inhibitors, pharmacokinetic properties, lead optimization, Lineweaver-Burk plot evaluation and binding analysis.

    Science.gov (United States)

    Sajid-Ur-Rehman; Saeed, Aamer; Saddique, Gufran; Ali Channar, Pervaiz; Ali Larik, Fayaz; Abbas, Qamar; Hassan, Mubashir; Raza, Hussain; Fattah, Tanzeela Abdul; Seo, Sung-Yum

    2018-06-02

    To seek the new medicinal potential of sulfadiazine drug, the free amino group of sulfadiazine was exploited to obtain acyl/aryl thioureas using simple and straightforward protocol. Acyl/aryl thioureas are well recognized bioactive pharmacophore containing moieties. A new series (4a-4j) of sulfadiazine derived acyl/aryl thioureas was synthesized and characterized through spectroscopic and elemental analysis. The synthesized derivatives 4a-4j were subjected to calf intestinal alkaline phosphatase (CIAP) activity. The derivative 4a-4j showed better inhibition potential compared to standard monopotassium phosphate (MKP). The compound 4c exhibited higher potential in the series with IC 50 0.251 ± 0.012 µM (standard KH 2 PO 4 4.317 ± 0.201 µM). Lineweaver-Burk plots revealed that most potent derivative 4c inhibition CIAP via mixed type pathway. Pharmacological investigations showed that synthesized compounds 4a-4j obey Lipinsk's rule. ADMET parameters evaluation predicted that these molecule show significant lead like properties with minimum possible toxicity and can serve as templates in drug designing. The synthetic compounds show none mutagenic and irritant behavior. Molecular docking analysis showed that compound 4c interacts with Asp273, His317 and Arg166 amino acid residues. Copyright © 2018. Published by Elsevier Ltd.

  20. Pot-Economy Autooxidative Condensation of 2-Aryl-2-lithio-1,3-dithianes.

    Science.gov (United States)

    Vale, João R; Rimpiläinen, Tatu; Sievänen, Elina; Rissanen, Kari; Afonso, Carlos A M; Candeias, Nuno R

    2018-02-16

    The autoxidative condensation of 2-aryl-2-lithio-1,3-dithianes is here reported. Treatment of 2-aryl-1,3-dithianes with n-BuLi in the absence of any electrophile leads to condensation of three molecules of 1,3-dithianes and formation of highly functionalized α-thioether ketones orthothioesters in 51-89% yields upon air exposure. The method was further expanded to benzaldehyde dithioacetals, affording corresponding orthothioesters and α-thioether ketones in 48-97% yields. The experimental results combined with density functional theory studies support a mechanism triggered by the autoxidation of 2-aryl-2-lithio-1,3-dithianes to yield a highly reactive thioester that undergoes condensation with two other molecules of 2-aryl-2-lithio-1,3-dithiane.

  1. Synthesis and biological evaluation of novel tetrahydroisoquinoline-C-aryl glucosides as SGLT2 inhibitors for the treatment of type 2 diabetes.

    Science.gov (United States)

    Pan, Xuan; Huan, Yi; Shen, Zhufang; Liu, Zhanzhu

    2016-05-23

    A series of novel tetrahydroisoquinoline-C-aryl glucosides has been synthesized and evaluated for the inhibition of human SGLT2. Compared with dapagliflozin, compound 13h exhibited equivalent in vitro inhibitory activity against SGLT2, which might become a promising candidate for the treatment of type 2 diabetes. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  2. The failure of poly (ether ether ketone) in high speed contacts

    Science.gov (United States)

    Briscoe, B. J.; Stuart, B. H.; Sebastian, S.; Tweedale, P. J.

    1993-04-01

    The paper describes an experimental study, with an associated analysis incorporating supplementary data, of the anti-boundary lubricating action of an alkane-aliphatic carboxylic acid lubricant system in a poly (ether ether ketone)-mild steel contact. The experiments involve progressively increasing the load in a contact formed between a polymer plate and a rotating steel shaft and estimating the frictional work dissipated. Scuffing is identified when a rapid increase in frictional work is noted at a characteristic normal load. It is shown that the additive induces premature scuffing. Subsidiary data is provided using Raman spectroscopy and hardness probes, and confirms that certain additives such as decanoic acid and dodecylamine will induce surface plasticization in poly (ether ether ketone). The trends in the frictional data have been interpreted using the adhesive model of friction in conjunction with temperature-dependent interfacial theology and bulk mechanical property data. It is proposed that the scuffing process is induced prematurely as a consequence of excessive additive-induced subsurface plasticization. Restricted surface plasticization in this system provides an enhanced self-lubricating capacity.

  3. Aryl Insertion vs Aryl-Aryl Coupling in C,C-Chelated Organoborates: The "Missing Link" of Tetraarylborate Photochemistry.

    Science.gov (United States)

    Radtke, Julian; Mellerup, Soren K; Bolte, Michael; Lerner, Hans-Wolfram; Wang, Suning; Wagner, Matthias

    2018-06-14

    The photoreactivity of 9-borafluorene-based, C,C-chelated organoborates was investigated. Unlike the related tetraarylborates, the charge-transfer transitions imparted by the biphenyl chelate lead to selective insertion of one aryl substituent into the endocyclic B-C bond of the 9-borafluorene moiety, resulting in the formation of boratanorcaradienes. This photoreaction likely proceeds according to a Zimmerman rearrangement, which is analogous to one of the initially proposed mechanisms for tetraarylborates and provides additional insight into these long-debated photochemical reactions.

  4. Novel structural hybrids of pyrazolobenzothiazines with benzimidazoles as cholinesterase inhibitors.

    Science.gov (United States)

    Aslam, Sana; Zaib, Sumera; Ahmad, Matloob; Gardiner, John M; Ahmad, Aqeel; Hameed, Abdul; Furtmann, Norbert; Gütschow, Michael; Bajorath, Jürgen; Iqbal, Jamshed

    2014-05-06

    Two series of novel pyrazolobenzothiazine-based hybrid compounds were efficiently synthesized starting from saccharin sodium salt. Pyrazolo[4,3-c][1,2]benzothiazine scaffolds were N-arylated by using p-fluorobenzaldehyde, followed by the incorporation of a benzimidazole or similar ring systems by treatment with arylenediamines. These phenylene-connected hybrid compounds were investigated as potential inhibitors of acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE). Compounds 12d and 12k were the most potent AChE inhibitors with IC50 values of 11 and 13 nM, respectively, while 6j (IC50 = 17 nM) proved to be the most active inhibitor against BuChE with remarkable selectivity for BuChE over AChE. Molecular docking studies were also performed on human AChE and BuChE to suggest possible binding modes in which the inhibitor's extended structure is accommodated along the active site gorge of both enzymes. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  5. Manganese-Catalyzed Cross-Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism

    DEFF Research Database (Denmark)

    Antonacci, Giuseppe; Ahlburg, Andreas; Fristrup, Peter

    2017-01-01

    The substrate scope and the mechanism have been investigated for the MnCl2-catalyzed cross-coupling reaction between aryl halides and Grignard reagents. The transformation proceeds rapidly and in good yield when the aryl halide component is an aryl chloride containing a cyano or an ester group....... Two radical-clock experiments were carried out, and in both cases an intermediate aryl radical was successfully trapped. The cross-coupling reaction is therefore believed to proceed by an SRN1 mechanism, with a triorganomanganate complex serving as the most likely nucleophile and single-electron donor...

  6. Increasing human Th17 differentiation through activation of orphan nuclear receptor retinoid acid-related orphan receptor γ (RORγ) by a class of aryl amide compounds.

    Science.gov (United States)

    Zhang, Wei; Zhang, Jing; Fang, Leiping; Zhou, Ling; Wang, Shuai; Xiang, Zhijun; Li, Yuan; Wisely, Bruce; Zhang, Guifeng; An, Gang; Wang, Yonghui; Leung, Stewart; Zhong, Zhong

    2012-10-01

    In a screen for small-molecule inhibitors of retinoid acid-related orphan receptor γ (RORγ), we fortuitously discovered that a class of aryl amide compounds behaved as functional activators of the interleukin 17 (IL-17) reporter in Jurkat cells. Three of these compounds were selected for further analysis and found to activate the IL-17 reporter with potencies of ∼0.1 μM measured by EC₅₀. These compounds were shown to directly bind to RORγ by circular dichroism-based thermal stability experiments. Furthermore, they can enhance an in vitro Th17 differentiation process in human primary T cells. As RORγ remains an orphan nuclear receptor, discovery of these aryl amide compounds as functional agonists will now provide pharmacological tools for us to dissect functions of RORγ and facilitate drug discovery efforts for immune-modulating therapies.

  7. Design, synthesis, and protein crystallography of biaryltriazoles as potent tautomerase inhibitors of macrophage migration inhibitory factor.

    Science.gov (United States)

    Dziedzic, Pawel; Cisneros, José A; Robertson, Michael J; Hare, Alissa A; Danford, Nadia E; Baxter, Richard H G; Jorgensen, William L

    2015-03-04

    Optimization is reported for biaryltriazoles as inhibitors of the tautomerase activity of human macrophage migration inhibitory factor (MIF), a proinflammatory cytokine associated with numerous inflammatory diseases and cancer. A combined approach was taken featuring organic synthesis, enzymatic assaying, crystallography, and modeling including free-energy perturbation (FEP) calculations. X-ray crystal structures for 3a and 3b bound to MIF are reported and provided a basis for the modeling efforts. The accommodation of the inhibitors in the binding site is striking with multiple hydrogen bonds and aryl-aryl interactions. Additional modeling encouraged pursuit of 5-phenoxyquinolinyl analogues, which led to the very potent compound 3s. Activity was further enhanced by addition of a fluorine atom adjacent to the phenolic hydroxyl group as in 3w, 3z, 3aa, and 3bb to strengthen a key hydrogen bond. It is also shown that physical properties of the compounds can be modulated by variation of solvent-exposed substituents. Several of the compounds are likely the most potent known MIF tautomerase inhibitors; the most active ones are more than 1000-fold more active than the well-studied (R)-ISO-1 and more than 200-fold more active than the chromen-4-one Orita-13.

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

    KAUST Repository

    Fan, Lulu

    2016-09-23

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

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

    KAUST Repository

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

    2016-01-01

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

  10. Alkylation and arylation of alkenes by transition metal complexes

    International Nuclear Information System (INIS)

    Volkova, L.G.; Levitin, I.Ya.; Vol'pin, M.E.

    1975-01-01

    In this paper are reviewed methods of alkylation and irylation of unsaturated compounds with complexes of transition metals (Rh, Pd). Analysis of alkylation and arylation of olefines with organic derivatives of transition metals, obtained as a result of exchange reactions between organic compounds of transition metals and salts of metals of the 8th group of the periodic system, allows a conclusion as to the wide possibilities of these reactions in the synthesis of various derivatives of unsaturated compounds. In all the reactions under consideration, intermediate formation of sigma-complexes is assumed. Also considered are alkylation and arylation of olefines with organic derivatives of halogens in the presence of compounds of metals of the 8th group of the periodic system, as well as arylation of olefines with aromatic compounds in the presence of salts of transition metals

  11. Visible-light-mediated selective arylation of cysteine in batch and flow

    NARCIS (Netherlands)

    Bottecchia, C.; Rubens, M.; Gunnoo, S.B.; Hessel, V.; Madder, A.

    2017-01-01

    A mild visible-light-mediated strategy for cysteine arylation is presented. The method relies on the use of eosin Y as a metal-free photocatalyst and aryldiazonium salts as arylating agents. The reaction can be significantly accelerated in a microflow reactor, whilst allowing the in situ formation

  12. Palladium-catalysed arylation of acetoacetate esters to yield 2-arylacetic acid esters

    CSIR Research Space (South Africa)

    Zeevaart, JG

    2004-05-24

    Full Text Available , was developed simultaneously by Hart- wig and Buchwald.5 Typically the tert-butyl ester of propionic acid is treated with an aryl halide (bromide or chloride) in the presence of a strong base, palladium and a bulky phosphine ligand or a bulky imidazolinium CO2t... novel palladium- catalysed conditions for the arylation of acetoacetate esters resulting in the formation of 2-arylacetic acid esters. When we attempted the arylation of tert-butyl aceto- acetate 1a with bromobenzene 2a using mild reaction conditions (K3...

  13. Bedford-type palladacycle catalyzed Miyaura-borylation of aryl halides with tetrahydroxydiboron in water

    KAUST Repository

    Zernickel, Anna; Du, Weiyuan; Ghorpade, Seema; Sawant, Dinesh Nanaji; Makki, Arwa; Sekar, Nagaiyan; Eppinger, Jö rg

    2018-01-01

    A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 hours in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.

  14. Bedford-type palladacycle catalyzed Miyaura-borylation of aryl halides with tetrahydroxydiboron in water

    KAUST Repository

    Zernickel, Anna

    2018-01-09

    A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 hours in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.

  15. Silane Cross-Linked Sulfonted Poly(Ether Ketone/Ether Benzimidazoles for Fuel Cell Applications

    Directory of Open Access Journals (Sweden)

    Zilu Yao

    2017-11-01

    Full Text Available γ-(2,3-epoxypropoxy propyltrimethoxysilane (KH-560 was incorporated in various proportions into side-chain-type sulfonated poly(ether ketone/ether benzimidazole (SPEKEBI as a crosslinker, to make membranes with high ion exchange capacities and excellent performance for direct methanol fuel cells (DMFCs. Systematical measurements including Fourier transform infrared (FT-IR, scanning electron microscopy-energy-dispersive and X-ray photoelectron spectroscopy (XPS proved the complete disappearance of epoxy groups in KH-560 and the existence of Si in the membranes. The resulting membranes showed increased mechanical strength and thermal stability compared to the unmodified sulfonated poly(ether ketone/ether benzimidazole membrane in appropriate doping amount. Meanwhile, the methanol permeability has decreased, leading to the increase of relative selectivities of SPEKEBI-x-SiO2 membranes. Furthermore, the H2/O2 cell performance of SPEKEBI-2.5-SiO2 membrane showed a much higher peak power density compared with the pure SPEKEBI memrbrane.

  16. Critical properties of some aliphatic symmetrical ethers

    International Nuclear Information System (INIS)

    Nikitin, Eugene D.; Popov, Alexander P.; Bogatishcheva, Nataliya S.

    2014-01-01

    Highlights: • Critical properties of simple aliphatic ethers were measured. • The ethers decompose at near-critical temperatures. • Pulse-heating method with short residence times was used. -- Abstract: The critical temperatures T c and the critical pressures p c of dihexyl, dioctyl, and didecyl ethers have been measured. According to the measurements, the coordinates of the critical points are T c = (665 ± 7) K, p c = (1.44 ± 0.04) MPa for dihexyl ether, T c = (723 ± 7) K, p c = (1.19 ± 0.04) MPa for dioctyl ether, and T c = (768 ± 8) K, p c = (1.03 ± 0.03) MPa for didecyl ether. All the ethers studied degrade chemically at near-critical temperatures. A pulse-heating method applicable to measuring the critical properties of thermally unstable compounds has been used. The times from the beginning of a heating pulse to the moment of reaching the critical temperature were from 0.06 to 0.46 ms. The short residence times provide little decomposition of the substances in the course of the experiments. The critical properties of the ethers investigated in this work have been discussed together with those of methyl to butyl ethers. The experimental critical constants of the ethers have been compared with those estimated by the group-contribution methods of Wilson and Jasperson and Marrero and Gani. The Wilson/Jasperson method provides a better estimation of the critical temperatures and pressures of simple aliphatic ethers in comparison with the Marrero/Gani method if reliable normal boiling temperatures are used in the method of Wilson and Jasperson

  17. Radiation-induced cationic curing of vinyl ethers

    International Nuclear Information System (INIS)

    Lapin, S.C.

    1992-01-01

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

  18. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

    Science.gov (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

    2014-10-01

    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  19. Poly (ether ether ketone) membranes for fuel cells

    International Nuclear Information System (INIS)

    Marrero, Jacqueline C.; Gomes, Ailton de S.; Filho, Jose C.D.; Hui, Wang S.; Oliveira, Vivianna S. de

    2015-01-01

    Polymeric membranes were developed using a SPEEK polymer matrix (sulphonated poly (ether ether ketone)), containing hygroscopic particles of zirconia (Zr) (incorporated by sol-gel method), for use as electrolyte membranes in fuel cells. SPEEK with different sulfonation degrees were used: 63 and 86%. The thermal analysis (TGA and DSC) was carried out to characterize the membranes and electrochemical impedance spectroscopy (EIS) was carried out to evaluating the proton conductivity of the membranes. Additional analysis were underway in order to characterize these membranes, which include: X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in order to evaluate the influence of zirconia and sulfonation degree on the properties of the membranes. (author)

  20. Ion-Selective Ionic Polymer Metal Composite (IPMC) actuator based on crown ether containing sulfonated Poly(Arylene Ether Ketone)

    NARCIS (Netherlands)

    Tas, S.; Zoetebier, B.; Sukas, O.S.; Bayraktar, M.; Hempenius, M.; Vancso, G.J.; Nijmeijer, K.

    2017-01-01

    This study introduces the concept of ion selective actuation in polymer metal composite actuators, employing crown ether bearing aromatic polyether materials. For this purpose, sulfonated poly(arylene ether ketone) (SPAEK) and crown ether containing SPAEK with molar masses suitable for membrane

  1. Light-Induced C-H Arylation of (Hetero)arenes by In Situ Generated Diazo Anhydrides.

    Science.gov (United States)

    Cantillo, David; Mateos, Carlos; Rincon, Juan A; de Frutos, Oscar; Kappe, C Oliver

    2015-09-07

    Diazo anhydrides (Ar-N=N-O-N=N-Ar) have been known since 1896 but have rarely been used in synthesis. This communication describes the development of a photochemical catalyst-free C-H arylation methodology for the preparation of bi(hetero)aryls by the one-pot reaction of anilines with tert-butyl nitrite and (hetero)arenes under neutral conditions. The key step in this procedure is the in situ formation and subsequent photochemical (>300 nm) homolytic cleavage of a transient diazo anhydride intermediate. The generated aryl radical then efficiently reacts with a (hetero)arene to form the desired bi(hetero)aryls producing only nitrogen, water, and tert-butanol as byproducts. The scope of the reaction for several substituted anilines and (hetero)arenes was investigated. A continuous-flow protocol increasing selectivity and safety has been developed enabling the experimentally straightforward preparation of a variety of substituted bi(hetero)aryls within 45 min of reaction time. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Unprecedentedly mild direct Pd-catalyzed arylation of oxazolo[4,5-b]pyridine

    DEFF Research Database (Denmark)

    Zhuravlev, Fedor

    2006-01-01

    Pd-catalyzed C-2 arylation of oxazolo[4,5-b]pyridine proceeds efficiently at 30 degrees C and tolerates a variety of aryl halides, including derivatized amino acids for which no racemization was observed during the reaction. Experimental evidence for facile deprotonation of oxazolo[4,5-b...

  3. Palladium-catalyzed aryl amination-heck cyclization cascade: A one-flask approach to 3-substituted Indoles

    DEFF Research Database (Denmark)

    Jensen, Thomas; Pedersen, Henrik; Bang-Andersen, B.

    2008-01-01

    Two for the price of one: A Pd/dppf-based catalyst provides access to the title compounds from 1,2-dihalogenated aromatic compounds and allylic amines in a single reaction flask. The initial aryl amination step occurs with excellent selectivity for the aryl iodide to ensure the formation of a sin......Two for the price of one: A Pd/dppf-based catalyst provides access to the title compounds from 1,2-dihalogenated aromatic compounds and allylic amines in a single reaction flask. The initial aryl amination step occurs with excellent selectivity for the aryl iodide to ensure the formation...

  4. N-aryl pyrrolo-tetrathiafulvalene based ligands: synthesis and metal coordination.

    Science.gov (United States)

    Balandier, Jean-Yves; Chas, Marcos; Dron, Paul I; Goeb, Sébastien; Canevet, David; Belyasmine, Ahmed; Allain, Magali; Sallé, Marc

    2010-03-05

    A straightforward general synthetic access to N-aryl-1,3-dithiolo[4,5-c]pyrrole-2-thione derivatives 6 from acetylenedicarbaldehyde monoacetal is depicted. In addition to their potentiality as precursors to dithioalkyl-pyrrole derivatives, thiones 6 are key building blocks to N-aryl monopyrrolo-tetrathiafulvalene (MPTTF) derivatives 10. X-ray structures of four of these thiones intermediates, reminiscent of the corresponding MPTTF derivatives, are provided. When the aryl group is a binding pyridyl unit, the MPTTF derivative 10a can coordinate M(II) salts (M = Pt, Pd). The first examples of metal-directed orthogonal MPTTF-based dimers 11-14, obtained through coordination of 10a to cis-blocked square planar Pt or Pd complexes are described. Studies on the parameters influencing the dimer construction are presented, as well as first recognition properties of the resulting electron-rich clip for C(60).

  5. Expedient synthesis of C-aryl carbohydrates by consecutive biocatalytic benzoin and aldol reactions.

    Science.gov (United States)

    Hernández, Karel; Parella, Teodor; Joglar, Jesús; Bujons, Jordi; Pohl, Martina; Clapés, Pere

    2015-02-16

    The introduction of aromatic residues connected by a C-C bond into the non-reducing end of carbohydrates is highly significant for the development of innovative structures with improved binding affinity and selectivity (e.g., C-aril-sLex). In this work, an expedient asymmetric "de novo" synthetic route to new aryl carbohydrate derivatives based on two sequential stereoselectively biocatalytic carboligation reactions is presented. First, the benzoin reaction of aromatic aldehydes to dimethoxyacetaldehyde is conducted, catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I. Then, the α-hydroxyketones formed are reduced by using NaBH4 yielding the anti diol. After acetal hydrolysis, the aldol addition of dihydroxyacetone, hydroxyacetone, or glycolaldehyde catalyzed by the stereocomplementary D-fructose-6-phosphate aldolase and L-rhamnulose-1-phosphate aldolase is performed. Both aldolases accept unphosphorylated donor substrates, avoiding the need of handling the phosphate group that the dihydroxyacetone phosphate-dependent aldolases require. In this way, 6-C-aryl-L-sorbose, 6-C-aryl-L-fructose, 6-C-aryl-L-tagatose, and 5-C-aryl-L-xylose derivatives are prepared by using this methodology. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. All solid supercapacitor based on polyaniline and crosslinked sulfonated poly[ether ether ketone

    International Nuclear Information System (INIS)

    Sivaraman, P.; Kushwaha, R.K.; Shashidhara, K.; Hande, V.R.; Thakur, A.P.; Samui, A.B.; Khandpekar, M.M.

    2010-01-01

    All solid supercapacitor based on polyaniline (PANI) and crosslinked sulfonated poly[ether ether ketone] (XSPEEK,) is reported in this paper. The crosslinker used for sulfonated poly[ether ether ketone] (SPEEK) is 1,4-bis(hydroxymethyl) benzene. The XSPEEK is used as both solid electrolyte and separator membrane. Supercapacitors are fabricated using various PANI/XSPEEK weight ratios. These are characterized by cyclic voltammetry and galvanostatic charge-discharge studies. The supercapacitor with PANI/XSPEEK weight ratio 1:0.5, exhibit a specific capacitance of 480 F g -1 of PANI. To the best of authors' knowledge, the value reported here is the highest for a supercapacitor based on a proton conducting solid polymer electrolyte and PANI. Detailed electrochemical impedance spectroscopy analysis is carried out. The analysis shows that the complex capacitance of the supercapacitor depends on the XSPEEK content. The time constant (t 0 ), derived from the imaginary part of complex capacitance decreases with increase in the XSPEEK content in the supercapacitor. Cycle life characteristics of the supercapacitor show a decrease in specific capacitance during initial cycles and get stabilized during later cycles.

  7. Hydrogen storage by functionalised Poly(ether ether ketone)

    Energy Technology Data Exchange (ETDEWEB)

    Pedicini, R.; Giacoppo, G.; Carbone, A.; Passalacqua, E. [CNR-ITAE, Messina (Italy). Inst. for Advanced Energy Technologies

    2010-07-01

    In this work a functionalised polymer was studied as potential material for hydrogen storage in solid state. A Poly(ether ether ketone) (PEEK) matrix was modified by a manganese oxide in situ formation. Here we report the functionalisation process and the preliminary results on hydrogen storage capability of the synthesised polymer. The polymer was characterized by Scanning Electron Microscopy, X-ray diffraction, Transmission Electron Microscopy and Gravimetric Hydrogen Adsorption measurements. In the functionalised PEEK, morphological changes occur as a function of oxide precursor concentration and reaction time. Promising results by gravimetric measurements were obtained with a hydrogen sorption of 0.24%wt/wt at 50 C and 60 bar, moreover, reversibility hydrogen adsorption and desorption in a wide range of both temperature and pressure was confirmed. (orig.)

  8. Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

    International Nuclear Information System (INIS)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Ma, Lichun; Qi, Meiwei; Yu, Jiali; Huang, Yudong

    2014-01-01

    Highlights: • Carbon fibers are grafted with phenyl amine group via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 73%. • Tensile strength of the carbon fibers does not decrease distinctly. • Using water as the reaction medium can avoid pollution from organic solvents. • Grafting via aryl diazonium reaction in one step can improve modification efficiency. - Abstract: Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction “on water” to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction “on water” could be a facile green platform to functionalize carbon fibers for many interesting applications

  9. Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yuwei [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Meng, Linghui [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Fan, Liquan [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Ma, Lichun; Qi, Meiwei; Yu, Jiali [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Huang, Yudong, E-mail: ydhuang.hit1@yahoo.com.cn [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China)

    2014-10-15

    Highlights: • Carbon fibers are grafted with phenyl amine group via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 73%. • Tensile strength of the carbon fibers does not decrease distinctly. • Using water as the reaction medium can avoid pollution from organic solvents. • Grafting via aryl diazonium reaction in one step can improve modification efficiency. - Abstract: Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction “on water” to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction “on water” could be a facile green platform to functionalize carbon fibers for many interesting applications.

  10. Oxidative addition of aryl chlorides to monoligated palladium(0): A DFT-SCRF study

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Norrby, Per-Ola

    2007-01-01

    Oxidative addition of aryl chlorides to palladium has been investigated by hybrid density functional theory methods (B3LYP), including a continuum model describing the solvent implicitly. A series of para-substituted aryl chlorides were studied to see the influence of electronic effects...

  11. Rh(I)-Catalyzed Arylation of Heterocycles via C-H Bond Activation: Expanded Scope Through Mechanistic Insight

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Berman, Ashley; Bergman, Robert; Ellman, Jonathan

    2007-07-18

    A practical, functional group tolerant method for the Rh-catalyzed direct arylation of a variety of pharmaceutically important azoles with aryl bromides is described. Many of the successful azole and aryl bromide coupling partners are not compatible with methods for the direct arylation of heterocycles using Pd(0) or Cu(I) catalysts. The readily prepared, low molecular weight ligand, Z-1-tert-butyl-2,3,6,7-tetrahydrophosphepine, which coordinates to Rh in a bidentate P-olefin fashion to provide a highly active yet thermally stable arylation catalyst, is essential to the success of this method. By using the tetrafluoroborate salt of the corresponding phosphonium, the reactions can be assembled outside of a glove box without purification of reagents or solvent. The reactions are also conducted in THF or dioxane, which greatly simplifies product isolation relative to most other methods for direct arylation of azoles employing high-boiling amide solvents. The reactions are performed with heating in a microwave reactor to obtain excellent product yields in two hours.

  12. Activity relationships for aromatic crown ethers

    International Nuclear Information System (INIS)

    Wilson, Mark James

    1998-01-01

    This thesis involves an investigation of aromatic crown ethers and a study of their binding constants for alkali metals. The study was motivated by the current needs of the semiconductor industry to improve the scavenging of mobile ions from fabricated circuits. A number of aromatic crown ethers have been sulphonated in an attempt to improve their water solubility and cation binding activity. These materials have been extensively studied and their binding activity determined. In collaboration with a molecular modelling study, the effect of ionisable sulphonate groups on the macrocycles' behaviour has been investigated. The broader issue of the effect of substituents in aromatic crown ethers has also been studied with the preparation of a wide range of substituted crown ethers. The cation binding activity of these materials has been found to bear a simple relationship to the electron withdrawing nature of the aromatic substituents. This relationship can be accurately monitored using electronic charge densities from molecular modelling and this rational has been applied to the study of proton ionisable and lariating crown ethers. The incorporation of crown ethers into polyamic acid and polyimide frameworks has also been investigated, where the resulting materials have been found to exhibit unusual cation binding and uptake properties. These results imply that the combination of the crown ethers' macrocycle and adjacent carboxylic acid residues, from the polyamic acids, are conducive to effective cationic binding. NMR measurements, in conjunction with molecular modelling, have been used to explore the geometry changes encountered as the crown ether goes from it's uncomplexed to its complexed state. The energy requirement for these geometry changes has subsequently been used to examine the cation selectivity of these materials. The electronic charge changes associated with the complexation have also been investigated and correlated with the theoretical results. (author)

  13. Palladium-catalysed arylation of sulfonamide stabilised enolates

    CSIR Research Space (South Africa)

    Zeevaart, JG

    2005-03-07

    Full Text Available Alpha-Arylation of inethanesulfonamides using palladium catalysis is described. For example, treatment of N-benzyl-Nmethylmethanesulfonamide with catalytic Pd (OAc) (2) in the presence of sodium tert-butoxide, triphenylphosphine and toluene afforded...

  14. Biaxial deformation behaviour of poly-ether-ether-ketone

    Science.gov (United States)

    Turner, Josh; Menary, Gary; Martin, Peter

    2018-05-01

    The biaxial tensile properties of thin poly-ether-ether-ketone (PEEK) films are presented. Investigation into the biaxial mechanical behaviour of PEEK films will provide a preliminary insight into the anticipated stress/strain response, and potential suitability, to the possible fabrication of thin walled parts through stretch blow moulding and thermoforming processes - with the multi-axial state of strain imposed onto the heated thermoplastic sheet representative of the expected strain history experienced during these material forming processes. Following identification of the prospective forming temperature window, the biaxial mechanical behaviour of the material is characterized under differing modes of deformation, at a nominal strain rate of 1 s-1. The temperature dependence is outlined within - with an appreciable increase in flow behaviour correlated with specimen temperature exceeding its glass transition temperature (Tg).

  15. Reduction of Nitroarenes into Aryl Amines and N-Aryl hydroxylamines via Activation of NaBH4 and Ammonia-Borane Complexes by Ag/TiO2 Catalyst

    Directory of Open Access Journals (Sweden)

    Dimitrios Andreou

    2016-03-01

    Full Text Available In this study, we report the fabrication of mesoporous assemblies of silver and TiO2 nanoparticles (Ag/MTA and demonstrate their catalytic efficiency for the selective reduction of nitroarenes. The Ag/TiO2 assemblies, which show large surface areas (119–128 m2·g−1 and narrow-sized mesopores (ca. 7.1–7.4 nm, perform as highly active catalysts for the reduction of nitroarenes, giving the corresponding aryl amines and N-aryl hydroxylamines with NaBH4 and ammonia-borane (NH3BH3, respectively, in moderate to high yields, even in large scale reactions (up to 5 mmol. Kinetic studies indicate that nitroarenes substituted with electron-withdrawing groups reduced faster than those with electron-donating groups. The measured positive ρ values from the formal Hammett-type kinetic analysis of X-substituted nitroarenes are consistent with the proposed mechanism that include the formation of possible [Ag]-H hybrid species, which are responsible for the reduction process. Because of the high observed chemo selectivities and the clean reaction processes, the present catalytic systems, i.e., Ag/MTA-NaBH4 and Ag/MTA-NH3BH3, show promise for the efficient synthesis of aryl amines and N-aryl hydroxylamines at industrial levels.

  16. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin; Falivene, Laura; Drinkel, Emma E.; Grant, Sharday; Linden, Anthony; Cavallo, Luigi; Dorta, Reto

    2012-01-01

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin

    2012-02-06

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Novel crosslinked membranes based on sulfonated poly(ether ether ketone) for direct methanol fuel cells.

    Science.gov (United States)

    Zhu, Yuanqin; Zieren, Shelley; Manthiram, Arumugam

    2011-07-14

    Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.

  19. Preparation and Characterization of Sulfonated Poly (ether ether ...

    African Journals Online (AJOL)

    NJD

    2007-08-10

    Aug 10, 2007 ... Preparation and Characterization of Sulfonated Poly (ether ... Currently perfluori- ... with phosphoric acid solution according to the method described earlier.11,12 ... where A is the membrane area available for diffusion; CA is.

  20. A Modular Flow Design for the meta‐Selective C−H Arylation of Anilines

    Science.gov (United States)

    Gemoets, Hannes P. L.; Laudadio, Gabriele; Verstraete, Kirsten; Hessel, Volker

    2017-01-01

    Abstract Described herein is an effective and practical modular flow design for the meta‐selective C−H arylation of anilines. The design consists of four continuous‐flow modules (i.e., diaryliodonium salt synthesis, meta‐selective C−H arylation, inline copper extraction, and aniline deprotection) which can be operated either individually or consecutively to provide direct access to meta‐arylated anilines. With a total residence time of 1 hour, the desired product could be obtained in high yield and excellent purity without the need for column chromatography, and the residual copper content meets the standards for parenterally administered pharmaceutical substances. PMID:28543979

  1. Cu-Click Compatible Triazabutadienes To Expand the Scope of Aryl Diazonium Ion Chemistry.

    Science.gov (United States)

    Cornali, Brandon M; Kimani, Flora W; Jewett, John C

    2016-10-07

    Triazabutadienes can be used to readily generate reactive aryl diazonium ions under mild, physiologically relevant conditions. These conditions are compatible with a range of functionalities that do not tolerate traditional aryl diazonium ion generation. To increase the utility of this aryl diazonium ion releasing chemistry an alkyne-containing triazabutadiene was synthesized. The copper-catalyzed azide-alkyne cycloaddition ("Cu-click") reaction was utilized to modify the alkyne-containing triazabutadiene and shown to be compatible with the nitrogen-rich triazabutadiene. One of the triazole products was tethered to a fluorophore, thus enabling the direct fluorescent labeling of a model protein.

  2. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Chiu, K.-F.; Su, S.-H., E-mail: minimono42@gmail.com

    2013-10-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO{sub 4} were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO{sub 4}, the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance.

  3. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    International Nuclear Information System (INIS)

    Chiu, K.-F.; Su, S.-H.

    2013-01-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO 4 were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO 4 , the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance

  4. Microwave-assisted cyclizations promoted by polyphosphoric acid esters: a general method for 1-aryl-2-iminoazacycloalkanes

    Directory of Open Access Journals (Sweden)

    Jimena E. Díaz

    2016-09-01

    Full Text Available The first general procedure for the synthesis of 5 to 7-membered 1-aryl-2-iminoazacycloalkanes is presented, by microwave-assisted ring closure of ω-arylaminonitriles promoted by polyphosphoric acid (PPA esters. 1-Aryl-2-iminopyrrolidines were easily prepared from the acyclic precursors employing a chloroformic solution of ethyl polyphosphate (PPE. The use of trimethylsilyl polyphosphate (PPSE in solvent-free conditions allowed for the synthesis of 1-aryl-2-iminopiperidines and hitherto unreported 1-aryl-2-iminoazepanes. The cyclization reaction involves good to high yields and short reaction times, and represents a novel application of PPA esters in heterocyclic synthesis.

  5. Hardness and wear properties of boron-implanted poly(ether-ether-ketone) and poly-ether-imide

    International Nuclear Information System (INIS)

    Lee Youngchul; Lee, E.H.; Mansur, L.K.

    1992-01-01

    The effects of boron beam irradiation on the hardness, friction, and wear of polymer surfaces were investigated. Typical high-performance thermoplastics, poly(ether-ether-ketone) (PEEK) and a poly-ether-imide (Ultem) were studied after 200 keV boron ion beam treatment at ambient temperature to doses of 2.3x10 14 , 6.8x10 14 , and 2.2x10 15 ions cm -2 . The hardnesses of pristine and boron-implanted materials were characterized by a conventional Knoop method and a load-depth sensing nanoindentation technique. Both measurements showed a significant increase in hardness with increasing dose. The increase in hardness was also found to depend on the penetration depth of the diamond indenter. Wear and friction properties were characterized by a reciprocating sliding friction tester with an SAE 52100 high-carbon, chrome steel ball at 0.5 and 1 N normal loads. Wear and frictional properties varied in a complex fashion with polymer type and dose, but not much with normal load. A substantial reduction in friction coefficient was observed for PEEK at the highest dose but no reduction was observed for Ultem. The wear damage was substantially reduced at the highest dose for both Ultem and PEEK. For the system studied, the highest dose, 2.2x10 15 ions cm -2 , appears to be optimum in improving wear resistance for both PEEK and Ultem. (orig.)

  6. Optical anisotropy, molecular orientations, and internal stresses in thin sulfonated poly(ether ether ketone) films

    NARCIS (Netherlands)

    Koziara, B.T.; Nijmeijer, K.; Benes, N.E.

    2015-01-01

    The thickness, the refractive index, and the optical anisotropy of thin sulfonated poly(ether ether ketone) films, prepared by spin-coating or solvent deposition, have been investigated with spectroscopic ellipsometry. For not too high polymer concentrations (≤5 wt%) and not too low spin speeds

  7. Optical anisotropy, molecular orientations, and internal stresses in thin sulfonated poly(ether ether ketone) films

    NARCIS (Netherlands)

    Koziara, Beata; Nijmeijer, Dorothea C.; Benes, Nieck Edwin

    2015-01-01

    The thickness, the refractive index, and the optical anisotropy of thin sulfonated poly(ether ether ketone) films, prepared by spin-coating or solvent deposition, have been investigated with spectroscopic ellipsometry. For not too high polymer concentrations (B5 wt%) and not too low spin speeds

  8. S-adenosylmethionine decarboxylase inhibitors: new aryl and heteroaryl analogues of methylglyoxal bis(guanylhydrazone).

    Science.gov (United States)

    Stanek, J; Caravatti, G; Capraro, H G; Furet, P; Mett, H; Schneider, P; Regenass, U

    1993-01-08

    A series of 3-acylbenzamidine (amidino)hydrazones 7a-h, the corresponding (hetero)aromatic congeners 7i-p, and 3,3'-bis-amidino-biaryls 25a-e were synthesized. The hydrazones 7a-p were prepared by conversion of the corresponding acyl nitriles 1a,c-d,i,n-p to the imido esters 3a,c-d,i and the amidines 5a,c-d,h-i, followed by a reaction with aminoguanidine, or vice versa. Similarly, the biaryl 3,3'-dinitriles 23a-e were converted, via the imino esters 24a-c or the imino thioesters 27d-e, to the diamidines 25a-e. These new products are conformationally constrained analogues of methylglyoxal bis(guanylhydrazone) (MGBG). They are up to 100 times more potent as inhibitors of rat liver S-adenosylmethionine decarboxylase (SMDC) and generally less potent inhibitors of rat small intestine diamine oxidase (DAO) than MGBG. Some of these SAMDC inhibitors, e.g., compounds 7a, 7e, 7i, 25a, and 25d, have shown antiproliferative effects against T24 human bladder carcinoma cells. These products, whose structure-activity relationships are discussed, are of interest as potential anticancer agents and drugs for the treatment of protozoal and Pneumocystis carinii infections.

  9. Synthesis and evaluation of 1,4-naphthoquinone ether derivatives as SmTGR inhibitors and new anti-schistosomal drugs.

    Science.gov (United States)

    Johann, Laure; Belorgey, Didier; Huang, Hsin-Hung; Day, Latasha; Chessé, Matthieu; Becker, Katja; Williams, David L; Davioud-Charvet, Elisabeth

    2015-08-01

    Investigations regarding the chemistry and mechanism of action of 2-methyl-1,4-naphthoquinone (or menadione) derivatives revealed 3-phenoxymethyl menadiones as a novel anti-schistosomal chemical series. These newly synthesized compounds (1-7) and their difluoromethylmenadione counterparts (8, 9) were found to be potent and specific inhibitors of Schistosoma mansoni thioredoxin-glutathione reductase (SmTGR), which has been identified as a potential target for anti-schistosomal drugs. The compounds were also tested in enzymic assays using both human flavoenzymes, i.e. glutathione reductase (hGR) and selenium-dependent human thioredoxin reductase (hTrxR), to evaluate the specificity of the inhibition. Structure-activity relationships as well as physico- and electro-chemical studies showed a high potential for the 3-phenoxymethyl menadiones to inhibit SmTGR selectively compared to hGR and hTrxR enzymes, in particular those bearing an α-fluorophenol methyl ether moiety, which improves anti-schistosomal action. Furthermore, the (substituted phenoxy)methyl menadione derivative (7) displayed time-dependent SmTGR inactivation, correlating with unproductive NADPH-dependent redox cycling of SmTGR, and potent anti-schistosomal action in worms cultured ex vivo. In contrast, the difluoromethylmenadione analog 9, which inactivates SmTGR through an irreversible non-consuming NADPH-dependent process, has little killing effect in worms cultured ex vivo. Despite ex vivo activity, none of the compounds tested was active in vivo, suggesting that the limited bioavailability may compromise compound activity. Therefore, future studies will be directed toward improving pharmacokinetic properties and bioavailability. © 2015 FEBS.

  10. Poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) membranes

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Mi-Lim; Choi, Jisun; Woo, Hyun-Su; Kumar, Vinod; Sohn, Joon-Yong; Shin, Junhwa, E-mail: shinj@kaeri.re.kr

    2014-02-15

    Highlights: • PEEK-g-PVBSA, a polymer electrolyte membrane was prepared by a radiation grafting technique. • Poly(ether ether ketone) (PEEK), an aromatic hydrocarbon polymer was used as a grafting backbone film. • The water uptake, proton conductivity, and methanol permeability of the membranes were evaluated. • PEEK-g-PVBSA membranes show considerably lower methanol permeability compared to a Nafion membrane. -- Abstract: In this study, an aromatic hydrocarbon based polymer electrolyte membrane, poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) (PEEK-g-PVBSA), has been prepared by the simultaneous irradiation grafting of vinylbenzyl chloride (VBC) monomer onto a PEEK film and subsequent sulfonation. Each chemical conversion was monitored by FT-IR and SEM–EDX instruments. The physicochemical properties including IEC, water uptake, proton conductivity, and methanol permeability of the prepared membranes were also investigated and found that the values of these properties increase with the increase of degree of grafting. It was observed that the IEC values of the prepared PEEK-g-PVBSA membranes with 32%, 58%, and 80% DOG values were 0.50, 1.05, and 1.22 meq/g while the water uptakes were 14%, 20%, and 21%, respectively. The proton conductivities (0.0272–0.0721 S/cm at 70 °C) were found to be somewhat lower than Nafion 212 (0.126 S/cm at 70 °C) at a relative humidity of 90%. However, the prepared membranes showed a considerably lower methanol permeability (0.61–1.92 × 10{sup −7} cm{sup 2}/s) compared to a Nafion 212 membrane (5.37 × 10{sup −7} cm{sup 2}/s)

  11. Thermal stability of sulfonated Poly(Ether Ether Ketone) films : on the role of Protodesulfonation

    NARCIS (Netherlands)

    Koziara, B.T.; Kappert, E.J.; Ogieglo, W.; Nijmeijer, Kitty; Hempenius, M.A.; Benes, N.E.

    Thin film and bulk, sulfonated poly(ether ether ketone) (SPEEK) have been subjected to a thermal treatment at 160–250 °C for up to 15 h. Exposing the films to 160 °C already causes partial desulfonation, and heating to temperatures exceeding 200 °C results in increased conjugation in the material,

  12. Photoinduced C-C Cross-Coupling of Aryl Chlorides and Inert Arenes

    Directory of Open Access Journals (Sweden)

    Lele Wang

    2016-01-01

    Full Text Available Here we report a facile, efficient, and catalyst-free method to realize C-C cross-coupling of aryl chlorides and inert arenes under UV light irradiation. The aryl radical upon homolytic cleavage of C-Cl bond initiated the nucleophilic substitution reaction with inert arenes to give biaryl products. This mild reaction mode can also be applied to other synthetic reactions, such as the construction of C-N bonds and trifluoromethylated compounds.

  13. 6-Alkyl-, 6-aryl- or 6-hetaryl-7-deazapurine ribonucleosides as inhibitors of human or MTB adenosine kinase and potential antimycobacterial agents

    Czech Academy of Sciences Publication Activity Database

    Perlíková, Pavla; Konečný, P.; Nauš, Petr; Snášel, Jan; Votruba, Ivan; Džubák, P.; Pichová, Iva; Hajdúch, M.; Hocek, Michal

    2013-01-01

    Roč. 4, č. 11 (2013), s. 1497-1500 ISSN 2040-2503 R&D Projects: GA ČR GAP207/11/0344 EU Projects: European Commission(XE) 241587 - SYSTEMTB Grant - others:Operational Programme Research and Development for Innovations(XE) CZ.1.05/2.1.00/01.0030 Institutional support: RVO:61388963 Keywords : mycobacterium- tuberculosis * enzyme-inhibition * 6-(het)aryl-7-deazapurine ribonucleosides Subject RIV: CC - Organic Chemistry Impact factor: 2.626, year: 2013

  14. Catalytic Asymmetric Alkylation of Aryl Heteroaryl Ketones

    NARCIS (Netherlands)

    Ortiz, Pablo; Harutyunyan, Syuzanna; del Hoyo, Ana

    Tertiary diarylmethanols are highly bioactive structural motifs. A new strategy to access chiral tertiary diarylmethanols through copper-catalyzed direct alkylation of (di)(hetero)aryl ketones by using Grignard reagents was developed. The low reactivity and the similarity of the enantiotopic faces

  15. Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

    Directory of Open Access Journals (Sweden)

    Burkhard Koenig

    2011-01-01

    Full Text Available N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald–Hartwig-type reactions, copper-mediated Ullmann-type and Chan–Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan–Lam reactions. Chan–Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald–Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis.

  16. A convenient catalyst system for microwave accelerated cross-coupling of a range of aryl boronic acids with aryl chlorides

    Directory of Open Access Journals (Sweden)

    Milton Edward J

    2007-05-01

    Full Text Available Abstract A convenient microwave accelerated cross-coupling procedure between aryl chlorides with a range of boronic acids has been developed. An explanation for the low reactivity of highly fluorinated boronic acids in Suzuki coupling is provided.

  17. Sulfonamidation of Aryl and Heteroaryl Halides through Photosensitized Nickel Catalysis.

    Science.gov (United States)

    Kim, Taehoon; McCarver, Stefan J; Lee, Chulbom; MacMillan, David W C

    2018-03-19

    Herein we report a highly efficient method for nickel-catalyzed C-N bond formation between sulfonamides and aryl electrophiles. This technology provides generic access to a broad range of N-aryl and N-heteroaryl sulfonamide motifs, which are widely represented in drug discovery. Initial mechanistic studies suggest an energy-transfer mechanism wherein C-N bond reductive elimination occurs from a triplet excited Ni II complex. Late-stage sulfonamidation in the synthesis of a pharmacologically relevant structure is also demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Synthesis of nanodispersible 6-aryl-2,4-diamino-1,3,5-triazine and its derivatives

    International Nuclear Information System (INIS)

    Padalkar, Vikas S.; Patil, Vikas S.; Phatangare, Kiran R.; Gupta, Vinod D.; Umape, Prashant G.; Sekar, N.

    2010-01-01

    A series of novel branched derivatives of 6-aryl-2,4-diamino-1,3,5-triazine from corresponding aryl nitriles and dicyanodiamide was synthesized. These compounds show a nanodispersibility and good thermal stability.

  19. A transition-metal-free synthesis of arylcarboxyamides from aryl diazonium salts and isocyanides.

    Science.gov (United States)

    Xia, Zhonghua; Zhu, Qiang

    2013-08-16

    A transition-metal-free carboxyamidation process, using aryl diazonium tetrafluoroborates and isocyanides under mild conditions, has been developed. This novel conversion was initiated by a base and solvent induced aryl radical, followed by radical addition to isocyanide and single electron transfer (SET) oxidation, affording the corresponding arylcarboxyamide upon hydration of the nitrilium intermediate.

  20. On new physical reality (on ψ-ether)

    International Nuclear Information System (INIS)

    Isaev, P.S.

    2002-01-01

    It is shown that there exists a new physical reality - the ψ-ether. All the achievements of quantum mechanics and quantum field theory are due to the fact that both the theories include the influence of ψ-ether on the physical processes occurring in the Universe. Physics of the XX century was first of all the physics of ψ-ether

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

    KAUST Repository

    Yue, Huifeng

    2017-12-06

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

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

    KAUST Repository

    Yue, Huifeng; Zhu, Chen; Rueping, Magnus

    2017-01-01

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

  3. An air-stable copper reagent for nucleophilic trifluoromethylthiolation of aryl halides

    KAUST Repository

    Weng, Zhiqiang

    2012-12-12

    A series of copper(I) trifluoromethyl thiolate complexes have been synthesized from the reaction of CuF2 with Me3SiCF 3 and S8 (see scheme; Cu red, F green, N blue, S yellow). These air-stable complexes serve as reagents for the efficient conversion of a wide range of aryl halides into the corresponding aryl trifluoromethyl thioethers in excellent yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. An air-stable copper reagent for nucleophilic trifluoromethylthiolation of aryl halides

    KAUST Repository

    Weng, Zhiqiang; He, Weiming; Chen, Chaohuang; Lee, Richmond; Tan, Davin; Lai, Zhiping; Kong, Dedao; Yuan, Yaofeng; Huang, Kuo-Wei

    2012-01-01

    A series of copper(I) trifluoromethyl thiolate complexes have been synthesized from the reaction of CuF2 with Me3SiCF 3 and S8 (see scheme; Cu red, F green, N blue, S yellow). These air-stable complexes serve as reagents for the efficient conversion of a wide range of aryl halides into the corresponding aryl trifluoromethyl thioethers in excellent yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Aryl hydrocarbon receptor overexpression in miniaturized follicles in female pattern hair loss.

    Science.gov (United States)

    Ramos, Paulo Müller; Brianezi, Gabrielli; Martins, Ana Carolina Pereira; Silva, Márcia Guimarães da; Marques, Mariângela Esther Alencar; Miot, Hélio Amante

    2017-01-01

    The etiopathogenesis of female pattern hair loss is still poorly understood. In addition to genetic and hormonal elements, environmental factors could be involved. The aryl hydrocarbon receptor is expressed in keratinocytes and can be activated by environmental pollutants leading to alterations in the cell cycle, inflammation, and apoptosis. Here we demonstrate the overexpression of nuclear aryl hydrocarbon receptors in miniaturized hair follicles in female pattern hair loss.

  6. Aryl sulfonate based anticancer alkylating agents.

    Science.gov (United States)

    Sheikh, Hamdullah Khadim; Arshad, Tanzila; Kanwal, Ghazala

    2018-05-01

    This research work revolves around synthesis of antineoplastic alkylating sulfonate esters with dual alkylating sites for crosslinking of the DNA strands. These molecules were evaluated as potential antineoplastic cross linking alkylating agents by reaction with the nucleoside of Guanine DNA nucleobase at both ends of the synthesized molecule. Synthesis of the alkylating molecules and the crosslinking with the guanosine nucleoside was monitored by MALDITOF mass spectroscopy. The synthesized molecule's crosslinking or adduct forming rate with the nucleoside was compared with that of 1,4 butane disulfonate (busulfan), in form of time taken for the appearance of [M+H] + . It was found that aryl sulfonate leaving group was causing higher rate of nucleophilic attack by the Lewis basic site of the nucleobase. Furthermore, the rate was also found to be a function of electron withdrawing or donating nature of the substituent on the aryl ring. Compound with strong electron withdrawing substituent on the para position of the ring reacted fastest. Hence, new alkylating agents were synthesized with optimized or desired reactivity.

  7. A Modular Flow Design for the meta-Selective C-H Arylation of Anilines.

    Science.gov (United States)

    Gemoets, Hannes P L; Laudadio, Gabriele; Verstraete, Kirsten; Hessel, Volker; Noël, Timothy

    2017-06-12

    Described herein is an effective and practical modular flow design for the meta-selective C-H arylation of anilines. The design consists of four continuous-flow modules (i.e., diaryliodonium salt synthesis, meta-selective C-H arylation, inline copper extraction, and aniline deprotection) which can be operated either individually or consecutively to provide direct access to meta-arylated anilines. With a total residence time of 1 hour, the desired product could be obtained in high yield and excellent purity without the need for column chromatography, and the residual copper content meets the standards for parenterally administered pharmaceutical substances. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  8. Synthesis and study of thiocarbonate derivatives of choline as potential inhibitors of acetylcholinesterase.

    Science.gov (United States)

    Boyle, N A; Talesa, V; Giovannini, E; Rosi, G; Norton, S J

    1997-09-12

    Fourteen alkyl and aryl thiocarbonate derivatives of choline were synthesized and studied as potential inhibitors of acetylcholinesterase (AChE). Twelve of the compounds inhibited AChEs derived from calf forebrain, human red blood cells, and octopus brain ranging from low to moderately high inhibition potency. The concentration of each inhibitory compound giving 50% inhibition of enzyme activity (IC50 values, which ranged from 1 x 10(-2) to 8 x 10(-7) M) was determined and is reported; inhibitor constants (Ki values) for the most inhibitory compounds, (1-pentylthiocarbonyl)choline chloride and (1-heptylthiocarbonyl)choline chloride, were calculated from kinetic data and are also reported. The inhibitors are competitive with substrate, and they are not hydrolyzed by the AChE activities. Certain of these new compounds may provide direction for the development of new drugs that have anticholinesterase activity and may be used for the treatment of Alzheimer's disease.

  9. Reaction of aryl diazonium tetrafluoro borates with allyl methacrylate in the presence of rhodanide-anion

    International Nuclear Information System (INIS)

    Grishchuk, B.D.; Baranovskij, V.S.; Simchak, R.V.; Tulajdan, G.N.; Gorbovoj, P.M.

    2006-01-01

    Reaction of aryl diazonium tetrafluoro borates (I) with allyl ester of methacrylic acid in the water-acetone (1:5) medium is studied by means of IR spectroscopy and 1 H NMR. It is established that (I) reacts with aryl methacrylate in the presence of rhodanide-anion and catalytic quantities of copper salts with the formation of allyl esters of 2-thiocyanato-2-methyl-3-aryl propionic acids with the yield of 32-56%. Allyl fragment of biunsaturated compound shows no reaction under the tested conditions [ru

  10. Biodegradability of fuel-ethers in environment; Biodegradabilite des ethers-carburants dans l'environnement

    Energy Technology Data Exchange (ETDEWEB)

    Fayolle-Guichard, F

    2005-04-01

    Fuel ethers (methyl tert-butyl ether or MTBE, ethyl tert-butyl ether or ETBE and tert-amyl methyl ether or TAME have been used as gasoline additives since about twenty years in order to meet the requirements for the octane index and to limit the polluting emission in exhaust pipe gas (unburnt hydrocarbons and carbon monoxide). The high water solubility and the poor biodegradability of these compounds make them pollutants frequently encountered in aquifers. The present manuscript summarizes the knowledge concerning the biodegradability of fuel ethers obtained both at IFP and during collaborations with the Pasteur Institute (Paris), the Biotechnology Research Institute (Montreal, Canada) and the Center for Environmental Biotechnology (University of Tennessee, USA). Rhodococcus ruber IFP 2001 and Mycobacterium austroafricanum IFP 2012, two microorganisms isolated at IFP for their ability to grow, respectively, on ETBE and MTBE, were studied in order to determine the intermediates produced during MTBE and ETBE biodegradation and the enzymes required for each biodegradation step, thus allowing us to propose MTBE and ETBE catabolic pathways. A proteomic approach, from the protein induced during the degradation of ETBE or MTBE to the genes encoding these different enzymes, was carried out. The isolation of such genes is required:1) to use them for help in determining the bio-remediation capacities in polluted aquifers (DNA micro-arrays), 2) to monitor the microorganisms isolated for their degradative capacities during bio-remediation processes (fluorescent in situ hybridization or FISH) and 3) to create new tools for the detection and the quantification of ETBE or MTBE in contaminated aquifers (bio-sensor). The manuscript also describes the different ways for the adaptation of microorganisms to the presence of a xenobiotic compound. (author)

  11. Synthesis and preliminary evaluation of antinociceptive activity of novel isoxazolyl-aryl-hydrazones

    International Nuclear Information System (INIS)

    Reis, Silvio Leandro Goncalves Bomfim; Almeida, Valderes Moraes de; Almeida, Gleybson Correia de; Boaviagem, Karinna Moura; Mendes, Charles Christophe du Barriere; Faria, Antonio Rodolfo de; Goes, Alexandre Jose da Silva; Magalhaes, Laudelina Rodrigues; Silva, Teresinha Goncalves da

    2011-01-01

    New 2-isoxazoline aldehydes were synthesized, in good yields, from cycloadduct of the 1,3-dipolar cycloaddition reaction between endocyclic enecarbamate and carboethoxyformonitrile oxide (CEFNO). Condensation of these 2-isoxazoline aldehydes with several phenyl-hydrazines produced new isoxazolyl-aryl-hydrazones, which showed low toxicity and excellent antinociceptive activity, when compared to dipyrone. The antinociceptive activity of isoxazolyl-aryl-hydrazones was performed using the acetic acid-induced mice abdominal constrictions test. (author)

  12. Camphyl-based α-diimine palladium complexes: highly efficient precatalysts for direct arylation of thiazoles in open-air.

    Science.gov (United States)

    Chen, Fu-Min; Lu, Dong-Dong; Hu, Li-Qun; Huang, Ju; Liu, Feng-Shou

    2017-07-21

    Based on the strategy of the development of phosphine-free palladium-catalyzed direct C-H arylation, a series of camphyl-based α-diimine palladium complexes bearing sterically bulky substituents were synthesized and characterized. The palladium complexes were applied for the cross-coupling of thiazole derivatives with aryl bromides. The effect of the sterically bulky substituent on the N-aryl moiety as well as the reaction conditions was screened. Under the optimal protocols, a wide range of aryl bromides can be smoothly coupled with thiazoles in good to excellent yields in the presence of a low palladium loading of 0.2 mol% under open-air conditions.

  13. Sulfonated poly(ether ether ketone) membranes for electric double layer capacitors

    International Nuclear Information System (INIS)

    Kim, Wan Ju; Kim, Dong-Won

    2008-01-01

    Sulfonated poly(ether ether ketone) (S-PEEK) with different degree of sulfonation (DS) has been prepared and evaluated as a proton conducting membrane for electric double layer capacitor (EDLC). The polymer electrolytes prepared with S-PEEK membrane exhibited ionic conductivities about 1.2 x 10 -3 -4.5 x 10 -3 S cm -1 at room temperature, which depended on both soaking solvent and degree of sulfonation. The quasi-solid-state EDLCs consisted of activated carbon electrodes and S-PEEK membrane were assembled, and their electrochemical characteristics were studied by cyclic voltammetry and charge-discharge cycle tests. The effect of DS on the electrochemical performances of EDLCs has been investigated

  14. Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

    Science.gov (United States)

    Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

    2018-04-01

    Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

  15. The evolution of the matrix metalloproteinase inhibitor drug discovery program at abbott laboratories.

    Science.gov (United States)

    Wada, Carol K

    2004-01-01

    Matrix metalloproteinases (MMPs) have been implicated in several pathologies. At Abbott Laboratories, the matrix metalloproteinases inhibitor drug discovery program has focused on the discovery of a potent, selective, orally bioavailable MMP inhibitor for the treatment of cancer. The program evolved from early succinate-based inhibitors to utilizing in-house technology such as SAR by NMR to develop a novel class of biaryl hydroxamate MMP inhibitors. The metabolic instability of the biaryl hydroxamates led to the discovery of a new class of N-formylhydroxylamine (retrohydroxamate) biaryl ethers, exemplified by ABT-770 (16). Toxicity issues with this pre-clinical candidate led to the discovery of another novel class of retrohydroxamate MMP inhibitors, the phenoxyphenyl sulfones such as ABT-518 (19j). ABT-518 is a potent, orally bioavailable, selective inhibitor of MMP-2 and 9 over MMP-1 that has been evaluated in Phase I clinical trials in cancer patients.

  16. Promoting environmentally sound management of polybrominated diphenyl ethers in Asia.

    Science.gov (United States)

    Li, Jinhui; Zhao, Nana; Liu, Xue; Wu, Xiaoyang

    2014-06-01

    Polybrominated diphenyl ethers with persistent organic pollutant properties are required to be controlled by the Stockholm Convention. Recently, polybrominated diphenyl ether contamination has become widespread in Asia, mainly because of the disposal and recycling processes of polybrominated diphenyl ether-containing wastes. The management status, production, usage, import/export, treatment, and disposal, as well as implementation deficiencies for the environmentally sound management of polybrominated diphenyl ethers and polybrominated diphenyl ether-containing materials in ten Asian countries were investigated and assessed in this study. This information could help the participating countries implement the Stockholm Convention and could promote the regional environmentally sound management of polybrominated diphenyl ether-containing articles and products. The results obtained were as follows. (1) Most of the countries studied lacked environmental policies and regulations, or even standards of polybrominated diphenyl ether pollution management and emission control actions. Accurate data on the consumption and importation of polybrominated diphenyl ether-containing materials, however, were not available for all the participating countries. In addition, there were no special treatment or disposal systems for polybrominated diphenyl ether-containing materials, or emission-cutting measures for the treatment of waste in these countries, owing to the lack of sufficient funding or technologies. (2) The improper dismantling of e-waste is a major source of polybrominated diphenyl ether emissions in these countries. (3) Proper e-waste management could result in a breakthrough in the environmentally sound management of this major polybrominated diphenyl ether-containing material flow, and could significantly reduce polybrominated diphenyl ether emissions. Finally, based on the study results, this article puts forward some recommendations for improving the environmentally

  17. Chemoselective Deprotection of Triethylsilyl Ethers

    Science.gov (United States)

    Chandra, Tilak; Broderick, William E.; Broderick, Joan B.

    2009-01-01

    An efficient and selective method was developed for the deprotection of triethylsilyl (TES) ethers using formic acid in methanol (5–10%) or in methylene chloride 2–5%) with excellent yields. TES ethers are selectively deprotected to the corresponding alcohols in high yields using formic acid in methanol under mild reaction conditions. Other hydroxyl protecting groups like t-butyldimethylsilyl (TBDMS) remain unaffected. PMID:20183570

  18. Oxidative cleavage of non-phenolic β-O-4 lignin model dimers by an extracellular aromatic peroxygenase

    Science.gov (United States)

    Matthias Kinne; Marzena Poraj-Kobielska; Rene Ullrich; Paula Nousiainen; Jussi Sipilä; Katrin Scheibner; Kenneth E. Hammel; Martin Hofrichter

    2011-01-01

    The extracellular aromatic peroxygenase of the agaric fungus Agrocybe aegerita catalyzed the H2O2-dependent cleavage of non-phenolic arylgiycerol-ß-aryl ethers (ß-O-4 ethers). For instance 1-(3,4-dimethoxyphenyl)-2-(2-methoxy-phenoxy)propane-1,3-diol, a recalcitrant dimeric lignin model compound that represents the major...

  19. [Early contributions from Erlangen to the theory and practice of ether and chloroform anesthesia. 1. Heyfelder's clinical trial with ether and chloroform].

    Science.gov (United States)

    Hintzenstern, U v; Schwarz, W

    1996-02-01

    The era of modern anaesthesia in Germany began on January 24th, 1847. This day, professor in ordinary Johann Ferdinand Heyfelder anaesthetized a patient with sulphuric ether in the clinic of surgery and ophthalmology of the University of Erlangen. By March 17th, 1847, Heyfelder had performed 121 surgical procedures under ether. The operations in majority were teeth-extractions, and a few more complex operations such as the treatment of a harelip or of lip cancer or the resection of the shoulder joint. Heyfelder described in detail 108 of these inhalations in a little book entitled The experiments with sulphuric ether. This monograph published in March, 1847, represents one of the first complete dissertations on sulphuric ether in the German literature. In a special chapter he analyzed the development of various physiological and psychological parameters during etherization. Heyfelder also examined blood and urine of some etherized patients and reported that he did not find any important or specific alterations. In 1847, Heyfelder was probably the first to apply salt-ether in man. After 4 administrations he concluded that salt ether acted more quickly but shorter than sulphuric ether. Advantageous were its application without problems and ease of induction. Disadvantageous were its high volatility, its price and the difficulty of getting it in a pure form. From December, 1847, on Heyfelder started to use chloroform. He was now able to perform more major operations, for example, the total resection of the hip-joint. In his book The experiments with sulphuric ether, salt ether, and chloroform he describes a great number of anaesthetic administrations using these 3 agents. In his summary Heyfelder concluded, that chloroform was undoubtly superior to sulphuric ether mainly because it was a quicker acting and longer lasting agent and leads to deeper narcosis. Moreover its application was much easier for it needed no special apparatus. However, because of its great

  20. Synthesis and Application of Pyrrolidone-containing Shale Inhibitors

    Science.gov (United States)

    Liu, Yonggui; Hou, Jie; Zhang, Yang; Yan, Jing; Song, Tao; Xu, Yongjun

    2018-03-01

    New generation polyamine inhibitors are amino-terminated polyethers with excellent inhibiting capabilities; they play a key role in borehole stabilization and reservoir protection. However, polyamine inhibitors are limited by their poor thermal stability, which can be attributed to the presence of ether bonds in their molecular structures. We propose a three-step synthesis approach fora novel pyrrolidone-containing polyamine inhibitor (DYNP) by introducing N-vinyl-2-pyrrolidone (NVP) on divinyloxyethane. This polyamine inhibitor exhibits an optimized molecular structure and has enhanced heat resistance. Characterizations by infrared (IR) spectroscopy and evaluation tests demonstrate several advantages of DYNP inhibitors, including excellent inhibiting capability (superior to similar materials such as polyamines), improved heat resistance (reasonable stability at temperatures up to 240°C), and good compatibility with both fresh water and salt water drilling fluids. These can be attributed to the presence of considerable amounts of amino groups in the repeating unit of DYNP molecules. The DYNP inhibitor was applied in over 20 boreholes in tight oil blocks in Daqing Oilfield to relieve hydration of formations with high shale contents. For instance, drilling in the 2033.5m horizontal section of Dragon 2 borehole was smooth, with a borehole diameter expansion ratio below 10%.

  1. Molecular structure impacts on secondary organic aerosol formation from glycol ethers

    Science.gov (United States)

    Li, Lijie; Cocker, David R.

    2018-05-01

    Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA

  2. Modified nanocrystal cellulose/fluorene-containing sulfonated poly(ether ether ketone ketone) composites for proton exchange membranes

    Science.gov (United States)

    Wei, Yingcong; Shang, Yabei; Ni, Chuangjiang; Zhang, Hanyu; Li, Xiaobai; Liu, Baijun; Men, Yongfeng; Zhang, Mingyao; Hu, Wei

    2017-09-01

    Highly sulfonated poly(ether ether ketone ketone)s (SFPEEKKs) with sulfonation degrees of 2.34 (SFPEEKK5) and 2.48 (SFPEEKK10) were synthesized through the direct sulfonation of a fluorene-containing poly(ether ether ketone ketone) under a relatively mild reaction condition. Using the solution blending method, sulfonated nanocrystal cellulose (sNCC)-enhanced SFPEEKK composites (SFPEEKK/sNCC) were successfully prepared for investigation as proton exchange membranes. Transmission electron microscopy showed that sNCC was uniformly distributed in the composite membranes. The properties of the composite membranes, including thermal stability, mechanical properties, water uptake, swelling ratio, oxidative stability and proton conductivity were thoroughly evaluated. Results indicated that the insertion of sNCC could contribute to water management and improve the mechanical performance of the membranes. Notably, the proton conductivity of SFPEEKK5/sNCC-5 was as high as 0.242 S cm-1 at 80 °C. All data proved the potential of SFPEEKK/sNCC composites for proton exchange membranes in medium-temperature fuel cells.

  3. A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol.

    Science.gov (United States)

    Leo, Pedro; Orcajo, Gisela; Briones, David; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Martínez, Fernando

    2017-06-16

    The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K₂CO₃ base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven.

  4. Microwave sintering of poly-ether-ether-ketone (PEEK) based coatings deposited on metallic substrate

    International Nuclear Information System (INIS)

    Zhang, G.; Leparoux, S.; Liao, H.; Coddet, C.

    2006-01-01

    In this paper, the feasibility of microwave (MW) sintering PEEK (poly-ether-ether-ketone) based coatings was investigated. Three coatings were studied: pure PEEK, micron-SiC and nano-SiC particles filled (wt.10%) PEEK coatings. The results indicate that, for the two composite coatings, the SiC particles distributed in the polymer matrix, as a good MW susceptor, could be heated preferentially by MW radiation. Consequently, the polymer matrix was heated by these particles

  5. Photolytic inhibition and labeling of proteins with aryl diazonium compounds

    International Nuclear Information System (INIS)

    Tometsko, A.M.; Turula, J.; Comstock, J.

    1978-01-01

    In the course of preparing aryl azide derivatives for use as photoprobes, we have observed significant light sensitivity in the precursor aryl diazonium compounds. The photosensitive properties of this class of compounds are of interest since they will seek out cationic binding sites in biological targets, and can be employed to inhibit complementary targets at acid pH. The relationship between photolytic change in the structure of diazonium compounds and the corresponding change in function of a biological target are presented. Experiments are described in which the dark and light sensitive properties of a model diazonium compound, diazobenzene sulfonate (DBS), were determined. The ultraviolet spectra were used to evaluate the dark stability and light sensitivity og DBS. Chymotrypsin and trypsin served as functioning targets for further evaluation of the photochemical properties. Both enzymes are stable to the probe in the dark at acid pH. A rapid loss of enzyme activity was observed following flash photolysis of DBS-enzyme solutions. Photolytic incorporation of radioactive DBS into chymotrypsin was observed. Aryl diazonium salts can be employed to probe the availability of complementary sites in biological targets at different acid pH values. (Author)

  6. Biodegradability of fuel-ethers in environment; Biodegradabilite des ethers-carburants dans l'environnement

    Energy Technology Data Exchange (ETDEWEB)

    Fayolle-Guichard, F.

    2005-04-01

    Fuel ethers (methyl tert-butyl ether or MTBE, ethyl tert-butyl ether or ETBE and tert-amyl methyl ether or TAME have been used as gasoline additives since about twenty years in order to meet the requirements for the octane index and to limit the polluting emission in exhaust pipe gas (unburnt hydrocarbons and carbon monoxide). The high water solubility and the poor biodegradability of these compounds make them pollutants frequently encountered in aquifers. The present manuscript summarizes the knowledge concerning the biodegradability of fuel ethers obtained both at IFP and during collaborations with the Pasteur Institute (Paris), the Biotechnology Research Institute (Montreal, Canada) and the Center for Environmental Biotechnology (University of Tennessee, USA). Rhodococcus ruber IFP 2001 and Mycobacterium austroafricanum IFP 2012, two microorganisms isolated at IFP for their ability to grow, respectively, on ETBE and MTBE, were studied in order to determine the intermediates produced during MTBE and ETBE biodegradation and the enzymes required for each biodegradation step, thus allowing us to propose MTBE and ETBE catabolic pathways. A proteomic approach, from the protein induced during the degradation of ETBE or MTBE to the genes encoding these different enzymes, was carried out. The isolation of such genes is required:1) to use them for help in determining the bio-remediation capacities in polluted aquifers (DNA micro-arrays), 2) to monitor the microorganisms isolated for their degradative capacities during bio-remediation processes (fluorescent in situ hybridization or FISH) and 3) to create new tools for the detection and the quantification of ETBE or MTBE in contaminated aquifers (bio-sensor). The manuscript also describes the different ways for the adaptation of microorganisms to the presence of a xenobiotic compound. (author)

  7. Composite perfluorohydrocarbon membranes, their preparation and use

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Yong; Bikson, Benjamin

    2017-04-04

    Composite porous hydrophobic membranes are prepared by forming a perfluorohydrocarbon layer on the surface of a preformed porous polymeric substrate. The substrate can be formed from poly (aryl ether ketone) and a perfluorohydrocarbon layer can be chemically grafted to the surface of the substrate. The membranes can be utilized for a broad range of fluid separations, such as microfiltration, nanofiltration, ultrafiltration as membrane contactors for membrane distillation and for degassing and dewatering of fluids. The membranes can further contain a dense ultra-thin perfluorohydrocarbon layer superimposed on the porous poly (aryl ether ketone) substrate and can be utilized as membrane contactors or as gas separation. membranes for natural gas treatment and gas dehydration.

  8. Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

    Science.gov (United States)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Ma, Lichun; Qi, Meiwei; Yu, Jiali; Huang, Yudong

    2014-10-01

    Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction "on water" to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction "on water" could be a facile green platform to functionalize carbon fibers for many interesting applications.

  9. Highly Efficient Synthesis of 2-Aryl-3-methoxyacrylates via Suzuki-Miyaura Coupling Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyung Ho; Lee, Chun Ho; Song, Young Seob; Park, No Kyun; Kim, Bum Tae; Heo, Jung Nyoung [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of)

    2006-02-15

    We have developed a highly efficient and convergent synthesis of 2-aryl-3-methoxyacrylates via the Suzuki-Miyaura coupling reaction of α-iodo-β-methoxy-acrylate with arylboronic acids. The biological activities of 2-aryl-3-methoxyacrylate derivatives will be reported in due course. The Suzuki-Miyaura coupling reaction provides a convenient access to the carbon-carbon bond formation with high efficiency. Recently, a number of 2-aryl-3-methoxy-acrylates served as a key scaffold for the development of biologically active pharmaceuticals and agrochemicals. Especially, the discovery of the naturally-occurring fungicides, such as strobilurin A and oudemansin A, possessing a β-methoxyacrylate moiety was immediately seized great attention by industrial research groups to open a new era of the strobilurin family including azoxy-strobin and picoxystrobin.

  10. Actinide/crown ether chemistry

    International Nuclear Information System (INIS)

    Benning, M.M.

    1988-01-01

    A structural survey of actinide/crown ether compounds was conducted in order to investigate the solid state chemistry of these complexes. Several parameters - the metal size, crown type, counterion, solvent systems and reaction and crystallization conditions - were varied to correlate their importance in complexation. Under atmospheric conditions, two types of complexes were isolated, those containing only hydrogen-bonded crown interactions and instances where the crown interacts directly with the metal center. In both cases, water seems to play a very important role. When coordinated to the metal, water molecules exhibit the necessary donor properties required for the formation of hydrogen-bonded contacts. The water molecules also provide fierce competition with the crown ethers for metal-binding sites and in most cases prohibit the formation of complexes in which direct metal-ligand association exists. The results of this study indicate that direct interaction between the metal atoms and the crown ethers, in the presence of water, can only occur with polyether conformations which limit the steric replusions within the metal coordination sphere

  11. Copper-Catalyzed Synthesis of Mixed Alkyl Aryl Phosphonates

    NARCIS (Netherlands)

    Fañanás-Mastral, Martín; Feringa, Ben L

    2014-01-01

    Copper-catalysis allows the direct oxygenarylation of dialkyl phosphonates with diaryliodonium salts. This novel methodology proceeds with a wide range of phosphonates and phosphoramidates under mild conditions and gives straightforward access to valuable mixed alkyl aryl phosphonates in very good

  12. Facile Arylation of Four-Coordinate Boron Halides by Borenium Cation Mediated Boro-desilylation and -destannylation.

    Science.gov (United States)

    Crossley, Daniel L; Cid, Jessica; Curless, Liam D; Turner, Michael L; Ingleson, Michael J

    2015-12-28

    The addition of AlCl 3 to four-coordinate boranes of the general formula (C-N-chelate)BCl 2 results in halide abstraction and formation of three-coordinate borenium cations of the general formula [(C-N-chelate)BCl] + . The latter react with both arylstannanes and arylsilanes by boro-destannylation and -desilylation, respectively, to form arylated boranes. Catalytic quantities of AlCl 3 were sufficient to effect high-yielding arylation of (C-N-chelate)BCl 2 . Boro-destannylation is more rapid than boro-desilylation and leads to double arylation at the boron center, whereas in reactions with arylsilanes either single or double arylation occurs dependent on the nucleophilicity of the arylsilane and on the electrophilicity of the borenium cation. The electrophilicity of the borenium cation derived from 2-phenylpyridine was greater than that of the benzothiadiazole analogues, enabling the boro-desilyation of less nucleophilic silanes and the direct electrophilic borylation of 2-methylthiophene.

  13. Synthesis of Secondary Aromatic Amides via Pd-Catalyzed Aminocarbonylation of Aryl Halides Using Carbamoylsilane as an Amide Source.

    Science.gov (United States)

    Tong, Wenting; Cao, Pei; Liu, Yanhong; Chen, Jianxin

    2017-11-03

    Using N-methoxymethyl-N-organylcarbamoyl(trimethyl)silanes as secondary amides source, the direct transformation of aryl halides into the corresponding secondary aromatic amides via palladium-catalyzed aminocarbonylation is described. The reactions tolerated a broad range of functional groups on the aryl ring except big steric hindrance of substituent. The types and the relative position of substituents on the aryl ring impact the coupling efficiency.

  14. Ether: Bitcoin's competitor or ally?

    OpenAIRE

    Bouoiyour, Jamal; Selmi, Refk

    2017-01-01

    Although Bitcoin has long been dominant in the crypto scene, it is certainly not alone. Ether is another cryptocurrency related project that has attracted an intensive attention because of its additional features. This study seeks to test whether these cryptocurrencies differ in terms of their volatile and speculative behaviors, hedge, safe haven and risk diversification properties. Using different econometric techniques, we show that a) Bitcoin and Ether are volatile and relatively more resp...

  15. Copper-Catalyzed N-Arylation of Amides Using (S-N-Methylpyrrolidine-2-carboxylate as the Ligand

    Directory of Open Access Journals (Sweden)

    Dong-Sheng Ma

    2010-03-01

    Full Text Available (S-N-methylpyrrolidine-2-carboxylate, a derivative of natural L-proline, was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides with aryl halides under mild conditions. A variety of N-arylamides were synthesized in good to high yields.

  16. Microsomal aryl hydrocarbon hydroxylase comparison of the direct, indirect and radiometric assays

    International Nuclear Information System (INIS)

    Denison, M.S.; Murray, M.; Wilkinson, C.F.

    1983-01-01

    The direct fluorometric assay of aryl hydrocarbon hydroxlyase has been compared to the more commonly used indirect fluorometric and radiometric assays. Although rat hepatic microsomal activities measured by the direct assay were consistently higher than those obtained by the other assays, the relative changes in activity following enzyme induction and/or inhibition were similar. The direct assay provides an accurate and rapid measure of aryl hydrocarbon hydroxylase activity and avoids several problems inherent in the indirect and radiometric assays. 2 tables

  17. Catalytic hydroprocessing of lignin β-O-4 ether bond model compound phenethyl phenyl ether over ruthenium catalysts

    NARCIS (Netherlands)

    Gomez-Monedero, B.; Faria, J.; Bimbela, F.; Ruiz, M.P.

    2017-01-01

    The catalytic hydroprocessing of phenethyl phenyl ether (PPE), a model compound of one of the most significant ether linkages within lignin structure, β-O-4, has been studied. Reactions were carried out using two ruthenium-based catalysts, supported on different materials: 3.8 wt.% Ru/C and 3.9 wt.%

  18. Radiolabeled cholesteryl ethers: A need to analyze for biological stability before use

    Directory of Open Access Journals (Sweden)

    Denny Joseph Manual Kollareth

    2018-03-01

    Full Text Available Radiolabeled cholesteryl ethers are widely used as non-metabolizable tracers for lipoproteins and lipid emulsions in a variety of in vitro and in vivo experiments. Since cholesteryl ethers do not leave cells after uptake and are not hydrolyzed by mammalian cellular enzymes, these compounds can act as markers for cumulative cell uptakes of labeled particles. We have employed [3H]cholesteryl oleoyl ether to study the uptake and distribution of triglyceride-rich emulsion particles on animal models. However, questionable unexpected results compelled us to analyze the stability of these ethers. We tested the stability of two commercially available radiolabeled cholesteryl ethers - [3H]cholesteryl oleoyl ether and [3H]cholesteryl hexadecyl ether from different suppliers, employing in vitro, in vivo and chemical model systems. Our results show that, among the two cholesteryl ethers tested, one ether was hydrolyzed to free cholesterol in vitro, in vivo and chemically under alkaline hydrolyzing agent. Free cholesterol, unlike cholesteryl ether, can then re-enter the circulation leading to confounding results. The other ether was not hydrolyzed to free cholesterol and remained as a stable ether. Hence, radiolabeled cholesteryl ethers should be analyzed for biological stability before utilizing them for in vitro or in vivo experiments. Keywords: Cholesteryl ether, J774 A2 macrophages, Soy oil emulsion, Thin layer chromatography, triDHA emulsion

  19. Protein resistance of surfaces modified with oligo(ethylene glycol) aryl diazonium derivatives.

    Science.gov (United States)

    Fairman, Callie; Ginges, Joshua Z; Lowe, Stuart B; Gooding, J Justin

    2013-07-22

    Anti-fouling surfaces are of great importance for reducing background interference in biosensor signals. Oligo(ethylene glycol) (OEG) moieties are commonly used to confer protein resistance on gold, silicon and carbon surfaces. Herein, we report the modification of surfaces using electrochemical deposition of OEG aryl diazonium salts. Using electrochemical and contact angle measurements, the ligand packing density is found to be loose, which supports the findings of the fluorescent protein labelling that aryl diazonium OEGs confer resistance to nonspecific adsorption of proteins albeit lower than alkane thiol-terminated OEGs. In addition to protein resistance, aryl diazonium attachment chemistry results in stable modification. In common with OEG species on gold electrodes, OEGs with distal hydroxyl moieties do confer superior protein resistance to those with a distal methoxy group. This is especially the case for longer derivatives where superior coiling of the OEG chains is possible. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Radiolabeled cholesteryl ethers: A need to analyze for biological stability before use.

    Science.gov (United States)

    Manual Kollareth, Denny Joseph; Chang, Chuchun L; Hansen, Inge H; Deckelbaum, Richard J

    2018-03-01

    Radiolabeled cholesteryl ethers are widely used as non-metabolizable tracers for lipoproteins and lipid emulsions in a variety of in vitro and in vivo experiments. Since cholesteryl ethers do not leave cells after uptake and are not hydrolyzed by mammalian cellular enzymes, these compounds can act as markers for cumulative cell uptakes of labeled particles. We have employed [ 3 H]cholesteryl oleoyl ether to study the uptake and distribution of triglyceride-rich emulsion particles on animal models. However, questionable unexpected results compelled us to analyze the stability of these ethers. We tested the stability of two commercially available radiolabeled cholesteryl ethers - [ 3 H]cholesteryl oleoyl ether and [ 3 H]cholesteryl hexadecyl ether from different suppliers, employing in vitro , in vivo and chemical model systems. Our results show that, among the two cholesteryl ethers tested, one ether was hydrolyzed to free cholesterol in vitro , in vivo and chemically under alkaline hydrolyzing agent. Free cholesterol, unlike cholesteryl ether, can then re-enter the circulation leading to confounding results. The other ether was not hydrolyzed to free cholesterol and remained as a stable ether. Hence, radiolabeled cholesteryl ethers should be analyzed for biological stability before utilizing them for in vitro or in vivo experiments.

  1. Antioxidant Functions of the Aryl Hydrocarbon Receptor

    Directory of Open Access Journals (Sweden)

    Cornelia Dietrich

    2016-01-01

    Full Text Available The aryl hydrocarbon receptor (AhR is a transcription factor belonging to the basic helix-loop-helix/PER-ARNT-SIM family. It is activated by a variety of ligands, such as environmental contaminants like polycyclic aromatic hydrocarbons or dioxins, but also by naturally occurring compounds and endogenous ligands. Binding of the ligand leads to dimerization of the AhR with aryl hydrocarbon receptor nuclear translocator (ARNT and transcriptional activation of several xenobiotic phase I and phase II metabolizing enzymes. It is generally accepted that the toxic responses of polycyclic aromatic hydrocarbons, dioxins, and structurally related compounds are mediated by activation of the AhR. A multitude of studies indicate that the AhR operates beyond xenobiotic metabolism and exerts pleiotropic functions. Increasing evidence points to a protective role of the AhR against carcinogenesis and oxidative stress. Herein, I will highlight data demonstrating a causal role of the AhR in the antioxidant response and present novel findings on potential AhR-mediated antioxidative mechanisms.

  2. Numerical investigation on the effect of injection pressure on the internal flow characteristics for diethyl ether, dimethyl ether and diesel fuel injectors using CFD

    Directory of Open Access Journals (Sweden)

    Vijayakumar Thulasi

    2011-01-01

    Full Text Available The spray characteristics of the diesel fuel are greatly affected by the cavitation formed inside the injector due to the high pressure differential across the nozzle. Many researchers across the globe are exploring the potential of using diethyl ether and dimethyl ether as an alternate for diesel fuel to meet the strict emission norms. Due to the variation in the fuel properties the internal flow characteristics in injectors for ether fuels are expected to be different from that of the diesel fuel. In this paper computational technique is used to study and compare the internal flow characteristics of diethyl ether, dimethyl ether and diesel fuel. The two phase flow model considering the fuel as a mixture of liquid and vapor is adopted for the simulation study. The injection pressure is varied from 100 to 400 bar and the flow characteristics of all three fuels are simulated and compared. Results indicate that all three fuels have distinct cavitating patterns owing to different property values. The dimethyl ether is found to be more cavitating than diesel and diethyl ether fuels as expected. The mass of fuel injected are found to be decreasing for the ether fuels when compared with diesel fuel at all injection pressures.

  3. Cobalt-promoted regioselective preparation of aryl tetrazole amines

    Indian Academy of Sciences (India)

    KONDRAGANTI LAKSHMI

    2018-04-17

    Apr 17, 2018 ... To the best of .... coupled product with aryl iodide under mild reaction ..... Having the optimal conditions studied, the scope of ... ity, environmental acceptability and cost-effectiveness ... lite as a new and reusable heterogeneous catalyst Chem. ... Aminotetrazoles from Thioureas: A Strategy for Diver-.

  4. Inhibition of the pore-forming protein perforin by a series of aryl-substituted isobenzofuran-1(3H)-ones.

    Science.gov (United States)

    Spicer, Julie A; Huttunen, Kristiina M; Miller, Christian K; Denny, William A; Ciccone, Annette; Browne, Kylie A; Trapani, Joseph A

    2012-02-01

    An aryl-substituted isobenzofuran-1(3H)-one lead compound was identified from a high throughput screen designed to find inhibitors of the lymphocyte pore-forming protein perforin. A series of analogs were then designed and prepared, exploring structure-activity relationships through variation of 2-thioxoimidazolidin-4-one and furan subunits on an isobenzofuranone core. The ability of the resulting compounds to inhibit the lytic activity of both isolated perforin protein and perforin delivered in situ by intact KHYG-1 natural killer effector cells was determined. Several compounds showed excellent activity at concentrations that were non-toxic to the killer cells. This series represents a significant improvement on previous classes of compounds, being substantially more potent and largely retaining activity in the presence of serum. Copyright © 2011 Elsevier Ltd. All rights reserved.

  5. AIRBORNE POLYBROMINATED DIPHENYL ETHERS IN A COMPUTER CLASSROOM OF COLLEGE IN TAIWAN

    Directory of Open Access Journals (Sweden)

    F. H. Chang ، C. R. Yang ، C. Y. Tsai ، W. C. Lin

    2009-04-01

    Full Text Available This study characterized the airborne exposure of students to thirty polybrominated diphenyl ether congeners inside and outside a computer classroom in a southern Taiwan college. Arithmetic mean values of total indoor and outdoor polybrominated diphenyl ether concentrations were 125.0 pg/m3 (89.8 to 203.9 pg/m3 and 110.3 pg/m3 (83.5 to 157.0 pg/m3, respectively. Total indoor polybrominated diphenyl ether concentrations were one order of magnitude lower than those detected in homes in Birmingham, United Kingdom and in Ottawa, Canada but were several times higher than those measured in the ambient air in Ottawa, Canada and from the Bohai Sea to the Arctic. The five highest indoor concentrations of polybrominated diphenyl ether congeners were decabromodiphenyl ether (23.0 pg/m3, 4,4’-dibromodiphenyl ether (15.9 pg/m3, 2,2’,3,4,4’,5,5’,6-octabromodiphenyl ether (10.6 pg/m3, 2,4-dibromodiphenyl ether (10.3 pg/m3 and 2,2’,3,4,4’,5’,6-heptabromodiphenyl ether (10.0 pg/m3. Although indoor and outdoor total polybrominated diphenyl ether concentrations did not significantly differ, the indoor concentrations of 2,4-dibromodiphenyl ether, 2,2’,4-tribromodiphenyl ether, 2,4,4’-tribromodiphenyl ether, 2,2’,4,5’-tetrabromodiphenyl ether and 2,3’,4’,6-tetrabromodiphenyl ether were significantly higher than their outdoor concentrations. This study suggests the following measures: 1 to increase the air exchange rate and open classroom doors and windows for several minutes before classes to reduce indoor PBDE concentrations; 2 to reduce polybrominated diphenyl ether emissions from new devices, it’s better to use computer-related products that meet the Restriction of Hazardous Substances Directive adopted by the European Union.

  6. Thermally reversible cross-linked poly(ether-urethanes

    Directory of Open Access Journals (Sweden)

    V. Gaina

    2013-07-01

    Full Text Available Cross-linked poly(ether-urethanes were prepared by Diels-Alder (DA reaction of the furan-containing poly(ether-urethane to bismaleimides and showed thermal reversibility evidenced by differential scanning calorimetry and attenuated total reflectance in conjunction with Fourier transform infrared spectroscopy (ATR-FTIR. The furan-containing poly(ether-urethanes were synthesized by the polyaddition reaction of 1,6-hexamethylene diisocyanate (HMDI or 4,4'- dibenzyl diisocyanate (DBDI to poly(tetramethylene ether glycol (PTMEG having Mn = 250, 650, 1000, 1500 and 2000 and 2-[N,N-bis(2-methyl-2-hydroxyethylamino]furfuryl as chain extender by the solution prepolymer method. The molar ratio of isocyanate: PTMEG:chain extender varied from 2:1:1 to 4:1:3, which produces a molar concentration of furyl group ranging between 3.65•10–4 and 1.25•10–3 mol/g.

  7. Thermal Stability of Sulfonated Poly(Ether Ether Ketone) Films: on the Role of Protodesulfonation

    OpenAIRE

    Koziara, Beata; Kappert, Emiel; Ogieglo, Wojciech; Nijmeijer, Dorothea C.; Hempenius, Mark A.; Benes, Nieck Edwin

    2016-01-01

    Thin film and bulk, sulfonated poly(ether ether ketone) (SPEEK) have been subjected to a thermal treatment at 160–250 °C for up to 15 h. Exposing the films to 160 °C already causes partial desulfonation, and heating to temperatures exceeding 200 °C results in increased conjugation in the material, most likely via a slight cross-linking by H-substitution. It is well-known that the sulfonate proton plays a major role in the desulfonation reactions, and exchanging the protons with other cations ...

  8. α-Diazo oxime ethers for N-heterocycle synthesis.

    Science.gov (United States)

    Choi, Subin; Ha, Sujin; Park, Cheol-Min

    2017-06-01

    This Feature Article introduces the preparation and synthetic utility of α-diazo oxime ethers. α-Oximino carbenes are useful synthons for N-heterocycles, and can be easily prepared from α-diazo oxime ethers as precursors. We begin with the preparation of α-diazo oxime ethers and their application in [3+2] cycloaddition. It turns out that the nature of metals bound to carbenes plays a crucial role in modulating the reactivity of α-oximino carbenes, in which copper carbenes smoothly react with enamines, whereas the less reactive enol ethers and nitriles require gold carbenes. In Section 3.2, a discussion on N-O and C-H bond activation is presented. Carbenes derived from diazo oxime ethers show unique reactivity towards N-O and C-H bond activation, in which the proximity of the two functionalities, carbene and oxime ether, dictates the preferred reaction pathways toward pyridines, pyrroles, and 2H-azirines. In Section 3.3, the development of tandem reactions based on α-diazo oxime ethers is discussed. The nature of carbenes in which whether free carbenes or metal complexes are involved dissects the pathway and forms different types of 2H-azirines. The 2H-azirine formation turned out to be an excellent platform for the tandem synthesis of N-heterocycles including pyrroles and pyridines. In the last section, we describe the electrophilic activation of 2H-azirines with vinyl carbenes and oximino carbenes. The resulting azirinium species undergo rapid ring expansion rearrangements to form pyridines and pyrazines.

  9. Pd-Catalyzed N-Arylation of Secondary Acyclic Amides: Catalyst Development, Scope, and Computational Study

    Science.gov (United States)

    Hicks, Jacqueline D.; Hyde, Alan M.; Cuezva, Alberto Martinez; Buchwald, Stephen L.

    2009-01-01

    We report the efficient N-arylation of acyclic secondary amides and related nucleophiles with aryl nonaflates, triflates, and chlorides. This method allows for easy variation of the aromatic component in tertiary aryl amides. A new biaryl phosphine with P-bound 3,5-(bis)trifluoromethylphenyl groups was found to be uniquely effective for this amidation. The critical aspects of the ligand were explored through synthetic, mechanistic, and computational studies. Systematic variation of the ligand revealed the importance of (1) a methoxy group on the aromatic carbon of the “top ring” ortho to the phosphorus and (2) two highly electron-withdrawing P-bound 3,5-(bis)trifluoromethylphenyl groups. Computational studies suggest the electron-deficient nature of the ligand is important in facilitating amide binding to the LPd(II)(Ph)(X) intermediate. PMID:19886610

  10. Aryl- and heteroaryl-substituted aminobenzo[a]quinolizines as dipeptidyl peptidase IV inhibitors.

    Science.gov (United States)

    Boehringer, Markus; Fischer, Holger; Hennig, Michael; Hunziker, Daniel; Huwyler, Joerg; Kuhn, Bernd; Loeffler, Bernd M; Luebbers, Thomas; Mattei, Patrizio; Narquizian, Robert; Sebokova, Elena; Sprecher, Urs; Wessel, Hans Peter

    2010-02-01

    Synthesis and SAR are described for a structurally distinct class of DPP-IV inhibitors based on aminobenzo[a]quinolizines bearing (hetero-)aromatic substituents in the S1 specificity pocket. The m-(fluoromethyl)-phenyl derivative (S,S,S)-2g possesses the best fit in the S1 pocket. However, (S,S,S)-2i, bearing a more hydrophilic 5-methyl-pyridin-2-yl residue as substituent for the S1 pocket, displays excellent in vivo activity and superior drug-like properties. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

  11. Novel amide derivatives as inhibitors of histone deacetylase: design, synthesis and SAR

    DEFF Research Database (Denmark)

    Andrianov, V.; Gailite, V.; Lola, D.

    2009-01-01

    Enzymatic inhibition of histone deacetylase (HDAC) activity is emerging as an innovative and effective approach for the treatment of cancer. A series of novel amide derivatives have been synthesized and evaluated for their ability to inhibit human HDACs. Multiple compounds were identified as potent...... HDAC inhibitors (HDACi), with IC(50) values in the low nanomolar (nM) range against enzyme activity in HeLa cell extracts and sub-microM for their in vitro anti-proliferative effect on cell lines. The introduction of an unsaturated linking group between the terminal aryl ring and the amide moiety...

  12. Synthesis of Quinolines through Three-Component Cascade Annulation of Aryl Diazonium Salts, Nitriles, and Alkynes.

    Science.gov (United States)

    Wang, Hao; Xu, Qian; Shen, Sheng; Yu, Shouyun

    2017-01-06

    An efficient and rapid synthesis of multiply substituted quinolines is described. This method is enabled by a three-component cascade annulation of readily available aryl diazonium salts, nitriles, and alkynes. This reaction is catalyst- and additive-free. Various aryl diazonium salts, nitriles, and alkynes can participate in this transformation, and the yields are up to 83%.

  13. Dimethyl ether as a drift-chamber gas

    International Nuclear Information System (INIS)

    Bari, G.; Basile, M.; Bonvicini, G.; Cara Romeo, G.; Casaccia, R.; Cifarelli, L.; Cindolo, F.; Contin, A.; D'Ali, G.; Del Papa, C.; Focardi, S.; Iacobucci, G.; Maccarrone, G.; Massam, T.; Motta, F.; Nania, R.; Palmonari, F.; Prisco, G.; Sartorelli, G.; Susinno, G.; Votano, L.; Zichichi, A.; Istituto Nazionale di Fisica Nucleare, Bologna; European Organization for Nuclear Research, Geneva; Istituto Nazionale di Fisica Nucleare, Frascati; Michigan Univ., Ann Arbor; Palermo Univ.

    1986-01-01

    We have continued the testing of dimethyl ether as a drift-chamber gas in order to improve the understanding of its properties. In particular, we report on measurement accuracy, on systematic effects, and some preliminary data on the ageing of a detector filled with dimethyl ether. (orig.)

  14. Process for making propenyl ethers and photopolymerizable compositions containing them

    Science.gov (United States)

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  15. RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

    Science.gov (United States)

    Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d14, di-n-butyl ether and di-n-butyl ether-d18 have been measured at 296 ? 2 K and atmos...

  16. Selective crystallization of cations with crown ethers

    International Nuclear Information System (INIS)

    Heffels, Dennis Egidius

    2014-01-01

    The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

  17. Oxidative electrochemical aryl C-C coupling of spiropyrans

    NARCIS (Netherlands)

    Ivashenko, Oleksii; van Herpt, Jochem T.; Rudolf, Petra; Feringa, Ben L.; Browne, Wesley R.

    2013-01-01

    The isolation and definitive assignment of the species formed upon electrochemical oxidation of nitro-spiropyran (SP) is reported. The oxidative aryl C-C coupling at the indoline moiety of the SP radical cation to form covalent dimers of the ring-closed SP form is demonstrated. The coupling is

  18. Radiation-induced transformations of cellulose ethers

    International Nuclear Information System (INIS)

    Nud'ga, L.A.; Petropavlovskii, G.S.; Plisko, E.A.; Isakova, O.V.; Ershov, B.G.

    1988-01-01

    The purpose of this investigation was to study the transformation which take place under the action of γ-radiation in a number of cellulose ethers containing both saturated (carboxymethyl, hydroxyethyl) and unsaturated (allyl, methacryloyl) groups. Irradiation was carried out on a 60 Co unit in air at 77 and 300 K; the dose rate was 37 and 50 kGy/h respectively. The EPR spectra of γ-irradiated hydroxyethyl- and allylhydroxyethylcelluloses are identical. Under the action of γ-radiation extensive changes took place in cellulose ethers which are exhibited in degradation or the formation of three-dimensional structures and are accompanied by a change in the functional composition. The efficiency in the formation of radicals and their localization are determined by the nature and number of substituents in the cellulose ethers

  19. Aryl-derivatized, water-soluble functionalized carbon nanotubes for biomedical applications

    International Nuclear Information System (INIS)

    Karousis, N.; Ali-Boucetta, H.; Kostarelos, K.; Tagmatarchis, N.

    2008-01-01

    The functionalization of very-thin multi-walled carbon nanotubes (VT-MWNTs) with an aniline derivative, via the protocol of in situ generated aryl diazonium salts results, upon acidic deprotection of the terminal BOC group, on the formation of the water-soluble positively charged ammonium functionalized VT-MWNTs-NH 3 + material. The new materials have been structurally and morphologically characterized by infra-red (ATR-IR) spectroscopy and transmission electron microscopy (TEM). The quantitative calculation of the grafted aryl units onto the skeleton of VT-MWNTs has been estimated by thermogravimetric analysis (TGA), while the quantitative Kaiser test showed the amine group loaded onto VT-MWNTs-NH 3 + material. The aqueous solubility of this material has allowed the performance of some initial toxicological in vitro investigations

  20. Thermodynamics of Hydrogen Production from Dimethyl Ether Steam Reforming and Hydrolysis

    Energy Technology Data Exchange (ETDEWEB)

    T.A. Semelsberger

    2004-10-01

    The thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the process of dimethyl ether (DME) steam reforming were investigated as a function of steam-to-carbon ratio (0-4), temperature (100 C-600 C), pressure (1-5 atm), and product species: acetylene, ethanol, methanol, ethylene, methyl-ethyl ether, formaldehyde, formic acid, acetone, n-propanol, ethane and isopropyl alcohol. Results of the thermodynamic processing of dimethyl ether with steam indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure was observed to shift the equilibrium toward the reactants; increasing the pressure from 1 atm to 5 atm decreased the conversion of dimethyl ether from 99.5% to 76.2%. The order of thermodynamically stable products in decreasing mole fraction was methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol--formaldehyde, formic acid, and acetylene were not observed. The optimal processing conditions for dimethyl ether steam reforming occurred at a steam-to-carbon ratio of 1.5, a pressure of 1 atm, and a temperature of 200 C. Modeling the thermodynamics of dimethyl ether hydrolysis (with methanol as the only product considered), the equilibrium conversion of dimethyl ether is limited. The equilibrium conversion was observed to increase with temperature and steam-to-carbon ratio, resulting in a maximum dimethyl ether conversion of approximately 68% at a steam-to-carbon ratio of 4.5 and a processing temperature of 600 C. Thermodynamically, dimethyl ether processed with steam can produce hydrogen-rich fuel-cell feeds--with hydrogen concentrations exceeding 70%. This substantiates dimethyl ether as a viable source of hydrogen for PEM fuel cells.

  1. Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

    International Nuclear Information System (INIS)

    Tewatia, Arya; Hendrix, Justin; Dong, Zhizhong; Taghon, Meredith; Tse, Stephen; Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas; Lynch, Jennifer

    2017-01-01

    Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

  2. Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Tewatia, Arya; Hendrix, Justin [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Dong, Zhizhong [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Taghon, Meredith [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Tse, Stephen [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Lynch, Jennifer, E-mail: jklynch@rci.rutgers.edu [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States)

    2017-02-15

    Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

  3. Inhibition of the MEK-1/p42 MAP kinase reduces aryl hydrocarbon receptor-DNA interactions

    International Nuclear Information System (INIS)

    Yim, Sujin; Oh, Myoungsuk; Choi, Su Mi; Park, Hyunsung

    2004-01-01

    2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) induces expression of the cytochrome P450 1A1 gene, cyp1a1, by binding to its receptor, aryl hydrocarbon receptor (AhR). TCDD-bound AhR translocates to the nucleus and forms a heterodimer with its partner protein, AhR nuclear translocator (Arnt). The AhR/Arnt heterodimer then binds to the dioxin-response elements (DREs) in the cyp1a1 enhancer and stimulates transcription of cyp1a1. We tested whether kinase pathways are involved in this process by treating Hepa1c1c7 cells with kinase inhibitors. The MEK-1 inhibitor PD98059 reduced TCDD-induced transcription of cyp1a1. TCDD treatment results in phosphorylation of p44/p42 mitogen-activated protein kinase (MAPK), a substrate of MEK-1. Overexpression of dominant negative form of p42 MAPK suppressed TCDD-dependent transcription of a reporter gene controlled by dioxin-response elements (DREs), and pretreatment with PD98059 also blocked this transcription. PD98059 pretreatment also inhibited TCDD-induced DRE binding of the AhR/Arnt heterodimer. Together these results indicate that TCDD activates the MEK-1/p44/p42 MAPK pathway, which in turn activates AhR and so facilitates binding of AhR to the cyp1a1 DRE

  4. Discovery of aryl-tri-fluoroborates as potent sodium/iodide sym-porter (NIS) inhibitors

    International Nuclear Information System (INIS)

    Lecat-Guillet, N.; Ambroise, Y.

    2008-01-01

    The structure-based design of sodium/iodide sym-porter (NIS) inhibitors identified new active compounds. The organo-tri-fluoroborate shown was found to inhibit iodide uptake with an IC50 value of 0.4 μM on rat-derived thyroid cells. The biological activity is rationalized by the presence of the BF3 - ion as a minimal binding motif for substrate recognition at the iodide binding site. (authors)

  5. Discovery of aryl-tri-fluoroborates as potent sodium/iodide sym-porter (NIS) inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Lecat-Guillet, N.; Ambroise, Y. [CEA, DSV, Dept Bioorgan Chem and Isotop Labelling, Inst Biol and Technol, iBiTecS, F-91191 Gif Sur Yvette (France)

    2008-07-01

    The structure-based design of sodium/iodide sym-porter (NIS) inhibitors identified new active compounds. The organo-tri-fluoroborate shown was found to inhibit iodide uptake with an IC50 value of 0.4 {mu}M on rat-derived thyroid cells. The biological activity is rationalized by the presence of the BF3{sup -} ion as a minimal binding motif for substrate recognition at the iodide binding site. (authors)

  6. Decrease of intracellular pH as possible mechanism of embryotoxicity of glycol ether alkoxyacetic acid metabolites

    International Nuclear Information System (INIS)

    Louisse, Jochem; Bai Yanqing; Verwei, Miriam; Sandt, Johannes J.M. van de; Blaauboer, Bas J.; Rietjens, Ivonne M.C.M.

    2010-01-01

    Embryotoxicity of glycol ethers is caused by their alkoxyacetic acid metabolites, but the mechanism underlying the embryotoxicity of these acid metabolites is so far not known. The present study investigates a possible mechanism underlying the embryotoxicity of glycol ether alkoxyacetic acid metabolites using the methoxyacetic acid (MAA) metabolite of ethylene glycol monomethyl ether as the model compound. The results obtained demonstrate an MAA-induced decrease of the intracellular pH (pH i ) of embryonic BALB/c-3T3 cells as well as of embryonic stem (ES)-D3 cells, at concentrations that affect ES-D3 cell differentiation. These results suggest a mechanism for MAA-mediated embryotoxicity similar to the mechanism of embryotoxicity of the drugs valproic acid and acetazolamide (ACZ), known to decrease the pH i in vivo, and therefore used as positive controls. The embryotoxic alkoxyacetic acid metabolites ethoxyacetic acid, butoxyacetic acid and phenoxyacetic acid also caused an intracellular acidification of BALB/c-3T3 cells at concentrations that are known to inhibit ES-D3 cell differentiation. Two other embryotoxic compounds, all-trans-retinoic acid and 5-fluorouracil, did not decrease the pH i of embryonic cells at concentrations that affect ES-D3 cell differentiation, pointing at a different mechanism of embryotoxicity of these compounds. MAA and ACZ induced a concentration-dependent inhibition of ES-D3 cell differentiation, which was enhanced by amiloride, an inhibitor of the Na + /H + -antiporter, corroborating an important role of the pH i in the embryotoxic mechanism of both compounds. Together, the results presented indicate that a decrease of the pH i may be the mechanism of embryotoxicity of the alkoxyacetic acid metabolites of the glycol ethers.

  7. On the ether-like Lorentz-breaking actions

    International Nuclear Information System (INIS)

    Petrov, A.Yu; Nascimento, J.R.; Gomes, M.; Silva, A. J. da

    2011-01-01

    We demonstrate the generation of the CPT-even, ether-like Lorentz-breaking actions for the scalar and electro-magnetic fields via their appropriate Lorentz-breaking coupling to spinor fields in three, four and five space-time dimensions. Besides, we show that the ether-like terms for the spinor field also can be generated as a consequence of the same couplings. The key result which will be presented here is the finiteness of the ether-like term for the electromagnetic field not only in three and five space-time dimensions where it is natural due to known effects of the dimensional regularization but also in four space-time dimensions. Moreover, we present the calculation of the last result within different calculational schemes and conclude that the result for the four-dimensional ether-like term for the electromagnetic field essentially depending on the calculation scheme, similarly to the result for the Carroll-Field-Jackiw (CFJ) term which probably signalizes a possibility for arising of a new anomaly. Also we discuss the dispersion relations in the theories with ether-like Lorentz-breaking terms which allows to discuss the consistency of the Lorentz-breaking modified theories for different (space-like or time-like) Lorentz-breaking vectors and find the tree-level effective (Breit) potential for fermion scattering and the one-loop effective potential corresponding to the action of the scalar field. (author)

  8. Design, synthesis and biological evaluation of uncharged catechol derivatives as selective inhibitors of PTP1B.

    Science.gov (United States)

    Li, Xiang-Qian; Xu, Qi; Luo, Jiao; Wang, Li-Jun; Jiang, Bo; Zhang, Ren-Shuai; Shi, Da-Yong

    2017-08-18

    Protein tyrosine phosphatases 1B (PTP1B) is a promising and validated therapeutic target to effectively treat T2DM and obesity. However, the development of charged PTP1B inhibitors was restricted due to their low cell permeability and poor bioavailability. Based on active natural products, two series of uncharged catechol derivatives were identified as PTP1B inhibitors by targeting a secondary aryl phosphate-binding site as well as the catalytic site. The most potent inhibitor 22 showed an IC 50 of 0.487 μM against PTP1B and strong selectivity (27-fold) over TCPTP. Kinetic studies were also performed that 22 act as a competitive PTP1B inhibitor. The treatment of C2C12 myotubes with 22 markedly increased the phosphorylation levels of IRβ, Akt and IRS1 phosphorylation. The similarity of its action profiling with that produced by insulin suggested its potential as a new non-insulin-dependent drug candidate. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  9. The photochemistry of ring-substituted cinnamyl acetates

    International Nuclear Information System (INIS)

    Fleming, S.A.; Renault, L.; Grundy, E.C.; Pincock, J.A.

    2006-01-01

    The photochemistry of the (E)-cinnamyl acetates ((E)-1-aryl-3-propenyl acetates, 8a-8e) with substituents H, 4-CH 3 O, 3-CH 3 O, 4-CF 3 , and 3-CF 3 , respectively, was examined in both cyclohexane and methanol solvents. Alkene isomerization (E to Z) occurred more efficiently than other reactions and evidence is presented that this process occurs from the excited triplet state. In a slower process, 1,3-migration of the acetoxy group led to the rearranged 3-aryl-3-propenyl acetate isomers (9a-9e) as the major pathway, particularly in cylohexane. In methanol, the isomeric ethers 3-aryl-3-methoxypropene (14) and 1-aryl-3-methoxypropene (15) were formed by reaction of methanol with the photochemically generated cation. The combined yield of 14 and 15 (95% and 5%, respectively) was quantitative for the 4-methoxyphenyl compound (8b). Independent irradiations of the isomers 9a-9c demonstrated that the ethers 14 and 15 were primary photoproducts from 8 and not secondary photoproducts from 9. Fluorescence quantum yields and excited singlet state lifetimes indicated that the reactions, other than the E to Z isomerization, are from the excited singlet state. (author)

  10. Characterization of Microsolvated Crown Ethers from Broadband Rotational Spectroscopy

    Science.gov (United States)

    Perez, Cristobal; Schnell, Melanie; Blanco, Susana; Lopez, Juan Carlos

    2016-06-01

    Since they were first synthetized, crown ethers have been extensively used in organometallic chemistry due to their unparalleled binding selectivity with alkali metal cations. From a structural point of view, crown ethers are heterocycles containing oxygen and/or other heteroatoms, although the most common ones are formed from ethylene oxide unit. Crown ethers are conventionally seen as being hydrophilic inside and hydrophobic outside when the structures found for the metal cation complexes are considered. However, crown ethers are extremely flexible and in isolation may present a variety of stable conformations so that their structure may be easily adapted in presence of a strong ligand as an alkali metal cation minimize the energy of the resulting complex. Water can be considered a soft ligand which interacts with crown ethers through moderate hydrogen bonds. It is thus interesting to investigate which conformers are selected by water to form complexes, the preferred interaction sites and the possible conformational changes due to the presence of one or more water molecules. Previous studies identified microsolvated crown ethers but in all cases with a chromophore group attached to the structure. Here we present a broadband rotational spectroscopy study of microsolvated crown ethers produced in a pulsed molecular jet expansion. Several 1:1 and 1:2 crown ether:water aggregates are presented for 12-crown-4, 15-crown-5 and 18-crown-6. Unambiguous identification of the structures has been achieved using isotopic substitution within the water unit. The subtle changes induced in the structures of the crown ether monomer upon complexation and the hydrogen-bonding network that hold them together will be also discussed. F. Gámez, B. Martínez-Haya, S. Blanco,J. C. López and J. L. Alonso, Phys. Chem. Chem. Phys. 2014, 14 12912-12918 V. A. Shubert, C.W. Müller and T. Zwier, J. Phys. Chem. A 2009, 113 8067-8079

  11. Study of damaged depth profiles of ion-irradiated PEEK

    Czech Academy of Sciences Publication Activity Database

    Vacík, Jiří; Hnatowicz, Vladimír; Červená, Jarmila; Apel, P. Yu.; Posta, S.; Kobayashi, Y.

    2007-01-01

    Roč. 201, 19-20 (2007), s. 8370-8372 ISSN 0257-8972 R&D Projects: GA MPO(CZ) 1H-PK2/05; GA MŠk 1P04LA213 Institutional research plan: CEZ:AV0Z10480505 Keywords : Oxygen irradiation * Poly-aryl-ether-ether ketone * Thermal neutron depth profiling (TNDP) Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.678, year: 2007

  12. One-pot radioiodination of aryl amines via stable diazonium salts: preparation of 125I-imaging agents

    OpenAIRE

    Sloan, Nikki L.; Luthra, Sajinder K.; McRobbie, Graeme; Pimlott, Sally L.; Sutherland, Andrew

    2017-01-01

    An operationally simple, one-pot, two-step tandem procedure that allows the incorporation of radioactive iodine into aryl amines via stable diazonium salts is described. The mild conditions are tolerant of various functional groups and substitution patterns, allowing late-stage, rapid access to a wide range of 125I-labelled aryl compounds and SPECT radiotracers.

  13. Synthesis of 2-aryl-1,2,4-oxadiazolo-benzimidazoles: Tubulin polymerization inhibitors and apoptosis inducing agents.

    Science.gov (United States)

    Kamal, Ahmed; Reddy, T Srinivasa; Vishnuvardhan, M V P S; Nimbarte, Vijaykumar D; Subba Rao, A V; Srinivasulu, Vunnam; Shankaraiah, Nagula

    2015-08-01

    A new series of 2-aryl 1,2,4-oxadiazolo-benzimidazole conjugates have been synthesized and evaluated for their antiproliferative activity in the sixty cancer cell line panel of the National Cancer Institute (NCI). Compounds 5l (NSC: 761109/1) and 5x (NSC: 761814/1) exhibited remarkable cytotoxic activity against most of the cancer cell lines in the one dose assay and were further screened at five dose concentrations (0.01, 0.1, 1, 10 and 100 μM) which showed GI50 values in the range of 0.79-28.2 μM. Flow cytometric data of these compounds showed increased cells in G2/M phase, which is suggestive of G2/M cell cycle arrest. Further, compounds 5l and 5x showed inhibition of tubulin polymerization and disruption of the formation of microtubules. These compounds induce apoptosis by DNA fragmentation and chromatin condensation as well as by mitochondrial membrane depolarization. In addition, structure activity relationship studies within the series are also discussed. Molecular docking studies of compounds 5l and 5x into the colchicine-binding site of the tubulin, revealed the possible mode of interaction by these compounds. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Cloning and heterologous expression of two aryl-aldehyde dehydrogenases from the white-rot basidiomycete Phanerochaete chrysosporium

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, Tomofumi [Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Fukuoka Institute of Health and Environmental Sciences, 39 Mukaizano, Dazaifu-shi, Fukuoka 818-0135 (Japan); Ichinose, Hirofumi [Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Wariishi, Hiroyuki, E-mail: hirowari@agr.kyushu-u.ac.jp [Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Bio-Architecture Center, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Innovation Center for Medical Redox Navigation, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan)

    2010-04-09

    We identified two aryl-aldehyde dehydrogenase proteins (PcALDH1 and PcALDH2) from the white-rot basidiomycete Phanerochaete chrysosporium. Both PcALDHs were translationally up-regulated in response to exogenous addition of vanillin, one of the key aromatic compounds in the pathway of lignin degradation by basidiomycetes. To clarify the catalytic functions of PcALDHs, we isolated full-length cDNAs encoding these proteins and heterologously expressed the recombinant enzymes using a pET/Escherichia coli system. The open reading frames of both PcALDH1 and PcALDH2 consisted of 1503 nucleotides. The deduced amino acid sequences of both proteins showed high homologies with aryl-aldehyde dehydrogenases from other organisms and contained ten conserved domains of ALDHs. Moreover, a novel glycine-rich motif 'GxGxxxG' was located at the NAD{sup +}-binding site. The recombinant PcALDHs catalyzed dehydrogenation reactions of several aryl-aldehyde compounds, including vanillin, to their corresponding aromatic acids. These results strongly suggested that PcALDHs metabolize aryl-aldehyde compounds generated during fungal degradation of lignin and various aromatic xenobiotics.

  15. Cloning and heterologous expression of two aryl-aldehyde dehydrogenases from the white-rot basidiomycete Phanerochaete chrysosporium

    International Nuclear Information System (INIS)

    Nakamura, Tomofumi; Ichinose, Hirofumi; Wariishi, Hiroyuki

    2010-01-01

    We identified two aryl-aldehyde dehydrogenase proteins (PcALDH1 and PcALDH2) from the white-rot basidiomycete Phanerochaete chrysosporium. Both PcALDHs were translationally up-regulated in response to exogenous addition of vanillin, one of the key aromatic compounds in the pathway of lignin degradation by basidiomycetes. To clarify the catalytic functions of PcALDHs, we isolated full-length cDNAs encoding these proteins and heterologously expressed the recombinant enzymes using a pET/Escherichia coli system. The open reading frames of both PcALDH1 and PcALDH2 consisted of 1503 nucleotides. The deduced amino acid sequences of both proteins showed high homologies with aryl-aldehyde dehydrogenases from other organisms and contained ten conserved domains of ALDHs. Moreover, a novel glycine-rich motif 'GxGxxxG' was located at the NAD + -binding site. The recombinant PcALDHs catalyzed dehydrogenation reactions of several aryl-aldehyde compounds, including vanillin, to their corresponding aromatic acids. These results strongly suggested that PcALDHs metabolize aryl-aldehyde compounds generated during fungal degradation of lignin and various aromatic xenobiotics.

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

    International Nuclear Information System (INIS)

    Danu, Sugiarto

    1998-01-01

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

  17. Solvent-Free Synthesis of Aryl Iodide Using Nano SiO2/HIO4 as a Reusable Acid Catalyst

    Directory of Open Access Journals (Sweden)

    A. Bamoniri

    2014-07-01

    Full Text Available An efficient and environmentally benign   method for the synthesis of aryl iodides have been developed by diazotization of aromatic amines with NaNO2 and nanosilica periodic acid (nano-SPIA as a green catalyst via grinding followed by a sandmeyer iodination by KI under solvent-free conditions at room temperature. The ensuing aryl diazonium salts supported on nano-SPIA were sufficiently stable to be kept at room temperature in the dry state. This method is a novel, efficient, eco-friendly route for solvent-free synthesis of aryl iodides.

  18. The convenient preparation of stable aryl-coated zerovalent iron nanoparticles

    Directory of Open Access Journals (Sweden)

    Olga A. Guselnikova

    2015-05-01

    Full Text Available A novel approach for the in situ synthesis of zerovalent aryl-coated iron nanoparticles (NPs based on diazonium salt chemistry is proposed. Surface-modified zerovalent iron NPs (ZVI NPs were prepared by simple chemical reduction of iron(III chloride aqueous solution followed by in situ modification using water soluble arenediazonium tosylate. The resulting NPs, with average iron core diameter of 21 nm, were coated with a 10 nm thick organic layer to provide long-term protection in air for the highly reactive zerovalent iron core up to 180 °C. The surface-modified iron NPs possess a high grafting density of the aryl group on the NPs surface of 1.23 mmol/g. FTIR spectroscopy, XRD, HRTEM, TGA/DTA, and elemental analysis were performed in order to characterize the resulting material.

  19. Homocoupling of aryl halides in flow: Space integration of lithiation and FeCl3 promoted homocoupling

    Directory of Open Access Journals (Sweden)

    Aiichiro Nagaki

    2011-08-01

    Full Text Available The use of FeCl3 resulted in a fast homocoupling of aryllithiums, and this enabled its integration with the halogen–lithium exchange reaction of aryl halides in a flow microreactor. This system allows the homocoupling of two aryl halides bearing electrophilic functional groups, such as CN and NO2, in under a minute.

  20. Palladium-Catalyzed ortho C-H Arylation of Benzaldehydes Using ortho-Sulfinyl Aniline Transient Auxiliary.

    Science.gov (United States)

    Mu, Delong; He, Gang; Chen, Gong

    2018-05-03

    A PdII-catalyzed ortho-(Csp2)-H arylation reaction of benzaldehydes using catalytic amount of 2-methylsulfinyl-aniline as transient auxiliary was developed. This reaction is compatible with a broad range of benzaldehyde and aryl iodide substrates. Compared with other related reaction systems, an excellent regioselectivity for ortho-C(sp2)-H bonds over benzylic C(sp3)-H bonds was obtained for ortho-alkyl-benzaldehyde substrates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Photochemical Aryl Radical Cyclizations to Give (E-3-Ylideneoxindoles

    Directory of Open Access Journals (Sweden)

    Michael Gurry

    2014-09-01

    Full Text Available (E-3-Ylideneoxindoles are prepared in methanol in reasonable to good yields, as adducts of photochemical 5-exo-trig of aryl radicals, in contrast to previously reported analogous radical cyclizations initiated by tris(trimethylsilylsilane and azo-initiators that gave reduced oxindole adducts.

  2. Exogenous ether lipids predominantly target mitochondria

    DEFF Research Database (Denmark)

    Kuerschner, Lars; Richter, Doris; Hannibal-Bach, Hans Kristian

    2012-01-01

    Ether lipids are ubiquitous constituents of cellular membranes with no discrete cell biological function assigned yet. Using fluorescent polyene-ether lipids we analyzed their intracellular distribution in living cells by microscopy. Mitochondria and the endoplasmic reticulum accumulated high......, accumulated to mitochondria and induced morphological changes and cellular apoptosis. These data indicate that edelfosine could exert its pro-apoptotic power by targeting and damaging mitochondria and thereby inducing cellular apoptosis. In general, this study implies an important role of mitochondria...

  3. Mass transport of direct methanol fuel cell species in sulfonated poly(ether ether ketone) membranes

    International Nuclear Information System (INIS)

    Silva, V.S.; Ruffmann, B.; Vetter, S.; Boaventura, M.; Mendes, A.M.; Madeira, L.M.; Nunes, S.P.

    2006-01-01

    Homogeneous membranes based on sulfonated poly(ether ether ketone) (sPEEK) with different sulfonation degrees (SD) were prepared and characterized. In order to perform a critical analysis of the SD effect on the polymer barrier and mass transport properties towards direct methanol fuel cell species, proton conductivity, water/methanol pervaporation and nitrogen/oxygen/carbon dioxide pressure rise method experiments are proposed. This procedure allows the evaluation of the individual permeability coefficients in hydrated sPEEK membranes with different sulfonation degrees. Nafion[reg] 112 was used as reference material. DMFC tests were also performed at 50 deg. C. It was observed that the proton conductivity and the permeability towards water, methanol, oxygen and carbon dioxide increase with the sPEEK sulfonation degree. In contrast, the SD seems to not affect the nitrogen permeability coefficient. In terms of selectivity, it was observed that the carbon dioxide/oxygen selectivity increases with the sPEEK SD. In contrast, the nitrogen/oxygen selectivity decreases. In terms of barrier properties for preventing the DMFC reactants loss, the polymer electrolyte membrane based on the sulfonated poly(ether ether ketone) with SD lower or equal to 71%, although having slightly lower proton conductivity, presented much better characteristics for fuel cell applications compared with the well known Nafion[reg] 112. In terms of the DMFC tests of the studied membranes at low temperature, the sPEEK membrane with SD = 71% showed to have similar performance, or even better, as that of Nafion[reg] 112. However, the highest DMFC overall efficiency was achieved using sPEEK membrane with SD = 52%

  4. Effects of a diphenyl-ether herbicide, oxyfluorfen, on human BFU-E/CFU-E development and haemoglobin synthesis.

    Science.gov (United States)

    Rio, B; Parent-Massin, D; Lautraite, S; Hoellinger, H

    1997-02-01

    The diphenyl-ether herbicides exert their phytotoxic activity by preventing chlorophyll formation in plants as a result of inhibition of protoporphyrinogen oxidase. This enzyme is the last step of the common pathway for chlorophyll and haem biosynthesis. The aim of this work is to determine whether herbicide inhibitors of plant protoporphyrinogen oxidase could act on the human protoporphyrinogen oxidase involved in haemoglobin synthesis and cause heamatologic diseases. Human erythroblastic progenitors (BFU-E/CFU-E: Burst Forming Unit-Erythroid and Colony Forming Unit-Erythroid) were exposed to oxyfluorfen, a diphenyl-ether herbicide in the presence of erythropoietin, and the haematoxicity evaluated in vitro by scoring the development of BFU-E/CFU-E colonies after 7 and 14 days of culture. The toxic effect on differentiation has been evaluated using four criteria: morphology, total protein, total porphyrin, and haemoglobin content. The study of BFU-E/CFU-E proliferation and differentiation showed a cytotoxic effect of oxyfluorfen only at very high concentrations. In contrast, haemoglobin synthesis can be inhibited by concentration of oxyfluorfen (10(-4) M) that have no adverse effect on cellular proliferation.

  5. Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

    Energy Technology Data Exchange (ETDEWEB)

    Mai, Zhensheng; Bi, Cheng; Dai, Hua [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100039 (China); Zhang, Huamin; Li, Xianfeng [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China)

    2011-01-01

    Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test. (author)

  6. Analysis of electron-irradiated poly-ether ether ketone by X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Oyabu, Matashige; Kobayashi, Yoshinori; Seguchi, Tadao; Sasuga, Tsuneo; Kudoh, Hisaaki.

    1995-01-01

    Organic polymers used in atomic power plants or space are damaged by ionizing irradiation. Radicals produced by irradiation cause oxidation, chain scission and crosslinking, all of which lead to degradation of the material. In this paper, the surface of electron-irradiated poly-ether ether ketone (PEEK) was studied by X-ray photoelectron spectroscopy (XPS). The irradiation in air was found to oxidize the PEEK surface producing carboxyl groups, the content of which dependant on the dose. Carboxyl groups were not produced in helium gas. Quantitative spectral analysis indicated that the aromatic structure might be decomposed. Some comparison was made between the semicrystalline and amorphous samples. The oxygen content resulting from irradiation, of semicrystalline PEEK increased more than that of amorphous PEEK. (author)

  7. Application of simplified PC-SAFT to glycol ethers

    DEFF Research Database (Denmark)

    Avlund, Ane Søgaard; Kontogeorgis, Georgios; Michelsen, Michael Locht

    2012-01-01

    The simplified PC-SAFT (sPC-SAFT) equation of state is applied for binary glycol ether-containing mixtures, and it is investigated how the results are influenced by inclusion of intramolecular association in the association theory. Three different glycol ethers are examined: 2-methoxyethanol, 2...

  8. Investigation into ramie whisker reinforced arylated soy protein composites

    CSIR Research Space (South Africa)

    Kumar, R

    2010-03-01

    Full Text Available isolate (SPI). Thiodiglycol was used as a plasticizer for the preparation of SW composites. The SW composites were arylated with 2,2-diphenyl-2-hydroxyethanoic acid through the process of “dip-coating” and coded as SW-B. In this paper, the characterization...

  9. Menthone aryl acid hydrazones: a new class of anticonvulsants.

    Science.gov (United States)

    Jain, Jainendra; Kumar, Y; Sinha, Reema; Kumar, Rajeev; Stables, James

    2011-01-01

    A series of ten compounds (Compounds J(1)-J(10)) of (±) 3-menthone aryl acid hydrazone was synthesized and characterized by thin layer chromatography and spectral analysis. Synthesized compounds were evaluated for anticonvulsant activity after intraperitoneal (i.p) administration to mice by maximal electroshock (MES) and subcutaneous pentylenetetrazole (scPTZ) induced seizure method and minimal clonic seizure test. Minimal motor impairment was also determined for these compounds. Results obtained showed that four compounds out of ten afforded significant protection in the minimal clonic seizure screen at 6 Hz. Compound J(6), 4-Chloro-N-(2-isopropyl-5-methylcyclohexylidene) benzohydrazide was found to be the most active compound with MES ED(50) of 16.1 mg/kg and protective index (pI) of greater than 20, indicating that (±) 3-menthone aryl acid hydrazone possesses better and safer anticonvulsant properties than other reported menthone derivatives viz. menthone Schiff bases, menthone semicarbazides and thiosemicarbazides.

  10. Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

    International Nuclear Information System (INIS)

    Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang; Boyer, François; Olivier, Philippe; Sapelkin, Andrei; King, Stephen; Heenan, Richard; Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri

    2014-01-01

    Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

  11. Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

    Energy Technology Data Exchange (ETDEWEB)

    Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang, E-mail: wolfgang.bacsa@cemes.fr [CEMES-CNRS and University of Toulouse, 29 Jeanne Marvig, 31055 Toulouse (France); Boyer, François; Olivier, Philippe [Université de Toulouse, Institut Clément Ader, I.U.T. Université Paul Sabatier - 133C Avenue de Rangueil - B.P. 67701, 31077 Toulouse CEDEX 4 (France); Sapelkin, Andrei [School of Physics and Astronomy, Queen Mary, University of London, Mile End Road, E1 4NS London (United Kingdom); King, Stephen; Heenan, Richard [ISIS Facility, Rutherford Appleton Laboratory, Chilton, OX11 0QX Didcot (United Kingdom); Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri [AIRBUS FRANCE (B.E. M and P Toulouse), 316 Route de Bayonne, 31060 Toulouse (France)

    2014-06-21

    Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

  12. Radiation chemistry of alternative fuel oxygenates - substituted ethers

    International Nuclear Information System (INIS)

    Mezyk, S. P.; Cooper, W. J.; Bartels, D. M.; Tobien, T.; O'Shea, K. E.

    1999-01-01

    The electron beam process, an advanced oxidation and reduction technology, is based in the field of radiation chemistry. Fundamental to the development of treatment processes is an understanding of the underlying chemistry. The authors have previously evaluated the bimolecular rate constants for the reactions of methyl tert-butyl ether (MTBE) and with this study have extended their studies to include ethyl tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and tert-amyl methyl ether (TAME) with the hydroxyl radical, hydrogen atom and solvated electron using pulse radiolysis. For all of the oxygenates the reaction with the hydroxyl radical appears to be of primary interest in the destruction of the compounds in water. The rates with the solvated electron are limiting values as the rates appear to be relatively low. The hydrogen atom rate constants are relatively low, coupled with the low yield in radiolysis, they concluded that these are of little significance in the destruction of the alternative fuel oxygenates (and MTBE)

  13. Diethyl Ether Production as a Substitute for Gasoline

    Directory of Open Access Journals (Sweden)

    Alviany Riza

    2018-01-01

    Full Text Available Diethyl ether is one of alternative fuel that could be used as a significant component of a blend or as a complete replacement for transportation fuel. The aim of this research is to produce diethyl ether through dehydration reaction of ethanol with fixed bed reactor using nanocrystalline γ-Al2O3 catalyst. Nanocrystalline γ-Al2O3 catalyst was synthesized by precipitation method using Al(NO33.9H2O as precursors and NH4OH as the precipitating agent. Dehydration reaction was performed at temperature range of 125 to 225°C. The result shows that synthesized γ-Al2O3 catalyst gave higher ethanol conversion and diethyl ether yield than that of commercial Al2O3 catalyst. The use of synthesized γ-Al2O3 catalyst could reach ethanol conversion as high as 94.71% and diethyl ether yield as high as 11,29%.

  14. Synthesis of enyne and aryl vinyl sulfoxides: functionalization via Pummerer rearrangement.

    Science.gov (United States)

    Souza, Frederico B; Shamim, Anwar; Argomedo, Luiz M Z; Pimenta, Daniel C; Stefani, Hélio A

    2015-11-01

    An efficient methodology for the synthesis of aryl-substituted vinyl sulfoxides through direct substitution of aryl-substituted alkynyl grignard reagents on menthyl-p-toluenesulfinate followed by Suzuki-Miyaura cross-coupling reaction has been developed. It has also been described that the reaction of alkyl-substituted and cycloalkyl-substituted alkynyl grignard reagents with menthyl-p-toluenesulfinate led to two products, i.e., alkynyl sulfoxide derivatives, as a result of substitution, and enyne sulfoxide derivatives, which resulted from substitution followed by Michael type addition. It was possible to selectively synthesize the enyne sulfoxide derivatives by changing the concentration of the grignard reagent. These alkenyl sulfoxides were transformed into the corresponding [Formula: see text]-thio aldehydes in high yields via additive Pummerer rearrangement.

  15. Thiocarbamate-Directed Tandem Olefination-Intramolecular Sulfuration of Two Ortho C-H Bonds: Application to Synthesis of a COX-2 Inhibitor.

    Science.gov (United States)

    Li, Wendong; Zhao, Yingwei; Mai, Shaoyu; Song, Qiuling

    2018-02-16

    A palladium-catalyzed dual ortho C-H bond activation of aryl thiocarbamates is developed. This tandem reaction initiates by thiocarbamate-directed ortho C-H palladation, which leads to favorable olefin insertion rather than reductive elimination. The oxidative Heck reaction followed by another C-H activation and sulfuration affords the dual-functionalized products. This reaction provides a concise route to the S,O,C multisubstituted benzene skeleton which could be successfully applied for the synthesis of a COX-2 inhibitor.

  16. Aryl substitution of pentacenes

    Directory of Open Access Journals (Sweden)

    Andreas R. Waterloo

    2014-07-01

    Full Text Available A series of 11 new pentacene derivatives has been synthesized, with unsymmetrical substitution based on a trialkylsilylethynyl group at the 6-position and various aryl groups appended to the 13-position. The electronic and physical properties of the new pentacene chromophores have been analyzed by UV–vis spectroscopy (solution and thin films, thermoanalytical methods (DSC and TGA, cyclic voltammetry, as well as X-ray crystallography (for 8 derivatives. X-ray crystallography has been specifically used to study the influence of unsymmetrical substitution on the solid-state packing of the pentacene derivatives. The obtained results add to our ability to better predict substitution patterns that might be helpful for designing new semiconductors for use in solid-state devices.

  17. Aryl substitution of pentacenes

    Science.gov (United States)

    Waterloo, Andreas R; Sale, Anna-Chiara; Lehnherr, Dan; Hampel, Frank

    2014-01-01

    Summary A series of 11 new pentacene derivatives has been synthesized, with unsymmetrical substitution based on a trialkylsilylethynyl group at the 6-position and various aryl groups appended to the 13-position. The electronic and physical properties of the new pentacene chromophores have been analyzed by UV–vis spectroscopy (solution and thin films), thermoanalytical methods (DSC and TGA), cyclic voltammetry, as well as X-ray crystallography (for 8 derivatives). X-ray crystallography has been specifically used to study the influence of unsymmetrical substitution on the solid-state packing of the pentacene derivatives. The obtained results add to our ability to better predict substitution patterns that might be helpful for designing new semiconductors for use in solid-state devices. PMID:25161729

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-01

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

  19. A highly sensitive and selective dimethyl ether sensor based on cataluminescence.

    Science.gov (United States)

    Zhang, Runkun; Cao, Xiaoan; Liu, Yonghui; Peng, Yan

    2010-07-15

    A sensor for detecting dimethyl ether was designed based on the cataluminescence phenomenon when dimethyl ether vapors were passing through the surface of the ceramic heater. The proposed sensor showed high sensitivity and selectivity to dimethyl ether at an optimal temperature of 279 degrees C. Quantitative analysis were performed at a wavelength of 425 nm, the flow rate of carrier air is around 300 mL/min. The linear range of the cataluminescence intensity versus concentration of dimethyl ether is 100-6.0x10(3) ppm with a detection limit of 80 ppm. The sensor response time is 2.5 s. Under the optimized conditions, none or only very low levels of interference were observed while the foreign substances such as benzene, formaldehyde, ammonia, methanol, ethanol, acetaldehyde, acetic acid, acrolein, isopropyl ether, ethyl acetate, glycol ether and 2-methoxyethanol were passing through the sensor. Since the sensor does not need to prepare and fix up the granular catalyst, the simple technology reduces cost, improves stability and extends life span. The method can be applied to facilitate detection of dimethyl ether in the air. The possible mechanism of cataluminescence from the oxidation of dimethyl ether on the surface of ceramic heater was discussed based on the reaction products. Copyright 2010 Elsevier B.V. All rights reserved.

  20. A one-pot radioiodination of aryl amines via stable diazonium salts: preparation of 125I-imaging agents.

    Science.gov (United States)

    Sloan, Nikki L; Luthra, Sajinder K; McRobbie, Graeme; Pimlott, Sally L; Sutherland, Andrew

    2017-10-05

    An operationally simple, one-pot, two-step tandem procedure that allows the incorporation of radioactive iodine into aryl amines via stable diazonium salts is described. The mild conditions are tolerant of various functional groups and substitution patterns, allowing late-stage, rapid access to a wide range of 125 I-labelled aryl compounds and SPECT radiotracers.

  1. Unitary information ether and its possible applications

    International Nuclear Information System (INIS)

    Horodecki, R.

    1991-01-01

    The idea of information ether as the unitary information field is developed. It rests on the assumption that the notion of information is a fundamental category in the description of reality and that it can be defined independently from the notion of probability itself. It is shown that the information ether provides a deterministic background for the nonlinear wave hypothesis and quantum cybernetics. (orig.)

  2. The Ether Wind and the Global Positioning System.

    Science.gov (United States)

    Muller, Rainer

    2000-01-01

    Explains how students can perform a refutation of the ether theory using information from the Global Positioning System (GPS). Discusses the functioning of the GPS, qualitatively describes how position determination would be affected by an ether wind, and illustrates the pertinent ideas with a simple quantitative model. (WRM)

  3. Palladium(II)-catalyzed desulfitative synthesis of aryl ketones from sodium arylsulfinates and nitriles: scope, limitations, and mechanistic studies.

    Science.gov (United States)

    Skillinghaug, Bobo; Sköld, Christian; Rydfjord, Jonas; Svensson, Fredrik; Behrends, Malte; Sävmarker, Jonas; Sjöberg, Per J R; Larhed, Mats

    2014-12-19

    A fast and efficient protocol for the palladium(II)-catalyzed production of aryl ketones from sodium arylsulfinates and various organic nitriles under controlled microwave irradiation has been developed. The wide scope of the reaction has been demonstrated by combining 14 sodium arylsulfinates and 21 nitriles to give 55 examples of aryl ketones. One additional example illustrated that, through the choice of the nitrile reactant, benzofurans are also accessible. The reaction mechanism was investigated by electrospray ionization mass spectrometry and DFT calculations. The desulfitative synthesis of aryl ketones from nitriles was also compared to the corresponding transformation starting from benzoic acids. Comparison of the energy profiles indicates that the free energy requirement for decarboxylation of 2,6-dimethoxybenzoic acid and especially benzoic acid is higher than the corresponding desulfitative process for generating the key aryl palladium intermediate. The palladium(II) intermediates detected by ESI-MS and the DFT calculations provide a detailed understanding of the catalytic cycle.

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

    OpenAIRE

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

    2013-01-01

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

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

    Science.gov (United States)

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

    2009-11-01

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

  6. Fast liquid chromatography-tandem mass spectrometry for the analysis of bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and their derivatives in canned food and beverages.

    Science.gov (United States)

    Gallart-Ayala, H; Moyano, E; Galceran, M T

    2011-03-25

    In this work a fast liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method using a C18 Fused Core™ column, was developed for the simultaneous analysis of bisphenol A diglycidyl ether (BADGE), bisphenol A (2,3-dihydroxypropyl) glycidyl ether (BADGE·H(2)O), bisphenol A bis(2,3-dihydroxypropyl) ether (BADGE·2H(2)O), bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether (BADGE·HCl), bisphenol A bis(3-chloro-2-hydroxypropyl) ether (BADGE·2HCl) and bisphenol A (3-chloro-2-hydroxypropyl)(2,3-dihydroxypropyl ether) (BADGE·HCl·H(2)O) and bisphenol F diglycidyl ether (BFDGE), bisphenol F bis(2,3-dihydroxypropyl) ether (BFDGE·2H(2)O), bisphenol F bis(3-chloro-2-hydroxypropyl) ether (BFDGE·2HCl). The LC method was coupled with a triple quadrupole mass spectrometer, using an ESI source in positive mode and using the [M+NH(4)](+) adduct as precursor ion for tandem mass spectrometry experiments. The method developed was applied to the determination of these compounds in canned soft drinks and canned food. OASIS HLB solid phase extraction (SPE) cartridges were used for the analysis of soft drinks, while solid canned food was extracted with ethyl acetate. Method limits of quantitation ranged from 0.13 μgL(-1) to 1.6 μgL(-1) in soft drinks and 1.0 μgkg(-1) to 4.0 μgkg(-1) in food samples. BADGE·2H(2)O was detected in all the analyzed samples, while other BADGEs such as BADGE·H(2)O, BADGE·HCl·H(2)O, BADGE·HCl and BADGE·2HCl were also detected in canned foods. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Aryl Polyenes, a Highly Abundant Class of Bacterial Natural Products, Are Functionally Related to Antioxidative Carotenoids.

    Science.gov (United States)

    Schöner, Tim A; Gassel, Sören; Osawa, Ayako; Tobias, Nicholas J; Okuno, Yukari; Sakakibara, Yui; Shindo, Kazutoshi; Sandmann, Gerhard; Bode, Helge B

    2016-02-02

    Bacterial pigments of the aryl polyene type are structurally similar to the well-known carotenoids with respect to their polyene systems. Their biosynthetic gene cluster is widespread in taxonomically distant bacteria, and four classes of such pigments have been found. Here we report the structure elucidation of the aryl polyene/dialkylresorcinol hybrid pigments of Variovorax paradoxus B4 by HPLC-UV-MS, MALDI-MS and NMR. Furthermore, we show for the first time that this pigment class protects the bacterium from reactive oxygen species, similarly to what is known for carotenoids. An analysis of the distribution of biosynthetic genes for aryl polyenes and carotenoids in bacterial genomes is presented; it shows a complementary distribution of these protective pigments in bacteria. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Activation of aryl hydrocarbon receptor reduces carbendazim-induced cell death

    International Nuclear Information System (INIS)

    Wei, Kuo-Liang; Chen, Fei-Yun; Lin, Chih-Yi; Gao, Guan-Lun; Kao, Wen-Ya; Yeh, Chi-Hui; Chen, Chang-Rong; Huang, Hao-Chun; Tsai, Wei-Ren; Jong, Koa-Jen; Li, Wan-Jung; Su, Jyan-Gwo Joseph

    2016-01-01

    Carbendazim inhibits microtubule assembly, thus blocking mitosis and inhibiting cancer cell proliferation. Accordingly, carbendazim is being explored as an anticancer drug. Data show that carbendazim increased mRNA and protein expressions and promoter activity of CYP1A1. In addition, carbendazim activated transcriptional activity of the aryl hydrocarbon response element, and induced nuclear translocation of the aryl hydrocarbon receptor (AhR), a sign the AhR is activated. Carbendazim-induced CYP1A1 expression was blocked by AhR antagonists, and was abolished in AhR signal-deficient cells. Results demonstrated that carbendazim activated the AhR, thereby stimulating CYP1A1 expression. In order to understand whether AhR-induced metabolic enzymes turn carbendazim into less-toxic metabolites, Hoechst 33342 staining to reveal carbendazim-induced nuclear changes and flow cytometry to reveal the subG 0 /G 1 population were applied to monitor carbendazim-induced cell apoptosis. Carbendazim induced less apoptosis in Hepa-1c1c7 cells than in AhR signal-deficient Hepa-1c1c7 mutant cells. Pretreatment with β-NF, an AhR agonist that highly induces CYP1A1 expression, decreased carbendazim-induced cell death. In addition, the lower the level of AhR was, the lower the vitality present in carbendazim-treated cells, including hepatoma cells and their derivatives with AhR RNA interference, also embryonic kidney cells, bladder carcinoma cells, and AhR signal-deficient Hepa-1c1c7 cells. In summary, carbendazim is an AhR agonist. The toxicity of carbendazim was lower in cells with the AhR signal. This report provides clues indicating that carbendazim is more potent at inducing cell death in tissues without than in those with the AhR signal, an important reference for applying carbendazim in cancer chemotherapy. - Highlights: • Carbendazim induced transcriptional activity of the aryl hydrocarbon response element. • Carbendazim induced nuclear translocation of the aryl hydrocarbon

  9. Activation of aryl hydrocarbon receptor reduces carbendazim-induced cell death

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Kuo-Liang [Division of Gastroenterology and Hepatology, Department of Internal Medicine, Chang Gung Memorial Hospital, Chiayi 61363, Taiwan, ROC (China); College of Medicine, Chang Gung University, Taoyuan 33302, Taiwan, ROC (China); Chen, Fei-Yun; Lin, Chih-Yi [Department of Biochemical Science and Technology, National Chiayi University, Chiayi 60004, Taiwan, ROC (China); Gao, Guan-Lun [Department of Biochemical Science and Technology, National Chiayi University, Chiayi 60004, Taiwan, ROC (China); Department of Biological Resources, National Chiayi University, Chiayi, 60004, Taiwan, ROC (China); Kao, Wen-Ya [Department of Biochemical Science and Technology, National Chiayi University, Chiayi 60004, Taiwan, ROC (China); Yeh, Chi-Hui [Department of Environmental Engineering, College of Engineering, Da-Yeh University, Dacun, Changhua 51591, Taiwan, ROC (China); Chen, Chang-Rong [Department of Biochemical Science and Technology, National Chiayi University, Chiayi 60004, Taiwan, ROC (China); Huang, Hao-Chun [Division of Gastroenterology and Hepatology, Department of Internal Medicine, Chang Gung Memorial Hospital, Chiayi 61363, Taiwan, ROC (China); Tsai, Wei-Ren [Division of Applied Toxicology, Taiwan Agricultural Chemicals and Toxic Substances Research Institute, Council of Agriculture, Executive Yuan, Taichung 41358, Taiwan, ROC (China); Jong, Koa-Jen [Department of Biological Resources, National Chiayi University, Chiayi, 60004, Taiwan, ROC (China); Li, Wan-Jung [Department of Biochemical Science and Technology, National Chiayi University, Chiayi 60004, Taiwan, ROC (China); Su, Jyan-Gwo Joseph, E-mail: jgjsu@mail.ncyu.edu.tw [Department of Biochemical Science and Technology, National Chiayi University, Chiayi 60004, Taiwan, ROC (China)

    2016-09-01

    Carbendazim inhibits microtubule assembly, thus blocking mitosis and inhibiting cancer cell proliferation. Accordingly, carbendazim is being explored as an anticancer drug. Data show that carbendazim increased mRNA and protein expressions and promoter activity of CYP1A1. In addition, carbendazim activated transcriptional activity of the aryl hydrocarbon response element, and induced nuclear translocation of the aryl hydrocarbon receptor (AhR), a sign the AhR is activated. Carbendazim-induced CYP1A1 expression was blocked by AhR antagonists, and was abolished in AhR signal-deficient cells. Results demonstrated that carbendazim activated the AhR, thereby stimulating CYP1A1 expression. In order to understand whether AhR-induced metabolic enzymes turn carbendazim into less-toxic metabolites, Hoechst 33342 staining to reveal carbendazim-induced nuclear changes and flow cytometry to reveal the subG{sub 0}/G{sub 1} population were applied to monitor carbendazim-induced cell apoptosis. Carbendazim induced less apoptosis in Hepa-1c1c7 cells than in AhR signal-deficient Hepa-1c1c7 mutant cells. Pretreatment with β-NF, an AhR agonist that highly induces CYP1A1 expression, decreased carbendazim-induced cell death. In addition, the lower the level of AhR was, the lower the vitality present in carbendazim-treated cells, including hepatoma cells and their derivatives with AhR RNA interference, also embryonic kidney cells, bladder carcinoma cells, and AhR signal-deficient Hepa-1c1c7 cells. In summary, carbendazim is an AhR agonist. The toxicity of carbendazim was lower in cells with the AhR signal. This report provides clues indicating that carbendazim is more potent at inducing cell death in tissues without than in those with the AhR signal, an important reference for applying carbendazim in cancer chemotherapy. - Highlights: • Carbendazim induced transcriptional activity of the aryl hydrocarbon response element. • Carbendazim induced nuclear translocation of the aryl

  10. Alkyl and aryl phosphorodiiodidites. Pt. 2

    International Nuclear Information System (INIS)

    Feshchenko, N.G.; Kostina, V.G.

    1976-01-01

    Alkyl phosphorodiiodidites are formed in the reactions of alkyl phosphorodichloridites with lithium iodide. They are stable at -60 to -50 0 . When warmed to 20 0 , they disproportionate with conversion into trialkyl phosphites and phosphorus triiodide. The latter also react together and give alkyl iodides, diphosphorus tetraiodide, and a polymer of unestablished structure. Diaryl and dialkyl phosphoriodidites are stable only in solution at low temperatures. They disproportionate in a similar way to aryl and alkyl phosphorodiiodidites. Alkyl phosphorodiiodidites react with iodine with the formation of alkyl iodides and phosphoryl iodide

  11. Silica-Supported Catalyst for Enantioselective Arylation of Aldehydes under Batch and Continuous-Flow Conditions.

    Science.gov (United States)

    Watanabe, Satoshi; Nakaya, Naoyuki; Akai, Junichiro; Kanaori, Kenji; Harada, Toshiro

    2018-05-04

    A silica-supported 3-aryl H 8 -BINOL-derived titanium catalyst exhibited high performance in the enantioselective arylation of aromatic aldehydes using Grignard and organolithium reagents not only under batch conditions but also under continuous-flow conditions. Even with a simple pipet reactor packed with the heterogeneous catalyst, the enantioselective production of chiral diarylmethanols could be achieved through a continuous introduction of aldehydes and mixed titanium reagents generated from the organometallic precursors. The pipet reactor could be used repeatedly in different reactions without appreciable deterioration of the activity.

  12. Poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers with Various Molecular Weights as Phase Change Materials

    Directory of Open Access Journals (Sweden)

    Dongfang Pei

    2018-02-01

    Full Text Available At present, research on the relationship of comb-like polymer phase change material structures and their heat storage performance is scarce. Therefore, this relationship from both micro and macro perspectives will be studied in this paper. In order to achieve a high phase change enthalpy, ethylene glycol segments were introduced between the vinyl and the alkyl side chains. A series of poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers (PC14EnVEs (n = 1, 2 with various molecular weights were polymerized by living cationic polymerization. The results of PC14E1VE and PC14E2VE showed that the minimum number of carbon atoms required for side-chain crystallization were 7.7 and 7.2, which were lower than that reported in the literature. The phase change enthalpy 89 J/g (for poly(mono ethylene glycol n-tetradecyl ether vinyl ethers and 86 J/g (for poly(hexadecyl acrylate were approximately equal. With the increase of molecular weight, the melting temperature, the melting enthalpy, and the initial thermal decomposition temperature of PC14E1VE changed from 27.0 to 28.0 °C, from 95 to 89 J/g, and from 264 to 287 °C, respectively. When the number average molar mass of PC14EnVEs exceeded 20,000, the enthalpy values remained basically unchanged. The introduction of the ethylene glycol chain was conducive to the crystallization of alkyl side chains.

  13. Enantioselective synthesis of chiral 3-aryl-1-indanones through rhodium-catalyzed asymmetric intramolecular 1,4-addition.

    Science.gov (United States)

    Yu, Yue-Na; Xu, Ming-Hua

    2013-03-15

    Enantioselective synthesis of potentially useful chiral 3-aryl-1-indanones was achieved through a rhodium-catalyzed asymmetric intramolecular 1,4-addition of pinacolborane chalcone derivatives using extraordinary simple MonoPhos as chiral ligand under relatively mild conditions. This novel protocol offers an easy access to a wide variety of enantioenriched 3-aryl-1-indanone derivatives in high yields (up to 95%) with excellent enantioselectivities (up to 95% ee).

  14. Carbon Dioxide-Mediated C(sp3)-H Arylation of Amine Substrates.

    Science.gov (United States)

    Kapoor, Mohit; Liu, Daniel; Young, Michael C

    2018-05-25

    Elaborating amines via C-H functionalization has been an important area of research over the past decade but has generally relied on an added directing group or sterically hindered amine approach. Since free-amine-directed C(sp 3 )-H activation is still primarily limited to cyclization reactions and to improve the sustainability and reaction scope of amine-based C-H activation, we present a strategy using CO 2 in the form of dry ice that facilitates intermolecular C-H arylation. This methodology has been used to enable an operationally simple procedure whereby 1° and 2° aliphatic amines can be arylated selectively at their γ-C-H positions. In addition to potentially serving as a directing group, CO 2 has also been demonstrated to curtail the oxidation of sensitive amine substrates.

  15. N-Aryl Arenedicarboximides as Tunable Panchromatic Dyes for Molecular Solar Cells

    Directory of Open Access Journals (Sweden)

    Zhi Cao

    2010-01-01

    Full Text Available Three organic dyes designed as molecular dyads were prepared that feature a common naphthalimide acceptor and N-aryl donors. One of these incorporated an additional cyanoacrylic acid linker and conjugated thiophene bridge inserted between donor and acceptor groups. Electrochemical and photochemical characterizations have been carried out on nanocrystalline TiO2 dye-sensitized solar cells which were fabricated with these dyes as the sensitizing component. HOMO and LUMO energies were also calculated using TDDFT methods and validated by the cyclic voltammetry method. A key finding from this study indicates that computational methods can provide energy values in close agreement to experimental for the N-aryl-naphthalimide system. Relative to HOMO/LUMO energy levels of N719, the dyes based on naphthalimide chromophore are promising candidates for metal-free DSSCs.

  16. Sulfonated polyphenyl ether by electropolymerization

    International Nuclear Information System (INIS)

    Hou Hongying; Vacandio, Florence; Di Vona, Maria Luisa; Knauth, Philippe

    2012-01-01

    Highlights: ► Sulfonated polyphenyl ether was for the first time electropolymerized. ► This technique allows the economical preparation of ionomeric membranes for electrochemical energy technologies. ► The mechanism of electropolymerization was discussed in detail. - Abstract: Electropolymerization of sulfonated phenol was for the first time achieved and studied by cyclic voltammetry (CV) and chronoamperometry on stainless steel substrates. The obtained sulfonated polyphenyl ether was characterized in terms of impedance spectroscopy, nuclear magnetic resonance (NMR), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and Fourier-Transform Infrared (FTIR) spectroscopy. Dense films of micrometer thickness can be obtained; the proton conductivity is about 3 mS/cm at room temperature.

  17. Diethyl Ether Production Process with Various Catalyst Type

    Directory of Open Access Journals (Sweden)

    Widayat Widayat

    2012-12-01

    Full Text Available Several H-zeolite and HZSM-5 catalysts was preparated and their characters have also been investigated. H-zeolit Catalyst was preparated from Natural Zeolite that obtained from Malang District and Gunung Kidul District. Diethyl ether was produced by Ethanol with concentration of 95%. This research use fixed bed reactor that 1 gram of catalyst as bed catalyst, atmospheric pressure and temperature 140oC as the operating condition. Ethanol vapor from vaporization tank was driven by 200 ml/min Nitrogen stream. The responds in this research is liquid product concentration; diethyl ether, ethanol, methanol and water concentration. The results showed that the largest ethanol conversion was produced by the use of 56.44% HZSM-5 and the largest yield of diethyl ether diethyl was produced by the use of alumina and H-zeolite catalyst. The larger ratio between natural zeolite with HCl solvent will produce the larger surface area of catalyst and ethanol conversion. The largest ethanol conversion was produced at reactan ratio 1:20. [Keywords:  catalyst; ethanol conversion; dehydration process; yield of diethyl ether; natural zeolite].

  18. Investigation of synthesis, thermal properties and curing kinetics of fluorene diamine-based benzoxazine by using two curing kinetic methods

    International Nuclear Information System (INIS)

    He, Xuan-yu; Wang, Jun; Ramdani, Noureddine; Liu, Wen-bin; Liu, Li-jia; Yang, Lei

    2013-01-01

    Graphical abstract: - Highlights: • A novel diamine-based benzoxazine monomer containing aryl ether and bulky fluorene groups (BEF-p) is synthesized. • Kinetic parameters can be calculated by Starink-LSR method and direct LSR method. • Cure reaction could be successfully described with the autocatalytic model. • The poly(BEF-p) exhibits high T g and superior thermal stability. • Aryl ether linkages had little influence on the thermal stability. - Abstract: A novel diamine-based benzoxazine monomer containing aryl ether and bulky fluorene groups (BEF-p) was prepared from the reaction of 9,9-bis-[4-(p-aminophenoxy)-phenyl]fluorene with paraformaldehyde and phenol. The chemical structure of monomer was confirmed by Fourier-transform infrared (FTIR) and 1 H and 13 C nuclear magnetic resonance spectroscopy ( 1 H and 13 C NMR). The polymerization behavior of monomer was analyzed by differential scanning calorimetry (DSC) and FTIR. The curing kinetics was studied by non-isothermal DSC, and the kinetic parameters were determined. The autocatalytic model based on two kinetic methods (Starink-LSR method and direct LSR method) showed good agreement with experimental results. The thermal and mechanical properties of poly(BEF-p) were evaluated with DSC, dynamic mechanical thermal analysis (DMTA), and thermogravimetric analysis (TGA). The results showed that the cured polymer exhibited higher glass transition temperature (T g ) and better thermal stability compared with diaminodiphenylmethane-based benzoxazine(P-ddm), and was slightly lower than those of fluorene diamine-phenol-based polybenzoxazine (poly(BF-p))

  19. Dihydroquinazolines as a novel class of Trypanosoma brucei trypanothione reductase inhibitors: discovery, synthesis, and characterization of their binding mode by protein crystallography.

    Science.gov (United States)

    Patterson, Stephen; Alphey, Magnus S; Jones, Deuan C; Shanks, Emma J; Street, Ian P; Frearson, Julie A; Wyatt, Paul G; Gilbert, Ian H; Fairlamb, Alan H

    2011-10-13

    Trypanothione reductase (TryR) is a genetically validated drug target in the parasite Trypanosoma brucei , the causative agent of human African trypanosomiasis. Here we report the discovery, synthesis, and development of a novel series of TryR inhibitors based on a 3,4-dihydroquinazoline scaffold. In addition, a high resolution crystal structure of TryR, alone and in complex with substrates and inhibitors from this series, is presented. This represents the first report of a high resolution complex between a noncovalent ligand and this enzyme. Structural studies revealed that upon ligand binding the enzyme undergoes a conformational change to create a new subpocket which is occupied by an aryl group on the ligand. Therefore, the inhibitor, in effect, creates its own small binding pocket within the otherwise large, solvent exposed active site. The TryR-ligand structure was subsequently used to guide the synthesis of inhibitors, including analogues that challenged the induced subpocket. This resulted in the development of inhibitors with improved potency against both TryR and T. brucei parasites in a whole cell assay.

  20. Cyprodinil as an activator of aryl hydrocarbon receptor

    International Nuclear Information System (INIS)

    Fang, Chien-Chung; Chen, Fei-Yun; Chen, Chang-Rong; Liu, Chien-Chiang; Wong, Liang-Chi; Liu, Yi-Wen; Su, Jyan-Gwo Joseph

    2013-01-01

    Highlights: ► Cyprodinil activated the aryl hydrocarbon receptor (AHR). ► Cyprodinil induced nuclear translocation of the AHR, and the expression of CYP1A1. ► Cyprodinil enhanced dexamethasone-induced gene expression. ► Cyprodinil phosphorylated ERK, indicating its deregulation of ERK activity. -- Abstract: Cyprodinil is a pyrimidinamine fungicide, used worldwide by agriculture. It is used to protect fruit plants and vegetables from a wide range of pathogens. Benzo[a]pyrene (BaP) and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) are toxic environmental pollutants and are prototypes of aryl hydrocarbon receptor (AHR) ligands. Although the structure of cyprodinil distinctly differs from those of BaP and TCDD, our results show that cyprodinil induced nuclear translocation of the AHR, and induced the transcriptional activity of aryl hydrocarbon response element (AHRE). Cyprodinil induced the expression of cytochrome P450 (CYP) 1A1, a well-known AHR-targeted gene, in ovarian granulosa cells, HO23, and hepatoma cells, Hepa-1c1c7. Its induction did not appear in AHR signal-deficient cells, and was blocked by the AHR antagonist, CH-223191. Cyprodinil decreased AHR expression in HO23 cells, resulting in CYP1A1 expression decreasing after it peaked at 9 h of treatment in HO23 cells. Dexamethasone is a synthetic agonist of glucocorticoids. Cyprodinil enhanced dexamethasone-induced gene expression, and conversely, its induction of CYP1A1 expression was decreased by dexamethasone in HO23 cells, indicating its induction of crosstalk between the AHR and glucocorticoid receptor and its role as a potential endocrine disrupter. In addition to BaP, TCDD, and an AHR agonist, β-NF, cyprodinil also phosphorylated extracellular signal-regulated kinase (ERK) in HO23 and Hepa-1c1c7 cells, indicating its deregulation of ERK activity. In summary, our results demonstrate that cyprodinil, similar to BaP, acts as an AHR activator, a potential endocrine disrupter, and an ERK disrupter

  1. Preliminary Investigation of Poly-Ether-Ether-Ketone Based on Fused Deposition Modeling for Medical Applications

    Directory of Open Access Journals (Sweden)

    Feng Zhao

    2018-02-01

    Full Text Available Poly-ether-ether-ketone (PEEK fabricated by fused deposition modeling for medical applications was evaluated in terms of mechanical strength and in vitro cytotoxicity in this study. Orthogonal experiments were firstly designed to investigate the significant factors on tensile strength. Nozzle temperature, platform temperature, and the filament diameter were tightly controlled for improved mechanical strength performance. These sensitive parameters affected the interlayer bonding and solid condition in the samples. Fourier transform infrared (FTIR spectrometry analysis was secondly conducted to compare the functional groups in PEEK granules, filaments, and printed parts. In vitro cytotoxicity test was carried out at last, and no toxic substances were introduced during the printing process.

  2. A novel application of 2-silylated 1,3-dithiolanes for the synthesis of aryl/hetaryl-substituted ethenes and dibenzofulvenes

    Directory of Open Access Journals (Sweden)

    Grzegorz Mlostoń

    2017-09-01

    Full Text Available Trimethylsilyldiazomethane (TMS-CHN2 reacts readily with hetaryl thioketones to give sterically crowded 2-trimethylsilyl-4,4,5,5-tetrahetaryl-1,3-dithiolanes with complete regioselectivity at −75 °C as well as at rt. Thiofluorenone, a relatively stable and highly reactive aryl thioketone, yields upon treatment with TMS-CHN2 at −60 °C the corresponding 1,3,4-thiadiazoline. This unstable cycloadduct undergoes decomposition at ca. −45 °C and the silylated thiocarbonyl S-methanide generated thereby is trapped with complete regioselectivity by aryl or hetaryl thioketones forming also sterically crowded 2-trimethylsilyl-1,3-dithiolanes. The obtained 1,3-dithiolanes, by treatment with an equimolar amount of TBAF in a one-pot procedure, are converted in high yields into hetaryl/aryl-substituted ethenes or dibenzofulvenes, respectively, via a cycloreversion reaction of the intermediate 1,3-dithiolane carbanion. The presented protocol offers a new, highly efficient approach to tetrasubstituted ethenes and dibenzofulvenes bearing aryl and/or hetaryl substituents.

  3. Design and stereoselective synthesis of a C-aryl furanoside as a conformationally constrained CHIR-090 analogue

    DEFF Research Database (Denmark)

    Oddo, Alberto; Holl, Ralph

    2012-01-01

    The UDP-3-O-[(R)-3-hydroxymyristoyl]-N-acetylglucosamine deacetylase (LpxC) is a promising target for the development of novel antibiotic substances against multidrug-resistant Gram-negative bacteria. The C-aryl glycoside 3 was designed as conformationally constrained analogue of the potent LpxC-......, and esterification. A Sonogashira reaction of the aryl iodide 11 led to the alkyne 17 which was transformed with H(2)NOH into the hydroxamic acid 3....

  4. Densely quaternized poly(arylene ether)s with distinct phase separation for highly anion-conductive membranes

    Science.gov (United States)

    Hu, Yuanfang; Wang, Bingxi; Li, Xiao; Chen, Dongyang; Zhang, Weiying

    2018-05-01

    To develop high performance anion exchange membranes (AEMs), a novel bisphenol monomer bearing eight benzylmethyl groups at the outer edge of the molecule was synthesized, which after condensation polymerization with various amounts of 4,4‧-dihydroxydiphenylsulfone and 4,4‧-difluorobenzophenone yielded novel poly(arylene ether)s with densely located benzylmethyl groups. These benzylmethyl groups were then converted to quaternary ammonium groups by radical-initiated bromination and quaternization in tandem, leading to the emergence of densely quaternized poly(arylene ether sulfone)s (QA-PAEs) with controlled ion exchange capacities (IECs) ranging from 1.61 to 2.32 mmol g-1. Both small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) studies revealed distinct phase separation in the QA-PAEs. The QA-PAE-40 with an IEC of 2.32 mmol g-1 exhibited a Br- conductivity of 9.2 mS cm-1 and a SO42- conductivity of 14.0 mS cm-1 at room temperature, much higher than those of a control membrane with a similar IEC but without obvious phase separation. Therefore, phase separation of AEMs was validated to be advantageous for the efficient conducting of anions. The experimental results also showed that the QA-PAEs were promising AEM materials, especially for non-alkaline applications.

  5. 40 CFR 721.10017 - Amine terminated bisphenol A diglycidyl ether polymer (generic).

    Science.gov (United States)

    2010-07-01

    ... diglycidyl ether polymer (generic). 721.10017 Section 721.10017 Protection of Environment ENVIRONMENTAL... ether polymer (generic). (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substances identified generically as amine terminated bisphenol A diglycidyl ether polymer (PMNs P...

  6. Silica-supported Macroporous Chitosan Bead for Affinity Purification of Trypsin Inhibitor

    Institute of Scientific and Technical Information of China (English)

    Feng Na XI; Jian Min WU; Ming Ming LUAN

    2005-01-01

    Macroporous cross-linking chitosan layer coated on silica gel (CTS-SiO2) was prepared by phase inversion and polyethylene glycol (PEG) molecular imprinting methods. Formation of macroporous surface was investigated by scanning electron microscopy (SEM) and BET analysis.The prepared bead was activated by reacting with 1,2-ethylene diglycidyl ether for introducing epoxy groups, and trypsin could be efficiently immobilized on the bead as a biospecific ligand.The bead bearing trypsin was employed to purify trypsin inhibitor (TIs) from egg white as affinity adsorbent.

  7. Congenital malformations and maternal occupational exposure to glycol ethers

    NARCIS (Netherlands)

    Cordier, S; Bergeret, A; Goujard, J; Ha, MC; Ayme, S; Calzolari, E; DeWalle, HEK; KnillJones, R; Candela, S; Dale, [No Value; Dananche, B; deVigan, C; Fevotte, J; Kiel, G; Mandereau, L

    Glycol ethers are found in a wide range of domestic and industrial products, many of which are used in women's work environments. Motivated by concern about their potential reproductive toxicity, we have evaluated the risk of congenital malformations related to glycol ether exposure during preg

  8. Catalytic arylation methods from the academic lab to industrial processes

    CERN Document Server

    Burke, Anthony J

    2014-01-01

    This "hands-on" approach to the topic of arylation consolidates the body of key research over the last ten years (and up to around 2014) on various catalytic methods which involve an arylation process. Clearly structured, the chapters in this one-stop resource are arranged according to the reaction type, and focus on novel, efficient and sustainable processes, rather than the well-known and established cross-coupling methods. The entire contents are written by two authors with academic and industrial expertise to ensure consistent coverage of the latest developments in the field, as well as industrial applications, such as C-H activation, iron and gold-catalyzed coupling reactions, cycloadditions or novel methodologies using arylboron reagents. A cross-section of relevant tried-and-tested experimental protocols is included at the end of each chapter for putting into immediate practice, along with patent literature. Due to its emphasis on efficient, "green" methods and industrial applications of the products c...

  9. Rational optimization of drug-target residence time: Insights from inhibitor binding to the S. aureus FabI enzyme-product complex

    Science.gov (United States)

    Chang, Andrew; Schiebel, Johannes; Yu, Weixuan; Bommineni, Gopal R.; Pan, Pan; Baxter, Michael V.; Khanna, Avinash; Sotriffer, Christoph A.; Kisker, Caroline; Tonge, Peter J.

    2013-01-01

    Drug-target kinetics has recently emerged as an especially important facet of the drug discovery process. In particular, prolonged drug-target residence times may confer enhanced efficacy and selectivity in the open in vivo system. However, the lack of accurate kinetic and structural data for series of congeneric compounds hinders the rational design of inhibitors with decreased off-rates. Therefore, we chose the Staphylococcus aureus enoyl-ACP reductase (saFabI) - an important target for the development of new anti-staphylococcal drugs - as a model system to rationalize and optimize the drug-target residence time on a structural basis. Using our new, efficient and widely applicable mechanistically informed kinetic approach, we obtained a full characterization of saFabI inhibition by a series of 20 diphenyl ethers complemented by a collection of 9 saFabI-inhibitor crystal structures. We identified a strong correlation between the affinities of the investigated saFabI diphenyl ether inhibitors and their corresponding residence times, which can be rationalized on a structural basis. Due to its favorable interactions with the enzyme, the residence time of our most potent compound exceeds 10 hours. In addition, we found that affinity and residence time in this system can be significantly enhanced by modifications predictable by a careful consideration of catalysis. Our study provides a blueprint for investigating and prolonging drug-target kinetics and may aid in the rational design of long-residence-time inhibitors targeting the essential saFabI enzyme. PMID:23697754

  10. The generation of singlet oxygen (o(2)) by the nitrodiphenyl ether herbicide oxyfluorfen is independent of photosynthesis.

    Science.gov (United States)

    Haworth, P; Hess, F D

    1988-03-01

    The mechanism of action of the p-nitrodiphenyl ether herbicides has remained ambiguous because of conflicting reports in the literature. The diphenyl ether herbicide oxyfluorfen causes a light induced consumption of oxygen which resembles the electron acceptor reaction of paraquat. However, this reaction is not linked to the transport of electrons through photosystem I. This conclusion is based on the observation that the rate of oxygen consumption, in the presence of oxyfluorfen, does not demonstrate a first order rate dependence on light intensity. Using the bleaching of N,N-dimethyl p-nitrosoaniline as a specific detector of singlet oxygen, we demonstrate that oxyfluorfen is a potent generator of this toxic radical. The production of singlet oxygen occurs in the presence of inhibitors of photosynthetic electron transport (oxyfluorfen at 10(-4) molar and paraquat) and also under temperature conditions (3 degrees C) which prevent electron transport. This light induced reaction results in oxygen consumption and is the primary cause of lethality for oxyfluorfen. The production of singlet oxygen occurs rapidly and at low herbicide concentrations (10(-9) molar). The reaction occurs without photosynthetic electron transport but does require an intact thylakoid membrane.

  11. On prediction of inhibiting properties of o-aryl-carboxylates in local dissolution of iron

    International Nuclear Information System (INIS)

    Kuznetsov, Yu.I.; Kerbeleva, I.Ya.; Brusnikina, V.M.; Rozenfel'd, I.L.

    1979-01-01

    The anodic behaviour of Armco iron in the borate buffer (ph 7.4), containing sulphates as agressive anions and inhibiting substances - aryl carboxilates is studied. The possibility of using the principle of free energy linearity for quantitative prediction of protective properties of aryl carboxilates at the metal local solution is shown. The latter characterized by the pitting formation potential (phi sub(pf)), the inhibiting criterion being Δphi=phisub(pf)sup(R)-phisub(pf)sup(H). The linear correlation between Δphi and delta constants, reflecting the summary electron effects of substituent induction and mesomeric effects have been found

  12. Direct transformation of silyl enol ethers into functionalized allenes.

    Science.gov (United States)

    Langer, P; Döring, M; Seyferth, D; Görls, H

    2001-02-02

    The first elimination reactions of silyl enol ethers to lithiated allenes are reported. These reactions allow a direct transformation of readily available silyl enol ethers into functionalized allenes. The action of three to four equivalents of lithium diisopropylamide (LDA) on silyl enol ethers results in the formation of lithiated allenes by initial allylic lithiation, subsequent elimination of a lithium silanolate, and finally, lithiation of the allene thus formed. Starting with amide-derived silyl imino ethers, lithiated ketenimines are obtained. A variety of reactions of the lithiated allenes with electrophiles (chlorosilanes, trimethylchlorostannane, dimethyl sulfate and ethanol) were carried out. Elimination of silanolate is observed only for substrates that contain the hindered SiMe2tBu or Si(iPr)3 moiety, but not for the SiMe3 group. The reaction of 1,1-dilithio-3,3-diphenylallene with ketones provides a convenient access to novel 1,1-di(hydroxymethyl)allenes which undergo a domino Nazarov-Friedel-Crafts reaction upon treatment with p-toluenesulfonic acid.

  13. Copper-mediated Synthesis of Mono- and Dichlorinated Diaryl Ethers

    Czech Academy of Sciences Publication Activity Database

    Čermák, Jan K.; Církva, Vladimír

    2014-01-01

    Roč. 55, č. 30 (2014), s. 4185-4188 ISSN 0040-4039 Institutional support: RVO:67985858 Keywords : O-arylation * Chan-Lam coupling * kovats indices Subject RIV: CC - Organic Chemistry Impact factor: 2.379, year: 2014

  14. Flax fabric reinforced arylated soy protein composites: A brittle-matrix behaviour

    CSIR Research Space (South Africa)

    Kumar, R

    2012-05-01

    Full Text Available Biocomposites were successfully prepared by the reinforcement of soy protein isolate (SPI) with different weight fractions of woven flax fabric. The flax-fabric-reinforced SPI-based composites were then arylated with 2,2-diphenyl-2-hydroxyethanoic...

  15. One-pot, Facile Synthesis of Quinoxaline Derivatives from Bis-aryl a ...

    African Journals Online (AJOL)

    NICO

    Bis-aryl a-Hydroxyketones and o-Arenediamines using. KMnO. 4. /CuSO. 4 ... Faculty of Chemistry, Bu-Ali Sina University, Hamedan 65174, Iran. Received 31 ... cent materials,6 organic semiconductors,7 building blocks for the synthesis of ...

  16. Interaction of model aryl- and alkyl-boronic acids and 1,2-diols in aqueous solution.

    Science.gov (United States)

    Marinaro, William A; Prankerd, Richard; Kinnari, Kaisa; Stella, Valentino J

    2015-04-01

    The goal of this work was to quantitate ester formation between alkyl and aryl boronic acids and vicinal-diols or 1,2-diols in aqueous solution. As used here, 1,2-diols includes polyols with one or more 1,2-diol pairs. Multiple techniques were used including apparent pKa shifts of the boronic acids using UV spectrophotometry (for aryl acids) and titration (for aryl and alkyl acids). Isothermal microcalorimetry was also used, with all reactions being enthalpically favored. For all the acids and 1,2-diols and the conditions studied, evidence only supported 1:1 ester formation. All the esters formed were found to be significantly more acidic, as Lewis acids, by 3-3.5 pKa units than the corresponding nonesterified boronic acid. The equilibrium constants for ester formation increased with increasing number of 1,2-diol pairs but stereochemistry may also play a role as sorbitol with five possible 1,2-diol pairs and five isomers (taking into account the stereochemistry of the alcohol groups) was twice as efficient at ester formation compared with mannitol, also with five possible 1,2-diol pairs but only three isomers. Alkyl boronic acids formed esters to a greater extent than aryl acids. Although some quantitative differences were seen between the various techniques used, rank ordering of the structure/reactivity was consistent. Formulation implications of ester formation between boronic acids and 1,2-diols are discussed. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  18. Direct arylation of benzene with aryl bromides using high-temperature/high-pressure process windows: expanding the scope of C-H activation chemistry.

    Science.gov (United States)

    Pieber, Bartholomäus; Cantillo, David; Kappe, C Oliver

    2012-04-16

    A detailed investigation on the direct arylation of benzene with aryl bromides by using first-row transition metals under high-temperature/high-pressure (high-T/p) conditions is described. By employing a parallel reactor platform for rapid reaction screening and discovery at elevated temperatures, various metal/ligand/base combinations were evaluated for their ability to enable biaryl formation through C-H activation. The combination of cobalt(III) acetylacetonate and lithium bis(trimethylsilyl)amide was subjected to further process intensification at 200 °C (15 bar), allowing a significant reduction of the catalyst/base loading and a dramatic increase in catalytic efficiency (turnover frequency) by a factor of 1000 compared to traditional protocols. The high-throughput screening additionally identified novel nickel- and copper-based metal/ligand combinations that favored an amination pathway competing with C-H activation, with the addition of ligands, such as 1,10-phenanthroline, having a profound influence on the selectivity. In addition to metal-based catalysts, high-T/p process windows were also successfully applied to transition-metal-free systems, utilizing 1,10-phenanthroline as organocatalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Synthesis of radiolabelled aryl azides from diazonium salts: experimental and computational results permit the identification of the preferred mechanism.

    Science.gov (United States)

    Joshi, Sameer M; de Cózar, Abel; Gómez-Vallejo, Vanessa; Koziorowski, Jacek; Llop, Jordi; Cossío, Fernando P

    2015-05-28

    Experimental and computational studies on the formation of aryl azides from the corresponding diazonium salts support a stepwise mechanism via acyclic zwitterionic intermediates. The low energy barriers associated with both transition structures are compatible with very fast and efficient processes, thus making this method suitable for the chemical synthesis of radiolabelled aryl azides.

  20. Cyclohexenones Through Addition of Ethyl Acetoacetate to 3-Aryl-1 ...

    African Journals Online (AJOL)

    Chalcone derivatives 3a–i containing a thiophene ring were prepared by the condensation of 1-(thiophen-3-yl)ethanone with aromatic aldehydes in excellent yields. The Michael addition of ethyl acetoacetate 4 to chalcone derivatives 3a–i resulted in the formation of nine novel ethyl 6-aryl ...

  1. Planck's constant and the three waves (TWs) of Einstein's covariant ether

    Science.gov (United States)

    Kostro, L.

    1985-11-01

    The implications of a three-wave model for elementary particles, satisfying the principles of both quantum mechanics and General Relativity (GR), are discussed. In GR, the ether is the fundamental source of all activity, where particles (waves) arise at singularities. Inertia and gravity are field properties of the ether. In flat regions of the space-time geodesic, wave excitations correspond to the presence of particles. A momentum-carrying excitation which occurs in the ether is a superluminal radiation (phase- or B-waves) which transports neither energy nor mass. Superposition of the B-waves produces soliton-like excitations on the ether to form C-waves, i.e., particles. The particle-waves travel through space-time on D-waves, and experience reflection, refraction and interference only where B-waves have interacted with the ether. The original particles, photons-maximons, existed at the Big Bang and had physical properties which are describable in terms of Planck's quantities.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1973-05-22

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

  3. 2-ARYL-6,8-DIBROMO-2,3-DIHYDROQUINAZOLIN-4(1H)

    African Journals Online (AJOL)

    Preferred Customer

    The first task in this investigation was to synthesize the requisite 2-aryl-6 .... carbonate as a base in aqueous DMF at 120 °C. We isolated after 2 h by ..... cool to room temperature and then quenched with saturated sodium thiosulfate solution.

  4. Aryl hydrocarbon receptor ligand effects in RBL2H3 cells

    DEFF Research Database (Denmark)

    Maaetoft-Udsen, Kristina; Shimoda, Lori M. N.; Frøkiær, Hanne

    2012-01-01

    The aryl hydrocarbon receptor (AHR) mediates toxic effects of dioxin and xenobiotic metabolism. AHR has an emerging role in the immune system, but its physiological ligands and functional role in immunocytes remain poorly understood. Mast cells are immunocytes that are central to inflammatory...

  5. Aryl diazonium salts: a new class of coupling agents for bonding polymers, biomacromolecules and nanoparticles to surfaces.

    Science.gov (United States)

    Mahouche-Chergui, Samia; Gam-Derouich, Sarra; Mangeney, Claire; Chehimi, Mohamed M

    2011-07-01

    This critical review summarizes existing knowledge on the use of diazonium salts as a new generation of surface modifiers and coupling agents for binding synthetic polymers, biomacromolecules, and nanoparticles to surfaces. Polymer grafts can be directly grown at surfaces through the so-called grafting from approaches based on several polymerization methods but can also be pre-formed in solution and then grafted to surfaces through grafting onto strategies including "click" reactions. Several routes are also described for binding biomacromolecules through aryl layers in view of developing biosensors and protein arrays, while the use of aryl diazonium coupling agents is extended to the attachment of nanoparticles. Patents and industrial applications of the surface chemistry of diazonium compounds are covered. This review stresses the paramount role of aryl diazonium coupling agents in adhesion, surface and materials sciences (114 references).

  6. Synthesis of positron labeled photoactive compounds: 18F labeled aryl azides for positron labeling of biochemical molecules

    International Nuclear Information System (INIS)

    Hashizume, Kazunari; Hashimoto, Naota; Miyake, Yoshihiro

    1995-01-01

    The authors have prepared various [ 18 F] fluorine labeled aryl azides as a novel photoactive compounds suitable for positron labeling of biochemical molecules. The introduction of fluorine substituents to aryl azides can be expected to have dramatic effects on their nature and reactivity toward photolysis. Positron labeled reagents for labeling proteins or peptides have recently attracted considerable attention due to their wide applicability in biochemistry and positron emission tomography (PET). Various labeled azide compounds are often used in biochemistry for radiolabeling biological molecules by photolysis, but there have been no reports on the preparation or use of fluorine-18 labeled azides. The authors now report a novel synthesis of 18 F-labeled aryl azides which will have wide application in the biochemistry and nuclear medicine as a means for 18 F-fluorine labeling for proteins, peptides, and nucleic acids. 2 tabs

  7. An improved synthesis process of calixcrown ethers and synthesis of novel calixcrown ether

    International Nuclear Information System (INIS)

    Wang Hairong; Zhang Ping; Wang Chunmiao; Wang Jianchen; Chen Jing

    2007-01-01

    The synthesis method of calixcrown ethers was simplified and improved, and 10 L- scale synthesis was carried out. In the synthesis of the intermediates of the first three steps, the synthesis of 5, 11, 17, 23-tetra-tert-butyl-25, 26, 27, 28-tetrahydroxyl-calix[4] and its dehydroxylation were considered together, the purification procedures of the former, including re-crystallization in toluene and decolorization with activated carbon, were cancelled, and thus these steps were simplified. In the synthesis of oligoethylene glycol ditosylate, the purification method was also improved and the time-consuming column chromatography was left out. In the final step, impurities were removed by repeating stirring-settlement steps, by following recrystallization, the pure product was obtained. With these measures, the whole process could be implemented easily. The industrial scale production of calixcrown ethers could be fulfilled with the improved process. In addition, a new extracant, 25, 27-bis (n-propyloxy)calix[4]-26, 28-crown-6, is prepared and identified. (authors)

  8. Synthesis of 4-aryl-2,6-dimethyl-3,5-bis-N-(aryl-carbamoyl-1,4-dihydropyridines as novel skin protecting and anti-aging agents

    Directory of Open Access Journals (Sweden)

    Aamer Saeed

    2017-06-01

    Full Text Available A series of 4-aryl-2,6-dimethyl-3,5-bis-N-(aryl-carbamoyl-1,4-dihydropyri-dines 6a-6h were prepared by using the one-pot three component synthetic method. The target compounds 6a-6h were synthesized by reacting two molar equivalents of ketone functionality and one mole of aromatic aldehydes in ammonium acetate to obtain the desired products. The structures of newly synthesized compounds were characterized by FT-IR, 1H-NMR, 13C-NMR, and elemental analysis. All the synthesized compounds were screened for their elastase inhibition and antioxidant activity. Almost all of the com-pounds 6a-h showed good to excellent activities against elastase enzyme more than the reference drug. Compounds 6d and 6b at 0.2 ± 0.0 µM and 0.2 ± 0.0 µM were found to most potent derivatives against elastase enzyme. Compound 6a exhibited prominent free radical scavenging activity. From the results of the biological activity, we infer that some derivatives can serve as lead molecules in pharmacology.

  9. Investigation of ammonium trinitratouranylate complexing with diethyl ether

    International Nuclear Information System (INIS)

    Khod'ko, N.N.; Kolevich, T.A.; Umrejko, D.S.

    1989-01-01

    Interaction of ammonium trinitratouranylate (ATNU) with diethyl ether is investigated. It is shown, that adduct of UO 2 (NO 3 ) 2 · 2(C 2 H 5 ) 2 O coposition is formed in the indicated solvent due to incongruent solubility of ANTU. Analogous compound is obtained at ether effect on uranyl anhydrous nitrate. The matter is determined and investigated by means of chemical, thermal analyses and oscillating spectroscopy

  10. Intramolecular anionic diels-alder reactions of 1-aryl-4-oxahepta-1,6-diyne systems in DMSO.

    Science.gov (United States)

    Kudoh, Takayuki; Mori, Tomoko; Shirahama, Mitsuhito; Yamada, Masashi; Ishikawa, Teruhiko; Saito, Seiki; Kobayashi, Hisayoshi

    2007-04-25

    Base-promoted cycloaddition reactions of 1-aryl- or 1-aryl-7-substituted-4-oxahepta-1,6-diyne systems in DMSO have proven to involve an anionic intramolecular Diels-Alder process taking place even at room temperature in spite of the reaction suffering from temporary disruption of aromaticity. Although initially formed alpha-arylallenide anion can be protonated by DMSO, it can be back to the allenide anion probably because of a small acidity difference between alpha-arylallene and DMSO. The alpha-arylallenide anion in combination with the alpha-aryl substituent can constitute an anionic diene structure that undergoes the intramolecular Diels-Alder reaction involving the C(6)-yne part, a very fast process probably because of the increased HOMO-1 level of the anionic diene, as shown by DFT calculations. Diversified substituted naphthalenes, benzofurans, phenanthrenes, and quinolines, including biaryl architectures, are available from 4-oxahepta-1,6-diynes in a highly expeditious way.

  11. Ring opening of a resin-bound chiral aziridine with phenol nucleophiles

    DEFF Research Database (Denmark)

    Ottesen, Lars Korsgaard; Jaroszewski, Jerzy W; Franzyk, Henrik

    2010-01-01

    An efficient and versatile solid-phase route for the preparation of aryl-alkyl ethers is described. Regioselective ring opening of a resin-bound chiral aziridine with phenolic nucleophiles constitutes the key feature of the present protocol that allows incorporation of fluorescent moieties...

  12. Study of the Air-Tolerant 1,3-Diphosphacyclobutane-2,4-diyl through the Direct Arylation.

    Science.gov (United States)

    Ito, Shigekazu

    2018-04-01

    Installing π-functional substituents on the skeletal phosphorus atoms of the air-tolerant 1,3-diphosphacyclobutane-2,4-diyl unit are promising for tuning the open-shell singlet P-heterocyclic chromophore. The sterically encumbered 1,3-diphosphaCycloButen-4-yl Anion (CBA), generated from the phosphorus-carbon triple bond, was available for the regioselective arylation via nucleophilic aromatic substitution (S N Ar) reaction, addition to arynes, and single-electron transfer (SET) process affording the corresponding P-arylated 1,3-diphosphacyclobutane-2,4-diyls. The photo-absorption and redox properties correlated with the effects of the aryl substituents on the 1,3-diphosphacyclobutane-2,4-diyl unit. The X-ray analyses enabled not only to discuss the metric parameters but also to visualize the radicalic electrons via the electron-density distribution analysis. The electron-donating character of the P-heterocyclic chromophores induced the p-type semiconductor behavior. Detection of hydrogen fluoride via formation of the 1λ 5 ,3λ 5 -diphosphete derivative was also developed. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Molecular Modeling Studies of Thiophenyl C-Aryl Glucoside SGLT2 Inhibitors as Potential Antidiabetic Agents

    Directory of Open Access Journals (Sweden)

    Mukesh C. Sharma

    2014-01-01

    Full Text Available A QSAR study on thiophenyl derivatives as SGLT2 inhibitors as potential antidiabetic agents was performed with thirty-three compounds. Comparison of the obtained results indicated the superiority of the genetic algorithm over the simulated annealing and stepwise forward-backward variable method for feature selection. The best 2D QSAR model showed satisfactory statistical parameters for the data set (r2=0.8499, q2=0.8267, and pred_r2=0.7729 with four descriptors describing the nature of substituent groups and the environment of the substitution site. Evaluation of the model implied that electron-rich substitution position improves the inhibitory activity. The good predictive 3D-QSAR models by k-nearest neighbor (kNN method for molecular field analysis (MFA have cross-validated coefficient q2 value of 0.7663 and predicted r2 value of 0.7386. The results have showed that thiophenyl groups are necessary for activity and halogen, bulky, and less bulky groups in thiophenyl nucleus enhanced the biological activity. These studies are promising for the development of novel SGLT2 inhibitor, which may have potent antidiabetic activity.

  14. The Generation of Singlet Oxygen (1O2) by the Nitrodiphenyl Ether Herbicide Oxyfluorfen Is Independent of Photosynthesis

    Science.gov (United States)

    Haworth, Phil; Hess, F. Dan

    1988-01-01

    The mechanism of action of the p-nitrodiphenyl ether herbicides has remained ambiguous because of conflicting reports in the literature. The diphenyl ether herbicide oxyfluorfen causes a light induced consumption of oxygen which resembles the electron acceptor reaction of paraquat. However, this reaction is not linked to the transport of electrons through photosystem I. This conclusion is based on the observation that the rate of oxygen consumption, in the presence of oxyfluorfen, does not demonstrate a first order rate dependence on light intensity. Using the bleaching of N,N-dimethyl p-nitrosoaniline as a specific detector of singlet oxygen, we demonstrate that oxyfluorfen is a potent generator of this toxic radical. The production of singlet oxygen occurs in the presence of inhibitors of photosynthetic electron transport (oxyfluorfen at 10−4 molar and paraquat) and also under temperature conditions (3°C) which prevent electron transport. This light induced reaction results in oxygen consumption and is the primary cause of lethality for oxyfluorfen. The production of singlet oxygen occurs rapidly and at low herbicide concentrations (10−9 molar). The reaction occurs without photosynthetic electron transport but does require an intact thylakoid membrane. PMID:16665968

  15. Metal ion separations with proton-ionizable Lariat Ethers and their polymers

    International Nuclear Information System (INIS)

    Bartsch, R.A.

    1993-01-01

    The preparation of novel and specific organic complexing agents may lead to the development of new separation systems for aqueous metal ions. Thus the introduction of highly lipophilic oximes led to the current utilization of these compounds as commercial extractants for the hydrometallurgy of nonferrous metals. Crown ethers (macrocyclic polyethers) have been employed in the laboratory-scale solvent extraction of alkali-metal, alkaline-earth, and other metal cations into organic phases. Attachment of side arms to crown ethers gives lariat ethers. The presence of one or more potential coordination sites in the side arm of the lariat ether may produce substantial changes in the selectivity and efficiency of metal ion complexation. It has been demonstrated that concomitant transfer of an aqueous phase anion into the organic medium is not required for metal ion extraction. This factor is of immense importance to potential practical applications of these proton-ionizable crown ethers in which the common, hard, aqueous phase anions would be involved. Another advantage of proton-ionizable lariat ethers is the ease with which extracted metal ions may be stripped from the organic phase by shaking with aqueous mineral acid. Thus both metal ion extraction and stripping are facilitated by pendent proton-ionizable groups. Most of the hazardous metal ion species in the Hanford Site tank wastes are members of the alkali-metal, alkaline-earth, lanthanide, and actinide families. These hard metal ion species prefer association with hard donor atoms, such as oxygens. Therefore, crown and lariat ethers are well-suited for complexation with such metal ion species

  16. Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp2 and sp3 C-H Bonds

    Science.gov (United States)

    Nadres, Enrico T.; Santos, Gerson Ivan Franco; Shabashov, Dmitry; Daugulis, Olafs

    2013-01-01

    The scope of palladium-catalyzed, auxiliary-assisted direct arylation and alkylation of sp2 and sp3 C-H bonds of amine and carboxylic acid derivatives has been investigated. The method employs a palladium acetate catalyst, substrate, aryl, alkyl, benzyl, or allyl halide, and inorganic base in t-amyl alcohol or water solvent at 100-140 °C. Aryl and alkyl iodides as well as benzyl and allyl bromides are competent reagents in this transformation. Picolinic acid auxiliary is used for amine γ-functionalization and 8-aminoquinoline auxiliary is used for carboxylic acid β-functionalization. Some optimization of base, additives, and solvent is required for achieving best results. PMID:24090404

  17. Spontaneous Generation of Chirality in Simple Diaryl Ethers.

    Science.gov (United States)

    Lennartson, Anders; Hedström, Anna; Håkansson, Mikael

    2015-07-01

    We studied the spontaneous formation of chiral crystals of four diaryl ethers, 3-phenoxybenzaldehyde, 1; 1,3-dimethyl-2-phenoxybenzene, 2; di(4-aminophenyl) ether, 3; and di(p-tolyl) ether, 4. Compounds 1, 3, and 4 form conformationally chiral molecules in the solid state, while the chirality of 2 arises from the formation of supramolecular helices. Compound 1 is a liquid at ambient temperature, but 2-4 are crystalline, and solid-state CD-spectroscopy showed that they could be obtained as optically active bulk samples. It should be noted that the optical activity arise upon crystallization, and no optically active precursors were used. Indeed, even commercial samples of 3 and 4 were found to be optically active, giving evidence for the ease at which total spontaneous resolution may occur in certain systems. © 2015 Wiley Periodicals, Inc.

  18. Enhanced response of microbial fuel cell using sulfonated poly ether ether ketone membrane as a biochemical oxygen demand sensor

    Energy Technology Data Exchange (ETDEWEB)

    Ayyaru, Sivasankaran; Dharmalingam, Sangeetha, E-mail: sangeetha@annauniv.edu

    2014-03-01

    Graphical abstract: - Highlights: • Sulfonated poly ether ether ketone (SPEEK) membrane in SCMFC used to determine the BOD. • The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm. • This sensing range was 62.5% higher than that of Nafion{sup ®}. • SPEEK exhibited one order lesser oxygen permeability than Nafion{sup ®}. • Nafion{sup ®} shows high anodic internal resistance (67 Ω) than the SPEEK (39 Ω). - Abstract: The present study is focused on the development of single chamber microbial fuel cell (SCMFC) using sulfonated poly ether ether ketone (SPEEK) membrane to determine the biochemical oxygen demand (BOD) matter present in artificial wastewater (AW). The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm when using artificial wastewater. This sensing range was 62.5% higher than that of Nafion{sup ®}. The most serious problem in using MFC as a BOD sensor is the oxygen diffusion into the anode compartment, which consumes electrons in the anode compartment, thereby reducing the coulomb yield and reducing the electrical signal from the MFC. SPEEK exhibited one order lesser oxygen permeability than Nafion{sup ®}, resulting in low internal resistance and substrate loss, thus improving the sensing range of BOD. The system was further improved by making a double membrane electrode assembly (MEA) with an increased electrode surface area which provide high surface area for electrically active bacteria.

  19. Poly (ether ether ketone) derivatives: Synthetic route and characterization of nitrated and sulfonated polymers

    International Nuclear Information System (INIS)

    Conceicao, T.F.; Bertolino, J.R.; Barra, G.M.O.; Pires, A.T.N.

    2009-01-01

    Nitrated and sulfonated poly (ether ether ketone) [SNPEEK] samples were prepared through sulfonation of nitrated PEEK (NPEEK) at different temperatures resulting in polymers with distinct sulfonation degrees (SD). The sulfonation occurred preferentially in the hydroquinone segment even after 81% of this moiety had been nitrated. Sulfonation in the benzophenone moiety was achieved only in 16% of this segment at the reaction temperature of 80 deg. C. The substitution degree was obtained through the TG curves, and values were in agreement with 1 H NMR data when SD is much higher as ND (nitration degree). The highest SD obtained was 72%. Membranes of the sulfonated and nitrated PEEK (SNPEEK) were prepared by casting and showed good ductility depending on the substitution degree, with proton conductivity in the order of 10 -2 S cm -1 , an important characteristic in some applications, such as in fuel cells

  20. Poly (ether ether ketone) derivatives: Synthetic route and characterization of nitrated and sulfonated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Conceicao, T.F.; Bertolino, J.R. [Grupo de Estudo em Materiais Polimericos-Departamento de Quimica, Universidade Federal de Santa Catarina, Florianopolis, SC (Brazil); Barra, G.M.O. [Departamento de Engenharia Mecanica, Universidade Federal de Santa Catarina, Florianopolis, SC (Brazil); Pires, A.T.N. [Grupo de Estudo em Materiais Polimericos-Departamento de Quimica, Universidade Federal de Santa Catarina, Florianopolis, SC (Brazil)], E-mail: alfredotiburcio@pq.cnpq.br

    2009-03-01

    Nitrated and sulfonated poly (ether ether ketone) [SNPEEK] samples were prepared through sulfonation of nitrated PEEK (NPEEK) at different temperatures resulting in polymers with distinct sulfonation degrees (SD). The sulfonation occurred preferentially in the hydroquinone segment even after 81% of this moiety had been nitrated. Sulfonation in the benzophenone moiety was achieved only in 16% of this segment at the reaction temperature of 80 deg. C. The substitution degree was obtained through the TG curves, and values were in agreement with {sup 1}H NMR data when SD is much higher as ND (nitration degree). The highest SD obtained was 72%. Membranes of the sulfonated and nitrated PEEK (SNPEEK) were prepared by casting and showed good ductility depending on the substitution degree, with proton conductivity in the order of 10{sup -2} S cm{sup -1}, an important characteristic in some applications, such as in fuel cells.

  1. Synthesis of Fluorescent 2-Substituted 6-(Het)aryl-7-deazapurine Bases {4-(Het)aryl-pyrrolo[2,3-d]pyrimidines} by Aqueous Suzuki-Miyaura Cross-Coupling Reactions

    Czech Academy of Sciences Publication Activity Database

    Sabat, Nazarii; Nauš, Petr; Matyašovský, Ján; Dziuba, Dmytro; Poštová Slavětínská, Lenka; Hocek, Michal

    2016-01-01

    Roč. 48, č. 7 (2016), s. 1029-1045 ISSN 0039-7881 R&D Projects: GA ČR GAP207/11/0344 Institutional support: RVO:61388963 Keywords : nucleobases * deazapurines * pyrrolo[2,3-d]pyrimidines * Suzuki cross - coupling * arylation Subject RIV: CC - Organic Chemistry Impact factor: 2.650, year: 2016

  2. Interpolymer complexses of vinyl ether copolymer with polyacrylic and polymethacrylic acids

    Directory of Open Access Journals (Sweden)

    E. Shaikhutdinov

    2012-03-01

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

  3. Absorption of decabromodiphenyl ether and other organohalogen chemicals by grey seals (Halichoerus grypus)

    International Nuclear Information System (INIS)

    Thomas, Gareth O.; Moss, Simon E.W.; Asplund, Lillemor; Hall, Ailsa J.

    2005-01-01

    An input-output balance study was performed for polybrominated diphenyl ethers, polychlorinated biphenyls and some organochlorine pesticides on three captive, juvenile grey seals (Halichoerus grypus). The animals were fed a diet of herring for six months, during the last three months of which this study was performed. A supplement of decabromodiphenyl ether was included in the diet during the second month of the study. Consistently high absorption (>89%) was observed for all of the chemicals studied, whereas work on other animals has generally shown high (>80%) net absorption at log K OW OW , and very low absorption of decabromodiphenyl ether. The half-life of decabromodiphenyl ether in blood was estimated to be between 8.5 and 13 days. Measurable concentrations of decabromodiphenyl ether were detected in seal blubber at the end of the study, indicating that this chemical can be stored in adipose and may bioaccumulate. Current understanding of the mechanism of absorption of organohalogen chemicals and the potential for accumulation of decabromodiphenyl ether will need reassessing in the light of these results. - Decabromodiphenyl ether is absorbed effectively from the diet by grey seals, and can be stored in the blubber even after exposure ceases

  4. One-pot four-component synthesis of 2-aryl-3,3-dihaloacrylonitriles using potassium hexacyanoferrate(II) as environmentally benign cyanide source

    International Nuclear Information System (INIS)

    Zhao, Zhouxing; Li, Zheng

    2011-01-01

    An efficient route to one-pot four-component reactions of aroyl chlorides, potassium hexacyanoferrate(II), triphenylphosphine and carbon tetrahalides to synthesize 2-aryl-3,3-dichloroacrylonitriles and 2-aryl-3,3-dibromoacrylonitriles was described. This protocol has advantages of use of non-toxic cyanide source, high yield and simple work-up procedure. (author)

  5. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

    Science.gov (United States)

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

    2016-03-14

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

  6. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

    Directory of Open Access Journals (Sweden)

    Wei Zheng

    2016-03-01

    Full Text Available Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

  7. Silicon dioxide surfaces with aryl interaction sites for chromatographic applications

    International Nuclear Information System (INIS)

    Gadzal-Kopciuch, R.; Kluska, M.; Welniak, M.; Buszewski, B.

    2005-01-01

    The paper presents the results of a study on aryl phases aimed at the increase of the separation selectivity of substances containing π electrons, and improving the reproducibility of retention data. The above phases contain not only a carbon chain of a different length, linking them to the support, but also one or two aromatic rings. The suitability of the newly obtained packings for the purposes of high-performance liquid chromatography was verified on the basis of a description of surface topography before and after the modification process. Various physicochemical methods were employed to determine the effectiveness of chemical modification, i.e., elemental analysis, infrared spectroscopy, and nuclear magnetic resonance. The aryl packings obtained were used for the separation of polynuclear aromatic hydrocarbons and budesonide epimers, tested under hydroorganic conditions (water/ethanol, water/methanol, water/acetonitrile). The application of a methanol/water mobile phase and a new-generation naphthylpropyl stationary phase for the separation of the 22R and 22S diastereoisomers of budesonide allowed the obtention of reproducible results and make qualitative and quantitative determinations of particular enantiomers

  8. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    Science.gov (United States)

    Smith, L.A. Jr.; Jones, E.M. Jr.; Hearn, D.

    1984-05-08

    Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150 to 250 F at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C[sub 3] to C[sub 6] and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom. 2 figs.

  9. Nikola Tesla, the Ether and his Telautomaton

    Science.gov (United States)

    Milar, Kendall

    2014-03-01

    In the nineteenth century physicists' understanding of the ether changed dramatically. New developments in thermodynamics, energy physics, and electricity and magnetism dictated new properties of the ether. These have traditionally been examined from the perspective of the scientists re-conceptualizing the ether. However Nikola Tesla, a prolific inventor and writer, presents a different picture of nineteenth century physics. Alongside the displays that showcased his inventions he presented alternative interpretations of physical, physiological and even psychical research. This is particularly evident in his telautomaton, a radio remote controlled boat. This invention and Tesla's descriptions of it showcase some of his novel interpretations of physical theories. He offered a perspective on nineteenth century physics that focused on practical application instead of experiment. Sometimes the understanding of physical theories that Tesla reached was counterproductive to his own inventive work; other times he offered new insights. Tesla's utilitarian interpretation of physical theories suggests a more scientifically curious and invested inventor than previously described and a connection between the scientific and inventive communities.

  10. Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry

    Science.gov (United States)

    Ryder, Christopher R.; Wood, Joshua D.; Wells, Spencer A.; Yang, Yang; Jariwala, Deep; Marks, Tobin J.; Schatz, George C.; Hersam, Mark C.

    2016-06-01

    Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)—a layered two-dimensional semiconductor—exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

  11. Antitumor activity of JS-K [O2-(2,4-dinitrophenyl) 1-[(4-ethoxycarbonyl)piperazin-1-yl]diazen-1-ium-1,2-diolate] and related O2-aryl diazeniumdiolates in vitro and in vivo.

    Science.gov (United States)

    Shami, Paul J; Saavedra, Joseph E; Bonifant, Challice L; Chu, Jingxi; Udupi, Vidya; Malaviya, Swati; Carr, Brian I; Kar, Siddhartha; Wang, Meifeng; Jia, Lee; Ji, Xinhua; Keefer, Larry K

    2006-07-13

    The literature provides evidence that metabolic nitric oxide (NO) release mediates the cytotoxic activities (against human leukemia and prostate cancer xenografts in mice) of JS-K, a compound of structure R(2)N-N(O)=NO-Ar for which R(2)N is 4-(ethoxycarbonyl)piperazin-1-yl and Ar is 2,4-dinitrophenyl. Here we present comparative data on the potencies of JS-K and 41 other O(2)-arylated diazeniumdiolates as inhibitors of HL-60 human leukemia cell proliferation, as well as in the NCI 51-cell-line screen for six of them. The data show JS-K to be the most potent of the 42 in both screens and suggest that other features of its structure and metabolism besides NO release may contribute importantly to its activity. Results with control compounds implicate JS-K's arylating ability, and the surprisingly low IC(50) value of the N-(ethoxycarbonyl)piperazine byproduct of NO release suggests a role for the R(2)N moiety. In addition to the above-mentioned in vivo activities, JS-K is shown here to be carcinostatic in a rat liver cancer model.

  12. Ion-irradiated polymer studied by a slow positron beam

    International Nuclear Information System (INIS)

    Kobayashi, Yoshinori; Kojima, Isao; Hishita, Shunichi; Suzuki, Takenori.

    1995-01-01

    Poly (aryl-ether-ether ketone) (PEEK) films were irradiated with 1MeV and 2MeV 0 + ions and the positron annihilation Doppler broadening was measured as a function of the positron energy. The annihilation lines recorded at relatively low positron energies were found to become broader with increasing the irradiation dose, suggesting that positronium (Ps) formation may be inhibited in the damaged regions. A correlation was observed between the Doppler broadening and spin densities determined by electron spin resonance (ESR). (author)

  13. Effect of ethylene glycol monomethyl ether and diethylene glycol monomethyl ether on hepatic metabolizing enzymes.

    Science.gov (United States)

    Kawamoto, T; Matsuno, K; Kayama, F; Hirai, M; Arashidani, K; Yoshikawa, M; Kodama, Y

    1990-06-01

    Glycol ethers have been extensively used in industry over the past 40-50 years. Numerous studies on the toxicity of glycol ethers have been performed, however, the effects of glycol ethers on the hepatic drug metabolizing enzymes are still unknown. We studied the changes of the putative metabolic enzymes, that is, the hepatic microsomal mixed function oxidase system and cytosolic alcohol dehydrogenase, by the oral administration of diEGME and EGME. Adult male Wistar rats were used. DiEGME was administered orally; 500, 1000, 2000 mg/kg for 1, 2, 5 or 20 days and EGME was 100, 300 mg/kg for 1, 2, 5 or 20 days. Decreases in liver weights were produced by highest doses of diEGME (2000 mg/kg body wt/day for 20 days) and EGME (300 mg/kg body wt/day for 20 days). DiEGME increased hepatic microsomal protein contents and induced cytochrome P-450, but not cytochrome b5 or NADPH-cytochrome c reductase. The activity of cytosolic ADH was not affected by diEGME administration. On the other hand, EGME did not change cytochrome P-450, cytochrome b5 or NADPH-cytochrome c reductase. The activity of cytosolic ADH was increased by repeated EGME treatment. Therefore it is suspected that the enzyme which takes part in the metabolism of diEGME is different from that of EGME, although diEGME is a structural homologue of EGME.

  14. Kynurenine 3-monooxygenase mediates inhibition of Th17 differentiation via catabolism of endogenous aryl hydrocarbon receptor ligands.

    Science.gov (United States)

    Stephens, Geoffrey L; Wang, Qun; Swerdlow, Bonnie; Bhat, Geetha; Kolbeck, Roland; Fung, Michael

    2013-07-01

    The aryl hydrocarbon receptor (AhR) is a key transcriptional regulator of Th17-cell differentiation. Although endogenous ligands have yet to be identified, evidence suggests that tryptophan metabolites can act as agonists for the AhR. Tryptophan metabolites are abundant in circulation, so we hypothesized that cell intrinsic factors might exist to regulate the exposure of Th17 cells to AhR-dependent activities. Here, we find that Th17 cells preferentially express kynurenine 3-monooxygenase (KMO), which is an enzyme involved in catabolism of the tryptophan metabolite kynurenine. KMO inhibition, either with a specific inhibitor or via siRNA-mediated silencing, markedly increased IL-17 production in vitro, whereas IFN-γ production by Th1 cells was unaffected. Inhibition of KMO significantly exacerbated disease in a Th17-driven model of autoimmune gastritis, suggesting that expression of KMO by Th17 cells serves to limit their continuous exposure to physiological levels of endogenous AhR ligands in vivo. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. The preparation and intramolecular radical cyclisation reactions of chiral oxyme ethers

    International Nuclear Information System (INIS)

    Booth, Susan E.; Jenkins, Paul R.

    1998-01-01

    Chiral oxime ether 2 and Oxime ester 4 have been prepared by alkylation and esterification of the oxime 1. Racemic hydroxylamine 6 and chiral hydroxylamine 10 have been synthesised from N-hydroxysuccinimide and the corresponding alcohol in the presence of diethyl azo dicarboxylate, the two product were converted into the oxime ethers 7 and 11 respectively. The intramolecular radical cyclisation reactions of these oxime ethers and esters has been studied, successful reaction was observed to produce alkyl hydroxylamines 3,8 and 12. (author)

  16. The Preparation and Intramolecular Radical Cyclisation Reactions of Chiral Oxime Ethers

    Directory of Open Access Journals (Sweden)

    Booth Susan E.

    1998-01-01

    Full Text Available Chiral oxime ether 2 and Oxime ester 4 have been prepared by alkylation and esterification of the oxime 1. Racemic hydroxylamine 6 and chiral hydroxylamine 10 have been synthesised from N-hydroxysuccinimide and the corresponding alcohol in the presence of diethylazodicarboxylate, the two products were converted into the oxime ethers 7 and 11 respectively. The intramolecular radical cyclisation reactions of these oxime ethers and esters has been studied, successful reaction was observed to produce alkyl hydroxylamines 3, 8 and 12.

  17. Enzymatic network for production of ether amines from alcohols

    DEFF Research Database (Denmark)

    Palacio, Cyntia M.; Crismaru, Ciprian G.; Bartsch, Sebastian

    2016-01-01

    We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production...... of the desired ether amines from the corresponding ether alcohols with inorganic ammonium as the only additional substrate. To examine conversion, individual and overall reaction equilibria were established. Using these data, it was found that the experimentally observed conversions of up to 60% observed...... for reactions containing 10mM alcohol and up to 280mM ammonia corresponded well to predicted conversions. The results indicate that efficient amination can be driven by high concentrations of ammonia and may require improving enzyme robustness for scale-up....

  18. Basic randomness of nature and ether-drift experiments

    International Nuclear Information System (INIS)

    Consoli, M.; Pluchino, A.; Rapisarda, A.

    2011-01-01

    Highlights: ► We re-consider the idea of a basic randomness of nature. ► We adopt Stochastic Electro Dynamics as a heuristic model. ► We represent the vacuum as a form of turbulent ether. ► This picture can be tested with forthcoming ether-drift experiments. - Abstract: We re-consider the idea that quantum fluctuations might reflect the existence of an ‘objective randomness’, i.e. a basic property of the vacuum state which is independent of any experimental accuracy of the observations or limited knowledge of initial conditions. Besides being responsible for the observed quantum behavior, this might introduce a weak, residual form of ‘noise’ which is intrinsic to natural phenomena and could be important for the emergence of complexity at higher physical levels. By adopting Stochastic Electro Dynamics as a heuristic model, we are driven to a picture of the vacuum as a form of highly turbulent ether, which is deep-rooted into the basic foundational aspects of both quantum physics and relativity, and to search for experimental tests of this scenario. An analysis of the most precise ether-drift experiments, operating both at room temperature and in the cryogenic regime, shows that, at present, there is some ambiguity in the interpretation of the data. In fact the average amplitude of the signal has precisely the magnitude expected, in a ‘Lorentzian’ form of relativity, from an underlying stochastic ether and, as such, might not be a spurious instrumental effect. This puzzle, however, should be solved in a next future with the use of new cryogenically cooled optical resonators whose stability should improve by about two orders of magnitude. In these new experimental conditions, the persistence of the present amplitude would represent a clean evidence for the type of random vacuum we are envisaging.

  19. A point mutation of valine-311 to methionine in Bacillus subtilis protoporphyrinogen oxidase does not greatly increase resistance to the diphenyl ether herbicide oxyfluorfen.

    Science.gov (United States)

    Jeong, Eunjoo; Houn, Thavrak; Kuk, Yongin; Kim, Eun-Seon; Chandru, Hema Kumar; Baik, Myunggi; Back, Kyoungwhan; Guh, Ja-Ock; Han, Oksoo

    2003-10-01

    In an effort to asses the effect of Val311Met point mutation of Bacillus subtilis protoporphyrinogen oxidase on the resistance to diphenyl ether herbicides, a Val311Met point mutant of B. subtilis protoporphyrinogen oxidase was prepared, heterologously expressed in Escherichia coli, and the purified recombinant Val311Met mutant protoporphyrinogen oxidase was kinetically characterized. The mutant protoporphyrinogen oxidase showed very similar kinetic patterns to wild type protoporphyrinogen oxidase, with slightly decreased activity dependent on pH and the concentrations of NaCl, Tween 20, and imidazole. When oxyfluorfen was used as a competitive inhibitor, the Val311Met mutant protoporphyrinogen oxidase showed an increased inhibition constant about 1.5 times that of wild type protoporphyrinogen oxidase. The marginal increase of the inhibition constant indicates that the Val311Met point mutation in B. subtilis protoporphyrinogen oxidase may not be an important determinant in the mechanism that protects protoporphyrinogen oxidase against diphenyl ether herbicides.

  20. Utilization of acidic α-amino acids as acyl donors: an effective stereo-controllable synthesis of aryl-keto α-amino acids and their derivatives.

    Science.gov (United States)

    Wang, Lei; Murai, Yuta; Yoshida, Takuma; Okamoto, Masashi; Tachrim, Zetryana Puteri; Hashidoko, Yasuyuki; Hashimoto, Makoto

    2014-05-16

    Aryl-keto-containing α-amino acids are of great importance in organic chemistry and biochemistry. They are valuable intermediates for the construction of hydroxyl α-amino acids, nonproteinogenic α-amino acids, as well as other biofunctional components. Friedel-Crafts acylation is an effective method to prepare aryl-keto derivatives. In this review, we summarize the preparation of aryl-keto containing α-amino acids by Friedel-Crafts acylation using acidic α-amino acids as acyl-donors and Lewis acids or Brönsted acids as catalysts.

  1. Bioassay directed identification of natural aryl hydrocarbon-receptor agonists in marmalade

    NARCIS (Netherlands)

    Ede, van K.I.; Li, A.; Antunes Fernandes, E.C.; Mulder, P.P.J.; Peijnenburg, A.A.C.M.; Hoogenboom, L.A.P.

    2008-01-01

    Citrus fruit and citrus fruit products, like grapefruit, lemon and marmalade were shown to contain aryl hydrocarbon receptor (AhR) agonists, as detected with the DR CALUX® bioassay. This is of interest regarding the role of the Ah-receptor pathway in the adverse effects of dioxins, PCBs and other

  2. Exploration of mild copper-mediated coupling of organotrifluoroborates in the synthesis of thiirane-based inhibitors of matrix metalloproteinases.

    Science.gov (United States)

    Testero, Sebastian A; Bouley, Renee; Fisher, Jed F; Chang, Mayland; Mobashery, Shahriar

    2011-05-01

    The copper-mediated and non-basic oxidative cross-coupling of organotrifluoroborates with phenols was applied to elaboration of the structures of thiirane-based inhibitors of matrix metalloproteinases. By revision of the synthetic sequence to allow this cross-coupling as the final step, and taking advantage of the neutral nature of organotrifluoroborate cross-coupling, a focussed series of inhibitors showing aryloxy and alkenyloxy replacement of the phenoxy substituent was prepared. This reaction shows exceptional promise as an alternative to the classic copper-mediated but strongly basic Ullmann reaction, for the diversification of ether segments within base-labile lead structures. Copyright © 2010 Elsevier Ltd. All rights reserved.

  3. Enantiomeric Separation of 1-(Benzofuran-2-yl)alkylamines on Chiral Stationary Phases Based on Chiral Crown Ethers

    International Nuclear Information System (INIS)

    Park, Soohyun; Kim, Sang Jun; Hyun, Myung Ho

    2012-01-01

    Optically active chiral amines are important as building blocks for pharmaceuticals and as scaffolds for chiral ligands and, consequently, many efforts have been devoted to the development of efficient methods for their preparation. For example, reduction of amine precursors with chiral catalysts, enzymatic kinetic resolution or dynamic kinetic resolution of racemic amines and the direct amination of ketones with transaminases have been developed as the efficient methods for the preparation of optically active chiral amines. During the process of developing or utilizing optically active chiral amines, the methods for the determination of their enantiomeric composition are essential. Among various methods, liquid chromatographic resolution of enantiomers on chiral stationary phases (CSPs) have been known to be one of the most accurate and economic means for the determination of the enantiomeric composition of optically active chiral compounds. Especially, CSPs based on chiral crown ethers have been successfully used for the resolution of racemic primary amines. For example, CSPs based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid (CSP 1, Figure 1) or (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6 (CSP 2 and CSP 3, Figure 1) have been known to be quite effective for the resolution of cyclic and non-cyclic amines, various fluoroquinolone antibacterials containing a primary amino group, tocainide (antiarrhythmic agent) and its analogues, aryl-a-amino ketones and 3-amino-1,4-benzodiazepin-2-ones

  4. Enhanced osteogenic activity of poly ether ether ketone using calcium plasma immersion ion implantation.

    Science.gov (United States)

    Lu, Tao; Qian, Shi; Meng, Fanhao; Ning, Congqin; Liu, Xuanyong

    2016-06-01

    As a promising implantable material, poly ether ether ketone (PEEK) possesses similar elastic modulus to that of cortical bones yet suffers from bio-inertness and poor osteogenic properties, which limits its application as orthopedic implants. In this work, calcium is introduced onto PEEK surface using calcium plasma immersion ion implantation (Ca-PIII). The results obtained from scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) confirm the modified layer with varying contents of calcium are formed on PEEK surfaces. Water contact angle measurements reveal the increasing hydrophobicity of both Ca-PIII treated surfaces. In vitro cell adhesion, viability assay, alkaline phosphatase activity and collagen secretion analyses disclose improved the adhesion, proliferation, and osteo-differentiation of rat bone mesenchymal stem cells (bMSCs) on Ca-PIII treated surfaces. The obtained results indicate that PEEK surface with enhanced osteogenic activity can be produced by calcium incorporation. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. ynthesis and Characterization of 1-Aryl-5-hepta-O-acetyl-β-D-maltosyl-2-S-benzyl-2,4-isodithiobiurets

    Directory of Open Access Journals (Sweden)

    R. D. Ghuge

    2012-01-01

    Full Text Available The facile synthesis of 1-aryl-5-hepta-o-acetyl-β-D-maltosyl-2-S-benzyl-2,4-isodithiobiurets (IIIa-g has been achieved by the interaction of 1-hepta-O-acetyl-β–D-maltosyl isothiocyanate (I with various1-aryl-S-benzyl isothiocarbamides (IIa-g. All the newly synthesized N-maltosylated compounds characterized by elemental analysis, IR, NMR and Mass spectral studies.

  6. Arylation of Rhodium(II) Azavinyl Carbenes with Boronic Acids

    Science.gov (United States)

    Selander, Nicklas; Worrell, Brady T.; Chuprakov, Stepan; Velaparthi, Subash; Fokin, Valery V.

    2013-01-01

    A highly efficient and stereoselective arylation of in situ generated azavinyl carbenes affording 2,2-diaryl enamines at ambient temperatures has been developed. These transition metal carbenes are directly produced from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of a rhodium carboxylate catalyst. In several cases, the enamines generated in this reaction can be cyclized into substituted indoles employing copper catalysts. PMID:22913576

  7. Gold-catalyzed alkylation of silyl enol ethers with ortho-alkynylbenzoic acid esters

    Directory of Open Access Journals (Sweden)

    Yoshinori Yamamoto

    2011-05-01

    Full Text Available Unprecedented alkylation of silyl enol ethers has been developed by the use of ortho-alkynylbenzoic acid alkyl esters as alkylating agents in the presence of a gold catalyst. The reaction probably proceeds through the gold-induced in situ construction of leaving groups and subsequent nucleophilic attack on the silyl enol ethers. The generated leaving compound abstracts a proton to regenerate the silyl enol ether structure.

  8. 1-[(3-Aryloxy-3-aryl)propyl]-1H-imidazoles, new imidazoles with potent activity against Candida albicans and dermatophytes. Synthesis, structure-activity relationship, and molecular modeling studies.

    Science.gov (United States)

    La Regina, Giuseppe; D'Auria, Felicia Diodata; Tafi, Andrea; Piscitelli, Francesco; Olla, Stefania; Caporuscio, Fabiana; Nencioni, Lucia; Cirilli, Roberto; La Torre, Francesco; De Melo, Nadja Rodrigues; Kelly, Steven L; Lamb, David C; Artico, Marino; Botta, Maurizio; Palamara, Anna Teresa; Silvestri, Romano

    2008-07-10

    New 1-[(3-aryloxy-3-aryl)propyl]-1 H-imidazoles were synthesized and evaluated against Candida albicans and dermatophytes in order to develop structure-activity relationships (SARs). Against C. albicans the new imidazoles showed minimal inhibitory concentrations (MICs) comparable to those of ketoconazole, miconazole, and econazole, and were more potent than fluconazole. Several derivatives ( 10, 12, 14, 18- 20, 24, 28, 29, 30, and 34) turned out to be potent inhibitors of C. albicans strains resistant to fluconazole, with MIC values less than 10 microg/mL. Against dermatophytes strains, compounds 20, 25, and 33 (MIC

  9. Lignin conversion to high-octane fuel additives

    Energy Technology Data Exchange (ETDEWEB)

    Shabtai, J.; Zmierczak, W.; Kadangode, S. [University of Utah, Salt Lake City (United States); Chornet, E.; Johnson, D.K. [National Renewable Energy Laboratory, Golden, CO (United States)

    1999-07-01

    Continuing previous studies on the conversion of lignin to reformulated gasoline compositions, new lignin upgrading processes were developed that allow preferential production of specific high-octane fuel additives of two distinct types: (1) C{sub 7}-C{sub 10} alkylbenzenes; and (2) aryl methyl ethers, where aryl mostly = phenyl, 2-methylphenyl, 4-methylphenyl, and dimethylphenyl. Process (1) comprises base-catalyzed depolymerization (BCD) and simultaneous partial ({approx} 50%) deoxygenation of lignin at 270 - 290{sup o}C, in the presence of supercritical methanol as reaction medium, followed by exhaustive hydrodeoxygenation and attendant mild hydrocracking of the BCD product with sulfided catalysts to yield C{sub 8}-C{sub 10} alkylbenzenes as main products. Process (2) involves mild BCD at 250 - 270{sup o}C with preservation of the lignin oxygen, followed by selective C-C hydrocracking with solid superacid catalysts. This method preferentially yields a mixture of alkylated phenols, which upon acid-catalyzed etherification with methanol are converted into corresponding aryl methyl ethers (see above) possessing blending octane numbers in the range of 142-166. In a recent extension of this work, a greatly advantageous procedure for performing the BCD stage of processes (1) and (2) in water as reaction medium was developed. (author)

  10. Microwave-Assisted Synthesis of a MK2 Inhibitor by Suzuki-Miyaura Coupling for Study in Werner Syndrome Cells

    Directory of Open Access Journals (Sweden)

    Mark C. Bagley

    2015-06-01

    Full Text Available Microwave-assisted Suzuki-Miyaura cross-coupling reactions have been employed towards the synthesis of three different MAPKAPK2 (MK2 inhibitors to study accelerated aging in Werner syndrome (WS cells, including the cross-coupling of a 2-chloroquinoline with a 3-pyridinylboronic acid, the coupling of an aryl bromide with an indolylboronic acid and the reaction of a 3-amino-4-bromopyrazole with 4-carbamoylphenylboronic acid. In all of these processes, the Suzuki-Miyaura reaction was fast and relatively efficient using a palladium catalyst under microwave irradiation. The process was incorporated into a rapid 3-step microwave-assisted method for the synthesis of a MK2 inhibitor involving 3-aminopyrazole formation, pyrazole C-4 bromination using N-bromosuccinimide (NBS, and Suzuki-Miyaura cross-coupling of the pyrazolyl bromide with 4-carbamoylphenylboronic acid to give the target 4-arylpyrazole in 35% overall yield, suitable for study in WS cells.

  11. Toxicogenomic assessment of 6-OH-BDE47 induced developmental toxicity in chicken embryo

    Science.gov (United States)

    Hydroxylated and methoxylated polybrominated diphenyl ethers (OH-/MeO-PBDEs) are analogs of PBDEs with hundreds of possible structures and many of them can activate aryl hydrocarbon receptor (AhR), however, the in vivo evidence on the toxicity of OH-/MeO-PBDEs are still very limi...

  12. Structuring of poly ether ether ketone by ArF excimer laser radiation in different atmospheres

    International Nuclear Information System (INIS)

    Feng, Y.; Gottmann, J.; Kreutz, E.W.

    2003-01-01

    Structuring of poly ether ether ketone (PEEK) by 193 nm ArF excimer laser radiation has been investigated. Experiments were carried out in different atmospheres (air, vacuum, Ar, O 2 ) in order to study its influence on the quality of the structures and the formation of the debris. Repetition rate makes little effect on the ablation rate and roughness of the structure in presence of any kind of atmosphere, indicating for the structuring of PEEK by ArF laser radiation a large window of processing. The roughness at the bottom of the structures and the morphology of the side walls are strongly affected by the properties of the atmosphere. The smallest roughness is achieved at 0.6 J/cm 2 for all kinds of processing gases. Debris around the structures can be diminished by structuring in vacuum. Plasma expansion speed has been measured by using high speed photography

  13. Microwave-Enhanced Cross-Coupling Reactions Involving Alkynyltrifluoroborates with Aryl Bromides

    Directory of Open Access Journals (Sweden)

    George W. Kabalka

    2013-01-01

    Full Text Available Palladium-catalyzed alkynylation has emerged as one of the most reliable methods for the synthesis of alkynes which are often used in natural product syntheses and material science. An efficient method for coupling alkynyltrifluoroborates with various aryl bromides in the presence of a palladium catalyst has been developed using microwave irradiation. The microwave reactions are rapid and efficient.

  14. Cigarette smoke-induced cell death of a spermatocyte cell line can be prevented by inactivating the Aryl hydrocarbon receptor

    Science.gov (United States)

    Esakky, P; Hansen, D A; Drury, A M; Cusumano, A; Moley, K H

    2015-01-01

    Cigarette smoke exposure causes germ cell death during spermatogenesis. Our earlier studies demonstrated that cigarette smoke condensate (CSC) causes spermatocyte cell death in vivo and growth arrest of the mouse spermatocyte cell line (GC-2spd(ts)) in vitro via the aryl hydrocarbon receptor (AHR). We hypothesize here that inactivation of AHR could prevent the CSC-induced cell death in spermatocytes. We demonstrate that CSC exposure generates oxidative stress, which differentially regulates mitochondrial apoptosis in GC-2spd(ts) and wild type (WT) and AHR knockout (AHR-KO) mouse embryonic fibroblasts (MEFs). SiRNA-mediated silencing of Ahr augments the extent of CSC-mediated cellular damage while complementing the AHR-knockout condition. Pharmacological inhibition using the AHR-antagonist (CH223191) modulates the CSC-altered expression of apoptotic proteins and significantly abrogates DNA fragmentation though the cleavage of PARP appears AHR independent. Pretreatment with CH223191 at concentrations above 50 μM significantly prevents the CSC-induced activation of caspase-3/7 and externalization of phosphatidylserine in the plasma membrane. However, MAPK inhibitors alone or together with CH223191 could not prevent the membrane damage upon CSC addition and the caspase-3/7 activation and membrane damage in AHR-deficient MEF indicates the interplay of multiple cell signaling and cytoprotective ability of AHR. Thus the data obtained on one hand signifies the protective role of AHR in maintaining normal cellular homeostasis and the other, could be a potential prophylactic therapeutic target to promote cell survival and growth under cigarette smoke exposed environment by receptor antagonism via CH223191-like mechanism. Antagonist-mediated inactivation of the aryl hydrocarbon receptor blocks downstream events leading to cigarette smoke-induced cell death of a spermatocyte cell line. PMID:27551479

  15. The influence of water mixtures on the dermal absorption of glycol ethers

    International Nuclear Information System (INIS)

    Traynor, Matthew J.; Wilkinson, Simon C.; Williams, Faith M.

    2007-01-01

    Glycol ethers are solvents widely used alone and as mixtures in industrial and household products. Some glycol ethers have been shown to have a range of toxic effects in humans following absorption and metabolism to their aldehyde and acid metabolites. This study assessed the influence of water mixtures on the dermal absorption of butoxyethanol and ethoxyethanol in vitro through human skin. Butoxyethanol penetrated human skin up to sixfold more rapidly from aqueous solution (50%, 450 mg/ml) than from the neat solvent. Similarly penetration of ethoxyethanol was increased threefold in the presence of water (50%, 697 mg/ml). There was a corresponding increase in apparent permeability coefficient as the glycol ether concentration in water decreased. The maximum penetration rate of water also increased in the presence of both glycol ethers. Absorption through a synthetic membrane obeyed Fick's Law and absorption through rat skin showed a similar profile to human skin but with a lesser effect. The mechanisms for this phenomenon involves disruption of the stratum corneum lipid bilayer by desiccation by neat glycol ether micelles, hydration with water mixtures and the physicochemical properties of the glycol ether-water mixtures. Full elucidation of the profile of absorption of glycol ethers from mixtures is required for risk assessment of dermal exposure. This work supports the view that risk assessments for dermal contact scenarios should ideally be based on absorption data obtained for the relevant formulation or mixture and exposure scenario and that absorption derived from permeability coefficients may be inappropriate for water-miscible solvents

  16. Induced production of halogenated diphenyl ethers from the marine-derived fungus Penicillium chrysogenum.

    Science.gov (United States)

    Yang, Guohua; Yun, Keumja; Nenkep, Viviane N; Choi, Hong Dae; Kang, Jung Sook; Son, Byeng Wha

    2010-11-01

    Manipulation of the fermentation of the marine-derived fungus Penicillium chrysogenum by addition of CaBr(2) resulted in induced production of bromodiphenyl ether analogs. Two new free-radical-scavenging polybrominated diphenyl ethers, 1 and 2, and three known diphenyl ethers, 3,3'-dihydroxy-5,5'-dimethyldiphenyl ether (3), and an inseparable mixture of violacerol-I (4) and violacerol-II (5) were isolated. The structures of the two new polybromodiphenyl ethers 1 and 2 were assigned by combined spectroscopic-data analysis, including deuterium-induced isotope effect. Compounds 1-3, and a mixture of 4 and 5 exhibited radical-scavenging activities against 1,1-diphenyl-2-picrylhydrazyl with IC(50) values of 18, 15, 42, and 6 μM, respectively. With the exception of 3, the compounds were, therefore, more active than the positive control, ascorbic acid (IC(50) 20 μM).

  17. Synthesis of 3-acetyl-N-aryl-4-diethylaminoselenet-2(2H)-imines from 4-diethylamino-3-butyn-2-one and aryl isoselenocyanates

    OpenAIRE

    Atanassov, Plamen K; Linden, Anthony; Heimgartner, Heinz

    2004-01-01

    The reaction of aryl isoselenocyanates (1a-d) with 4-diethylamino-3-butyn-2-one (6) in refluxing tetrahydrofuran afforded N-arylselenet-2(2H)-imines (7) in moderate yields. The structure of the stable 4-bromophenyl derivative (7b) has been established by X-Ray crystallography. A stepwise cycloaddition via an intermediate zwitterion (A/A¢) is proposed as the reaction mechanism. In boiling tetrahydrofuran, the selenetimines (7) are in equilibrium with ketenimines (B), which were intercepted by ...

  18. Induction of the p75NTR by Aryl Propionic Acids in Prostate Cancer Cells

    National Research Council Canada - National Science Library

    Quann, Emily

    2007-01-01

    .... I have found that treatment of prostate cancer cells with the aryl propionic acids R-flurbiprofen and ibuprofen induces reexpression of p75NTR, decreases cell survival, and increases apoptosis...

  19. Chemistry and phytotoxicity of thaxtomin A alkyl ethers.

    Science.gov (United States)

    Krasnoff, Stuart B; Lobkovsky, Emil B; Wach, Michael J; Loria, Rosemary; Gibson, Donna M

    2005-11-30

    The thaxtomin phytotoxins (1 and 2) from scab-producing Streptomyces pathogens of the potato are 2,5-dioxopiperazines consisting of modified l-tryptophanyl and l-phenylalanyl units. Thaxtomin A (1) is hydroxylated at C-14, the alpha carbon of the modified l-phenylalanyl moiety. Refluxing thaxtomin A in acidified MeOH, EtOH, and i-PrOH afforded C-14 thaxtomin A methyl- (3a and 3b), ethyl- (4a and 4b), and isopropyl- (5a and 5b) ethers, respectively, in both the 11S,14R (3a, 4a, and 5a) and 11S,14S (3b, 4b, and 5b) configurations. Crystal structures were determined for 3a and 4a. Extensive NMR as well as other spectroscopic data supported structural assignments for all of the derivatives. The 11S,14R-configured derivatives were slightly less potent than the natural products (1 and 2) as inhibitors of lettuce seedling root growth, whereas the activity of the 11S,14S epimers was much reduced, indicating that the configuration at C-14 found in the naturally occurring thaxtomins is essential for biological activity. Among the 11S,14R-configured compounds, potency decreased with an increasing size of the substituted alkoxy group.

  20. One-pot synthesis of multisubstituted 2-aminoquinolines from annulation of 1-aryl tetrazoles with internal alkynes via double C-H activation and denitrogenation.

    Science.gov (United States)

    Zhang, Lei; Zheng, Liyao; Guo, Biao; Hua, Ruimao

    2014-12-05

    An efficient, one-pot synthesis of multisubstituted 2-aminoquinolines from 1-aryl tetrazoles and internal alkynes has been developed. The reaction involves cyclization of 1-aryl tetrazoles with internal alkynes via rhodium(III)-catalyzed double C-H activation and copper(II)-mediated denitrogenation.

  1. Acidolysis small molecular phenolic ether used as accelerator in photosensitive diazonaphthaquinone systems

    Science.gov (United States)

    Zhou, Haihua; Zou, Yingquan

    2006-03-01

    The photosensitive compounds in the photosensitive coatings of positive PS plates are the diazonaphthaquinone derivatives. Some acidolysis small molecular phenolic ethers, which were synthesized by some special polyhydroxyl phenols with vinyl ethyl ether, are added in the positive diazonaphthaquinone photosensitive composition to improve its sensitivity, composed with photo-acid-generators. The effects to the photosensitivity, anti-alkali property, anti-isopropyl alcohol property, dot resolution and line resolution of the coatings are studied with different additive percent of the special phenolic ethers. In the conventional photosensitive diazonaphthaquinone systems for positive PS plates, the photosensitivity is improved without negative effects to resolution, anti-alkali and anti-isopropyl alcohol properties when added about 5% of the special acidolysis phenolic ethers, EAAE or DPHE, composed with photo-acid-generators.

  2. The simple ethers of glycerin

    International Nuclear Information System (INIS)

    Kimsanov, B.Kh.; Karimov, M.B.

    1998-01-01

    From glycerin derivatives the considerable interest is present simple ethers because many of them are biological active and found wide practical using as an effect drugs, inters for thin organic synthesis, vehicle for injections, regulators of plants growth, reagents, components for perfumery-cosmetic goods and etc

  3. The PROMETHEE multiple criteria decision making analysis for selecting the best membrane prepared from sulfonated poly(ether ketone)s and poly(ether sulfone)s for proton exchange membrane fuel cell

    International Nuclear Information System (INIS)

    Nikouei, Mohammad Ali; Oroujzadeh, Maryam; Mehdipour-Ataei, Shahram

    2017-01-01

    Proton exchange membrane as the heart of fuel cell has been the topic of many research activities in recent years. Finding a suitable alternative for Nafion membranes is one of the most important issues of interest. This study is dedicated to sulfonated poly(ether ketone) and poly(ether sulfone) membranes. For synthesis of these two groups of polymers, two different isomeric biphenols (meta- and para-) were used and each group of membranes with three different degree of sulfonation (25, 35, and 45%) was synthesized. In this way, twelve different membrane samples were obtained and their properties were evaluated. Since each membrane had some strong and some weak points of properties in comparison to the other ones, using a rational analysis for choosing the best membrane between prepared samples was inevitable. For this purpose a PROMETHEE based multiple criteria decision making approach was applied and for evaluation of the weight of each criterion, Shannon entropy method was used. Final results showed that poly(ether ketone) membranes in selected criteria were better than poly(ether sulfone) membranes and as expected, membranes with the highest degree of sulfonation (45%) were placed at the top ranking levels. - Highlights: • Sulfonated poly(ether ketone)s and Poly(ether sulfone)s were synthesized. • Related membranes for PEMFC were prepared. • The properties of membranes were measured. • Multiple criteria decision making approach was used to ranking the membranes. • PROMETHEE based approach selected poly(ether ketone)s as better choices.

  4. Cobaltous chloride and hypoxia inhibit aryl hydrocarbon receptor-mediated responses in breast cancer cells

    International Nuclear Information System (INIS)

    Khan, Shaheen; Liu Shengxi; Stoner, Matthew; Safe, Stephen

    2007-01-01

    The aryl hydrocarbon receptor (AhR) is expressed in estrogen receptor (ER)-positive ZR-75 breast cancer cells. Treatment with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) induces CYP1A1 protein and mRNA levels and also activates inhibitory AhR-ERα crosstalk associated with hormone-induced reporter gene expression. In ZR-75 cells grown under hypoxia, induction of these AhR-mediated responses by TCDD was significantly inhibited. This was not accompanied by decreased nuclear AhR levels or decreased interaction of the AhR complex with the CYP1A1 gene promoter as determined in a chromatin immunoprecipitation assay. Hypoxia-induced loss of Ah-responsiveness was not associated with induction of hypoxia-inducible factor-1α or other factors that sequester the AhR nuclear translocation (Arnt) protein, and overexpression of Arnt under hypoxia did not restore Ah-responsiveness. The p65 subunit of NFκB which inhibits AhR-mediated transactivation was not induced by hypoxia and was primarily cytosolic in ZR-75 cells grown under hypoxic and normoxic conditions. In ZR-75 cells maintained under hypoxic conditions for 24 h, BRCA1 (an enhancer of AhR-mediated transactivation in breast cancer cells) was significantly decreased and this contributed to loss of Ah-responsiveness. In cells grown under hypoxia for 6 h, BRCA1 was not decreased, but induction of CYP1A1 by TCDD was significantly decreased. Cotreatment of ZR-75 cells with TCDD plus the protein synthesis inhibitor cycloheximide for 6 h enhanced CYP1A1 expression in cells grown under hypoxia and normoxia. These results suggest that hypoxia rapidly induces protein(s) that inhibit Ah-responsiveness and these may be similar to constitutively expressed inhibitors of Ah-responsiveness (under normoxia) that are also inhibited by cycloheximide

  5. Preparation of poly(ether ether ketone)-based polymer electrolytes for fuel cell membranes using grafting technique

    International Nuclear Information System (INIS)

    Hasegawa, Shin; Suzuki, Yasuyuki; Maekawa, Yasunari

    2008-01-01

    Poly(ether ether ketone) (PEEK)-based polymer electrolyte membranes (PEMs) was successfully prepared by radiation grafting of a styrene monomer into PEEK films and the consequent selective sulfonation of the grafting chains in the film state. Using milder sulfonation, the sulfonation reactions proceeded at the grafted chains in preference to the phenylene rings of PEEK main chains; as a result, the grafted films could successfully transform to a PEM with conductivity of more than 0.1 S/cm. The ion exchange capacity (IEC) and conductivity of the grafted PEEK electrolyte membranes were controlled to the ranges of 1.2-2.9 mmol/g and 0.03-0.18 S/cm by changing the grafting degree. It should be noted that this is the first example of directly transforming super-engineering plastic films into a PEM using radiation grafting

  6. Sulfonated Poly(Ether Ether Ketone)/Functionalized Carbon Nanotube Composite Membrane for Vanadium Redox Flow Battery Applications

    International Nuclear Information System (INIS)

    Jia, Chuankun; Cheng, Yuanhang; Ling, Xiao; Wei, Guanjie; Liu, Jianguo; Yan, Chuanwei

    2015-01-01

    A novel sulfonated poly(ether ether ketone) (SPEEK) membrane embedded with the short-carboxylic multi-walled carbon nanotube (we name it as SPEEK/SCCT membrane) for vanadium redox flow battery (VRB) has been prepared with low capacity loss, low cost and high energy efficiency. The mechanical strength, vanadium ions permeability and performance of the membrane in the VRB single cell were characterized. Results showed that the SPEEK/SCCT membrane possessed low permeability of vanadium ions, accompanied by higher mechanical strength than the Nafion 212 membrane. The VRB single cell with SPEEK/SCCT membrane showed 7% higher coulombic efficiency (CE), 6% higher energy efficiency (EE) but lower capacity loss in comparison with the one with Nafion 212. The good cell performance, low capacity loss and high vanadium ions barrier properties of the blend membrane is of significant interest for VRB applications

  7. Influence of structure of crown ethers on their radiation stability

    International Nuclear Information System (INIS)

    Grigor'ev, E.I.; Myasoedova, T.G.; Nesterov, S.V.; Trakhtenberg, L.I.

    1988-01-01

    Primary products of γ-radiolysis of crown ethers with the same size of the macrocyclic ring and different substituents were studied by EPR and mass spectrometry. It was shown that introduction of substituents into the polyether ring increases the radiation stability of crown ethers due to intramolecular transfer of energy from the polyether ring to a substituent

  8. Degradation of Perfluorinated Ether Lubricants on Pure Aluminum Surfaces: Semiempirical Quantum Chemical Modeling

    Science.gov (United States)

    Slaby, Scott M.; Ewing, David W.; Zehe, Michael J.

    1997-01-01

    The AM1 semiempirical quantum chemical method was used to model the interaction of perfluoroethers with aluminum surfaces. Perfluorodimethoxymethane and perfluorodimethyl ether were studied interacting with aluminum surfaces, which were modeled by a five-atom cluster and a nine-atom cluster. Interactions were studied for edge (high index) sites and top (low index) sites of the clusters. Both dissociative binding and nondissociative binding were found, with dissociative binding being stronger. The two different ethers bound and dissociated on the clusters in different ways: perfluorodimethoxymethane through its oxygen atoms, but perfluorodimethyl ether through its fluorine atoms. The acetal linkage of perfluorodimeth-oxymethane was the key structural feature of this molecule in its binding and dissociation on the aluminum surface models. The high-index sites of the clusters caused the dissociation of both ethers. These results are consistent with the experimental observation that perfluorinated ethers decompose in contact with sputtered aluminum surfaces.

  9. Continuous flow photolysis of aryl azides: Preparation of 3H-azepinones

    Directory of Open Access Journals (Sweden)

    Farhan R. Bou-Hamdan

    2011-08-01

    Full Text Available Photolysis of aryl azides to give nitrenes, and their subsequent rearrangement in the presence of water to give 3H-azepinones, is performed in continuous flow in a photoreactor constructed of fluorinated ethylene polymer (FEP tubing. Fine tuning of the reaction conditions using the flow reactor allowed minimization of secondary photochemical reactions.

  10. Synthesis and conformational studies of a series of 5,17-bis-aryl-25,26,27,28-tetrapropoxycalix[4]arenes: The influence of π-π interactions on the molecular structure

    DEFF Research Database (Denmark)

    Larsen, M.; Krebs, Frederik C; Harrit, N.

    1999-01-01

    Four 5,17-bis-aryl-25,26,27,28-tetrapropoxycalix[4]arenes were prepared via Negishi, Suzuki and Ullman type couplings [aryl = phenyl (1), 3-bromophenyl (2), 1-naphthyl (3) and carbazol-9-yl (4)]. The influence of the aryl groups on the structure was studied by X-ray crystallography, NMR, electron...

  11. Synthesis of novel antimicrobial aryl himachalene derivatives from naturally occurring himachalenes

    Science.gov (United States)

    Chaudhary, Abha; Sood, Swati; Das, Pralay; Kaur, Pushpinder; Mahajan, Isha; Gulati, Arvind; Singh, Bikram

    2014-01-01

    Five new 2,9,9-trimethyl-6,7,8,9-tetrahydro-benzocyclohepten-5-ylidene-amine derivatives (16a-16e) were synthesized from α-dehydro-ar-himachalene (11) that was originally prepared from an isomeric mixture of α, β and γ himachalenes (10), the abundant sesquiterpenes of Cedrus deodara essential oil. In addition, different aryl himachalenes derivatives (9, 12, 14 and 15) were also formed from 11. The structures of the synthesized compounds were confirmed on the basis of their NMR, IR and mass spectral data. The prepared compounds were tested against a group of sixteen organisms including gram positive and gram negative bacterial and fungal strains. The introduction of a series of substituted imine groups into aryl himachalenes at 5th position (16a-16e) enhanced antimicrobial activity as compared to the aromatized derivatives (9, 12, 14 and 15) against gram-positive bacteria Bacillus subtilis, Micrococcus luteus and Staphylococcus aureus, and mycotoxigenic fungi Aspergillus parasiticus, A. ochraceous and A. sydowii. graphical Abstract, Figure 1(Fig. 1) PMID:26417335

  12. Increasing the thermopower of crown-ether-bridged anthraquinones

    Science.gov (United States)

    Ismael, Ali K.; Grace, Iain; Lambert, Colin J.

    2015-10-01

    We investigate strategies for increasing the thermopower of crown-ether-bridged anthraquinones. The novel design feature of these molecules is the presence of either (1) crown-ether or (2) diaza-crown-ether bridges attached to the side of the current-carrying anthraquinone wire. The crown-ether side groups selectively bind alkali-metal cations and when combined with TCNE or TTF dopants, provide a large phase-space for optimising thermoelectric properties. We find that the optimum combination of cations and dopants depends on the temperature range of interest. The thermopowers of both 1 and 2 are negative and at room temperature are optimised by binding with TTF alone, achieving thermpowers of -600 μV K-1 and -285 μV K-1 respectively. At much lower temperatures, which are relevant to cascade coolers, we find that for 1, a combination of TTF and Na+ yields a maximum thermopower of -710 μV K-1 at 70 K, whereas a combination of TTF and Li+ yields a maximum thermopower of -600 μV K-1 at 90 K. For 2, we find that TTF doping yields a maximum thermopower of -800 μV K-1 at 90 K, whereas at 50 K, the largest thermopower (of -600 μV K-1) is obtain by a combination TTF and K+ doping. At room temperature, we obtain power factors of 73 μW m-1 K-2 for 1 (in combination with TTF and Na+) and 90 μW m-1 K-2 for 2 (with TTF). These are higher or comparable with reported power factors of other organic materials.We investigate strategies for increasing the thermopower of crown-ether-bridged anthraquinones. The novel design feature of these molecules is the presence of either (1) crown-ether or (2) diaza-crown-ether bridges attached to the side of the current-carrying anthraquinone wire. The crown-ether side groups selectively bind alkali-metal cations and when combined with TCNE or TTF dopants, provide a large phase-space for optimising thermoelectric properties. We find that the optimum combination of cations and dopants depends on the temperature range of interest. The

  13. Efficient and Simple Synthesis of 6-Aryl-1,4-dimethyl-9H-carbazoles

    Directory of Open Access Journals (Sweden)

    Sylvain Rault

    2008-06-01

    Full Text Available A synthetic method for the preparation of 6-aryl-1,4-dimethyl-9H-carbazoles involving a palladium catalyzed coupling reaction of 1,4-dimethyl-9H-carbazole-6-boronic acids and (heteroaryl halides is described.

  14. Development and characterization of poli composites (ether ether ketone)(PEEK)(Hydroxyapatite(HA)

    International Nuclear Information System (INIS)

    Ferreira, V.P.; Santos, F.S.F.; Sa, M.D. de; Fook, M.V.L.

    2016-01-01

    The objective of this work was to develop PEEK / HA composites, combining the biological activity of the ceramic phase with the properties of the polymer phase, the materials used in this research were Poly (ether-ether-ketone) (PEEK) and Hydroxyapatite (HA) (50, 60, 70 and 80% m / v HA), this material was subjected to a load of two tons followed by a thermal treatment at 390 ° for a period of 30 minutes. Then they were characterized by FTIR, DRX and MO. In the physical-chemical characterization of FTIR and XRD, it was not possible to identify significant alterations. In the FTIR spectra of the composites, there is no formation of new identifiable chemical bonds. In the composites XRD diffractograms a profile similar to the ceramic phase was observed, with peaks increasing in intensity and narrowing proportional to the increase of the hydroxyapatite concentration in the composites. In optical microscopy it is possible to observe surfaces with heterogeneous morphology, with signs of roughness and in the cross section we observe a heterogeneous aspect, rich in regions with large agglomerates and lighter particles. Considering the processing aspects, the technique proved to be effective for the development of PEEK /HA composites. (author)

  15. General and efficient one-pot synthesis of novel sugar/heterocyclic(aryl) 1,2-diketones from sugar terminal alkynes by Sonogashira/tetra-n- butylammonium permanganate oxidation.

    Science.gov (United States)

    Zhang, Fuyi; Wu, Xiaopei; Wang, Liming; Liu, Hong; Zhao, Yufen

    2015-11-19

    A new approach for one-pot synthesis of novel sugar/heterocyclic(aryl) 1,2-diketones has been achieved by the reaction of various sugar terminal alkynes with heterocyclic(aryl) iodides at room temperature. This one-pot protocol includes Sonogashira coupling and mild n-Bu4NMnO4 oxidation reaction. This method is mild, general and efficient. Fifty-six examples have been given and the sugar/heterocyclic(aryl) 1,2-diketones were obtained in 71-94% yields. The sugar terminal alkynes include 9 structurally different sugars in pyranose, furanose, and acyclic form which have various protecting groups, sensitive groups, and sterically bulky substituents. The heterocyclic(aryl) iodides include sterically bulky heterocyclic compounds and iodobenzenes with electron-donating, electron-neutral, and electron-withdrawing substituents. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. A novel sulfonated poly(ether ether ketone) and cross-linked membranes for fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hongtao; Zhang, Gang; Wu, Jing; Zhao, Chengji; Zhang, Yang; Shao, Ke; Han, Miaomiao; Lin, Haidan; Zhu, Jing; Na, Hui [Alan G MacDiarmid Institute, College of Chemistry, Jilin University, Qianjin Street 2699, Changchun 130012, Jilin (China)

    2010-10-01

    A novel poly(ether ether ketone) (PEEK) containing pendant carboxyl groups has been synthesized by a nucleophilic polycondensation reaction. Sulfonated polymers (SPEEKs) with different ion exchange capacity are then obtained by post-sulfonation process. The structures of PEEK and SPEEKs are characterized by both FT-IR and {sup 1}H NMR. The properties of SPEEKs as candidates for proton exchange membranes are studied. The cross-linking reaction is performed at 140 C using poly(vinyl alcohol) (PVA) as the cross-linker. In comparison with the non-cross-linked membranes, some properties of the cross-linked membranes are significantly improved, such as water uptake, methanol resistance, mechanical and oxidative stabilities, while the proton conductivity decreases. The effect of PVA content on proton conductivity, water uptake, swelling ratio, and methanol permeability is also investigated. Among all the membranes, SPEEK-C-8 shows the highest selectivity of 50.5 x 10{sup 4} S s cm{sup -3}, which indicates that it is a suitable candidate for applications in direct methanol fuel cells. (author)

  17. Rheological, mechanical and tribological properties of carbon-nanofibre reinforced poly (ether ether ketone composites

    Directory of Open Access Journals (Sweden)

    Volker Altstaedt

    2003-12-01

    Full Text Available Poly(ether ether ketone nanocomposites containing vapour-grown carbon nanofibres (CNF were produced using standard polymer processing techniques. At high shear rates no significant increase in resin viscosity was observed. Nevertheless, the addition of the CNFs results in a higher melt strength at 360°C. Electron microscopy confirmed the homogeneous dispersion and alignment of nanofibres in the polymer matrix. Evaluation of the mechanical composite properties revealed a linear increase in tensile stiffness and strength with nanofibre loading fractions up to 15 wt% whilst matrix ductility was maintained up to 10 wt%. An interpretation of the composite performance by short-fibre theory resulted in rather low intrinsic stiffness properties of the vapour-grown CNF. Differential scanning calorimetry was used to investigate crystallization kinetics and degree of crystallinity. The CNFs were found not to act as nucleating sites. Furthermore, unidirectional sliding tests against two different counterpart materials (100Cr6 martensitic bearing steel, X5CrNi18-10 austenitic stainless steel were performed. The carbon nanofibres were found to reduce the wear rate of PEEK significantly.

  18. Ether gas-sensor based on Au nanoparticles-decorated ZnO microstructures

    Directory of Open Access Journals (Sweden)

    Roberto López

    Full Text Available An ether gas-sensor was fabricated based on gold nanoparticles (Au-NPs decorated zinc oxide microstructures (ZnO-MS. Scanning electron microscope (SEM and high-resolution transmission electron microscope (HRTEM measurements were performed to study morphological and structural properties, respectively, of the ZnO-MS. The gas sensing response was evaluated in a relatively low temperature regime, which ranged between 150 and 250 °C. Compared with a sensor fabricated from pure ZnO-MS, the sensor based on Au-NPs decorated ZnO-MS showed much better ether gas response at the highest working temperature. In fact, pure ZnO-MS based sensor only showed a weak sensitivity of about 25%. The improvement of the ether gas response for sensor fabricated with Au-NPs decorated ZnO-MS was attributed to the catalytic activity of the Au-NPs. Keywords: ZnO microstructures, Au nanoparticles, Ether, Gas sensor

  19. Spectroscopic Identification of the Au-C Bond Formation upon Electroreduction of an Aryl Diazonium Salt on Gold.

    Science.gov (United States)

    Guo, Limin; Ma, Lipo; Zhang, Yelong; Cheng, Xun; Xu, Ye; Wang, Jin; Wang, Erkang; Peng, Zhangquan

    2016-11-08

    Electroreduction of aryl diazonium salts on gold can produce organic films that are more robust than their analogous self-assembled monolayers formed from chemical adsorption of organic thiols on gold. However, whether the enhanced stability is due to the Au-C bond formation remains debated. In this work, we report the electroreduction of an aryl diazonium salt of 4,4'-disulfanediyldibenzenediazonium on gold forming a multilayer of Au-(Ar-S-S-Ar) n , which can be further degraded to a monolayer of Au-Ar-S - by electrochemical cleavage of the S-S moieties within the multilayer. By conducting an in situ surface-enhanced Raman spectroscopic study of both the multilayer formation/degradation and the monolayer reduction/oxidation processes, coupled to density functional theory calculations, we provide compelling evidence that an Au-C bond does form upon electroreduction of aryl diazonium salts on gold and that the enhanced stability of the electrografted organic films is due to the Au-C bond being intrinsically stronger than the Au-S bond for a given phenylthiolate compound by ca. 0.4 eV.

  20. Identification of the stereochemical requirements in the 4-aryl-2-cycloalkylidenhydrazinylthiazole scaffold for the design of selective human monoamine oxidase B inhibitors.

    Science.gov (United States)

    D'Ascenzio, Melissa; Carradori, Simone; Secci, Daniela; Mannina, Luisa; Sobolev, Anatoly P; De Monte, Celeste; Cirilli, Roberto; Yáñez, Matilde; Alcaro, Stefano; Ortuso, Francesco

    2014-05-15

    Exploring the effect that substituents on the cycloaliphatic ring had on the inhibitory activity against human monoamine oxidase B of a series of 4-aryl-2-cycloalkylidenhydrazinylthiazoles led to the synthesis of a new series of 2-methylcyclopentyl and 3-methylcyclopentyl derivatives which were tested in vitro as mixtures of diastereoisomers. In fact, due to the presence of a chiral center on the cycloaliphatic ring and a trisubstituted CN bond, they exist as four diastereoisomers ((E)-(R), (E)-(S), (Z)-(R), (Z)-(S)). 4-(2,4-Difluorophenyl)-2-(2-(3-methylcyclopentylidene)hydrazinyl)thiazole was chosen as a model to investigate the influence of stereochemical requirements on the inhibitory activity against hMAO-B of these derivatives after a stereoconservative synthesis and semi-preparative HPLC diastereoseparation. (R)-(Z) isomer of this compound was endowed with a potent and selective hMAO-B inhibition higher than that of reference drugs as also corroborated by molecular modeling studies. Copyright © 2014 Elsevier Ltd. All rights reserved.

  1. Vitamin K3 (menadione)-induced oncosis associated with keratin 8 phosphorylation and histone H3 arylation.

    Science.gov (United States)

    Scott, Gary K; Atsriku, Christian; Kaminker, Patrick; Held, Jason; Gibson, Brad; Baldwin, Michael A; Benz, Christopher C

    2005-09-01

    The vitamin K analog menadione (K3), capable of both redox cycling and arylating nucleophilic substrates by Michael addition, has been extensively studied as a model stress-inducing quinone in both cell culture and animal model systems. Exposure of keratin 8 (k-8) expressing human breast cancer cells (MCF7, T47D, SKBr3) to K3 (50-100 microM) induced rapid, sustained, and site-specific k-8 serine phosphorylation (pSer73) dependent on signaling by a single mitogen activated protein kinase (MAPK) pathway, MEK1/2. Normal nuclear morphology and k-8 immunofluorescence coupled with the lack of DNA laddering or other features of apoptosis indicated that K3-induced cytotoxicity, evident within 4 h of treatment and delayed but not prevented by MEK1/2 inhibition, was due to a form of stress-activated cell death known as oncosis. Independent of MAPK signaling was the progressive appearance of K3-induced cellular fluorescence, principally nuclear in origin and suggested by in vitro fluorimetry to have been caused by K3 thiol arylation. Imaging by UV transillumination of protein gels containing nuclear extracts from K3-treated cells revealed a prominent 17-kDa band shown to be histone H3 by immunoblotting and mass spectrometry (MS). K3 arylation of histones in vitro followed by electrospray ionization-tandem MS analyses identified the unique Cys110 residue within H3, exposed only in the open chromatin of transcriptionally active genes, as a K3 arylation target. These findings delineate new pathways associated with K3-induced stress and suggest a potentially novel role for H3 Cys110 as a nuclear stress sensor.

  2. Biomedical potentials of crown ethers: prospective antitumor agents.

    Science.gov (United States)

    Kralj, Marijeta; Tusek-Bozić, Ljerka; Frkanec, Leo

    2008-10-01

    Crown ethers are of enormous interest and importance in chemistry, biochemistry, materials science, catalysis, separation, transport and encapsulated processes, as well as in the design and synthesis of various synthetic systems with specific properties, diverse capabilities, and programmable functions. Classical crown ethers are macrocyclic polyethers that contain 3-20 oxygen atoms separated from each other by two or more carbon atoms. They are exceptionally versatile in selectively binding a range of metal ions and a variety of organic neutral and ionic species. Crown ethers are currently being studied and used in a variety of applications beyond their traditional place in chemistry. This review presents additional applications and the ever-increasing biomedical potentials of these intriguing compounds, with particular emphasis on the prospects of their relevance as anticancer agents. We believe that further research in this direction should be encouraged, as crown compounds could either induce toxicities that are different from those of conventional antitumor drugs, or complement drugs in current use, thereby providing a valuable adjunct to therapy.

  3. Diethyl Ether Production Process with Various Catalyst Type

    Directory of Open Access Journals (Sweden)

    Widayat

    2013-01-01

    Full Text Available Several H-zeolite and HZSM-5 catalysts was preparated and their characters have also been investigated. H-zeolit Catalyst was preparated from Natural Zeolite that obtained from Malang District and Gunung Kidul District. Diethyl ether was produced by Ethanol with concentration of 95%. This research use fixed bed reactor that 1 gram of catalyst as bed catalyst, atmospheric pressure and temperature 140oC as the operating condition. Ethanol vapor from vaporization tank was driven by 200 ml/min Nitrogen stream. The responds in this research is liquid product concentration; diethyl ether, ethanol, methanol and water concentration. The results showed that the largest ethanol conversion was produced by the use of 56.44% HZSM-5 and the largest yield of diethyl ether diethyl was produced by the use of alumina and H-zeolite catalyst. The larger ratio between natural zeolite with HCl solvent will produce the larger surface area of catalyst and ethanol conversion. The largest ethanol conversion was produced at reactan ratio 1:20.

  4. Synthesis of benzannelated sultams by intramolecular Pd-catalyzed arylation of tertiary sulfonamides

    Directory of Open Access Journals (Sweden)

    Valentin A. Rassadin

    2017-09-01

    Full Text Available A new and efficient approach to five- and six-membered benzannelated sultams by intramolecular C-arylation of tertiary 1-(methoxycarbonylmethanesulfonamides under palladium catalysis is described. In case of the α-toluenesulfonamide derivative, an unexpected formation of a 2,3-diarylindole was observed under the same conditions.

  5. Proton-conducting membranes based on benzimidazole-containing sulfonated poly(ether ether ketone) compared with their carboxyl acid form

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hongtao; Wu, Jing; Zhao, Chengji; Zhang, Gang; Zhang, Yang; Shao, Ke; Xu, Dan; Lin, Haidan; Han, Miaomiao; Na, Hui [Alan G MacDiarmid Institute, College of Chemistry, Jilin University, Changchun 130012 (China)

    2009-10-15

    A series of sulfonated poly(ether ether ketone) containing pendant carboxyl (C-SPEEKs) have been synthesized using a nucleophilic polycondesation reaction. A condensation reaction between 1,2-diaminobenzene and carboxyl resulted in a new series of copolymers containing benzimidazole groups (SPEEK-BIms). The expected structures of the sulfonated copolymers are confirmed by {sup 1}H NMR. The dependence of ion exchange capacity, water uptake, proton conductivity and methanol diffusion coefficient of SPEEK-BIm membranes has been studied and compared with their carboxyl acid form. The results suggest that the introduction of benzimidazole groups may be responsible for many excellent properties of the membranes for fuel cell. It is noticeable that the markedly improved oxidative stability is benefit for the application of membrane. (author)

  6. Protective effects of ether, oxygen and their mixture for radiation in Drosophila melanogaster

    International Nuclear Information System (INIS)

    Megumi, Tsuneo; Tsujii, Yukio; Gamo, Sumiko

    1992-01-01

    Protective effects of ether mixed with air or oxygen against ionizing radiation damages were demonstrated in adult flies of Drosophila melanogaster. The protective effects against knock-down on the second day and lethality on the eighth day after irradiation were not affected by the radiation sensitivity and DNA repair capacity of the strains. Ether (4.2%) in oxygen was more effective than ether in air for both endpoints. The protective effects may be due to damages not involving cell division, since no mitotic cells are observed in adult flies except in gonadal glands. A change in the orderliness of the cell membrane by ether is suggested to be the cause of the protective effects. (author). 16 refs.; 3 tabs

  7. Iron Oxide-Cobalt Nanocatalyst for O-tert-Boc Protection and O-Arylation of Phenols

    Directory of Open Access Journals (Sweden)

    Vilas B. Gade

    2018-04-01

    Full Text Available Efficient and general protocols for the O-tert-boc protection and O-arylation of phenols were developed in this paper using a recyclable magnetic Fe3O4-Co3O4 nanocatalyst (Nano-Fe-Co, which is easily accessible via simple wet impregnation techniques in aqueous mediums from inexpensive precursors. The results showed the catalysts were well characterized by XRD (X-ray Diffraction, ICP-AES (Inductive Coupled Plasma Atomic Emission Spectroscopy, TEM (Transmission Electron Microscopy, TOF-SIMS (Time-Of-Flight Secondary Ion Mass Spectrometry and XPS (X-ray Photoelectron Spectroscopy. The O-tert-boc protection and O-arylation of phenols was accomplished in good to excellent yields (85–95% and the catalyst was reusable and recyclable with no loss of catalytic activity for at least six repetitions.

  8. Radiolytic decomposition of 4-bromodiphenyl ether

    International Nuclear Information System (INIS)

    Tang Liang; Xu Gang; Wu Wenjing; Shi Wenyan; Liu Ning; Bai Yulei; Wu Minghong

    2010-01-01

    Polybrominated diphenyl ethers (PBDEs) spread widely in the environment are mainly removed by photochemical and anaerobic microbial degradation. In this paper, the decomposition of 4-bromodiphenyl ether (BDE -3), the PBDEs homologues, is investigated by electron beam irradiation of its ethanol/water solution (reduction system) and acetonitrile/water solution (oxidation system). The radiolytic products were determined by GC coupled with electron capture detector, and the reaction rate constant of e sol - in the reduction system was measured at 2.7 x 10 10 L · mol -1 · s -1 by pulsed radiolysis. The results show that the BDE-3 concentration affects strongly the decomposition ratio in the alkali solution, and the reduction system has a higher BDE-3 decomposition rate than the oxidation system. This indicates that the BDE-3 was reduced by effectively capturing e sol - in radiolytic process. (authors)

  9. Spino ether and its vortices: leptons and hadrons

    Energy Technology Data Exchange (ETDEWEB)

    Skorski, R [College of Engineering, Univ. of Alabama, Alabama (USA)

    1977-03-01

    According to the theory advanced by the author, space is occupied by a spino ether lattice. Where no spino lattice exists, there are black holes. The spino is a kind of massive neutrino with a rest mass of about 7.39x10/sup -47/g and a diameter of 4.56x10/sup -34/cm. The distance between spinos in the spino lattice is about 2x10/sup -10/cm. Spino ether is ubiquitous in all matter, pervades atoms and their nuclei and penetrates matter with no resistance. In fact, hadrons and leptons are shown to be vortices of the spino ether. About one km/sup 3/ of space contains spino ether having a mass equal to 10/sup 80/ baryons, equivalent to the total mass of our universe. If the distances between spinos equaled their diameters, 4.56x10/sup -34/cm instead of 2x10/sup -10/cm, then the diameter of the mass equivalent to our universe would be about 2cm. This is in agreement with the size of the premordial universe, before its explosion, as calculated earlier by other theories. It is conjectured that explosions of energy and mass in space are more frequent on a smaller scale than those in the universe, for example novas, or even on a still smaller scale usually associated with the birth of different nuclei. The abundance of iron in the solar corona, on the surface of Mars, and in the Martin sky appears to be due to hadron formation from space itself.

  10. Dimethylzinc-Initiated Radical Coupling of β-Bromostyrenes with Ethers and Amines

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Ahlburg, Andreas; Madsen, Robert

    2015-01-01

    A new coupling reaction has been developed in which β-bromostyrenes react with ethers and tertiary amines to introduce the styryl group in the α-position. The transformation is mediated by Me2Zn/O2 with 10 % MnCl2 and is believed to proceed by a radical addition-elimination mechanism. The ether...... and the amine are employed as solvent and the coupling takes place through the most stable α radical for unsymmetrical substrates. The products are obtained in moderate to good yields as the pure E isomers. The coupling can be achieved with a range of smaller cyclic and acyclic ethers/amines as well as various...

  11. Design and synthesis of prostate cancer antigen-1 (PCA-1/ALKBH3) inhibitors as anti-prostate cancer drugs.

    Science.gov (United States)

    Nakao, Syuhei; Mabuchi, Miyuki; Shimizu, Tadashi; Itoh, Yoshihiro; Takeuchi, Yuko; Ueda, Masahiro; Mizuno, Hiroaki; Shigi, Naoko; Ohshio, Ikumi; Jinguji, Kentaro; Ueda, Yuko; Yamamoto, Masatatsu; Furukawa, Tatsuhiko; Aoki, Shunji; Tsujikawa, Kazutake; Tanaka, Akito

    2014-02-15

    A series of 1-aryl-3,4-substituted-1H-pyrazol-5-ol derivatives was synthesized and evaluated as prostate cancer antigen-1 (PCA-1/ALKBH3) inhibitors to obtain a novel anti-prostate cancer drug. After modifying 1-(1H-benzimidazol-2-yl)-3,4-dimethyl-1H-pyrazol-5-ol (1), a hit compound found during random screening using a recombinant PCA-1/ALKBH3, 1-(1H-5-methylbenzimidazol-2-yl)-4-benzyl-3-methyl-1H-pyrazol-5-ol (35, HUHS015), was obtained as a potent PCA-1/ALKBH3 inhibitor both in vitro and in vivo. The bioavailability (BA) of 35 was 7.2% in rats after oral administration. As expected, continuously administering 35 significantly suppressed the growth of DU145 cells, which are human hormone-independent prostate cancer cells, in a mouse xenograft model without untoward effects. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. Poly (ether ether ketone) membranes for fuel cells; Membranas de poli (eter eter cetona) sulfonado para celulas a combustivel

    Energy Technology Data Exchange (ETDEWEB)

    Marrero, Jacqueline C.; Gomes, Ailton de S.; Filho, Jose C.D., E-mail: jacquecosta@gmail.com [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil); Hui, Wang S. [Universidade de Sao Paulo (USP), Sao Paulo, SP (Brazil); Oliveira, Vivianna S. de [Escola Tecnica Rezende-Rammel, Rio de Janeiro, RJ (Brazil)

    2015-07-01

    Polymeric membranes were developed using a SPEEK polymer matrix (sulphonated poly (ether ether ketone)), containing hygroscopic particles of zirconia (Zr) (incorporated by sol-gel method), for use as electrolyte membranes in fuel cells. SPEEK with different sulfonation degrees were used: 63 and 86%. The thermal analysis (TGA and DSC) was carried out to characterize the membranes and electrochemical impedance spectroscopy (EIS) was carried out to evaluating the proton conductivity of the membranes. Additional analysis were underway in order to characterize these membranes, which include: X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in order to evaluate the influence of zirconia and sulfonation degree on the properties of the membranes. (author)

  13. IRON(III) NITRATE-CATALYZED FACILE SYNTHESIS OF DIPHENYLMETHYL (DPM) ETHERS FROM ALCOHOLS

    Science.gov (United States)

    Diphenyl methyl (DPM) ethers constitute important structural portion of some pharmaceutical entities and also as protective group for hydroxyl groups in synthetic chemistry. DPM ethers are normally prepared using concentrated acids or base as catalysts, which may result in the fo...

  14. Covalent Allosteric Inactivation of Protein Tyrosine Phosphatase 1B (PTP1B) by an Inhibitor-Electrophile Conjugate.

    Science.gov (United States)

    Punthasee, Puminan; Laciak, Adrian R; Cummings, Andrea H; Ruddraraju, Kasi Viswanatharaju; Lewis, Sarah M; Hillebrand, Roman; Singh, Harkewal; Tanner, John J; Gates, Kent S

    2017-04-11

    Protein tyrosine phosphatase 1B (PTP1B) is a validated drug target, but it has proven difficult to develop medicinally useful, reversible inhibitors of this enzyme. Here we explored covalent strategies for the inactivation of PTP1B using a conjugate composed of an active site-directed 5-aryl-1,2,5-thiadiazolidin-3-one 1,1-dioxide inhibitor connected via a short linker to an electrophilic α-bromoacetamide moiety. Inhibitor-electrophile conjugate 5a caused time-dependent loss of PTP1B activity consistent with a covalent inactivation mechanism. The inactivation occurred with a second-order rate constant of (1.7 ± 0.3) × 10 2 M -1 min -1 . Mass spectrometric analysis of the inactivated enzyme indicated that the primary site of modification was C121, a residue distant from the active site. Previous work provided evidence that covalent modification of the allosteric residue C121 can cause inactivation of PTP1B [Hansen, S. K., Cancilla, M. T., Shiau, T. P., Kung, J., Chen, T., and Erlanson, D. A. (2005) Biochemistry 44, 7704-7712]. Overall, our results are consistent with an unusual enzyme inactivation process in which noncovalent binding of the inhibitor-electrophile conjugate to the active site of PTP1B protects the nucleophilic catalytic C215 residue from covalent modification, thus allowing inactivation of the enzyme via selective modification of allosteric residue C121.

  15. Stereoselective synthesis of 1,3-disubstituted isoindolines via Rh(III)-catalyzed tandem oxidative olefination-cyclization of 4-aryl cyclic sulfamidates.

    Science.gov (United States)

    Son, Se-Mi; Seo, Yeon Ji; Lee, Hyeon-Kyu

    2016-03-21

    Rh(III)-catalyzed tandem ortho C-H olefination of cyclic 4-aryl sulfamidates (1) and subsequent intramolecular cyclization are described. This reaction serves as a method for the direct and stereoselective synthesis of 1,3-disubstituted isoindolines (3) starting with enantiomerically enriched 4-aryl cyclic sulfamidates. In this process, the configurational integrity of the stereogenic center in the starting cyclic sulfamidate is completely retained. In addition, the process generates trans-1,3-disubstituted isoindolines exclusively.

  16. Thermal and oxidative degradation studies of formulated C-ethers by gel-permeation chromatography

    Science.gov (United States)

    Jones, W. R., Jr.; Morales, W.

    1982-01-01

    Gel-permeation chromatography was used to analyze C-ether lubricant formulations from high-temperature bearing tests and from micro-oxidation tests. Three mu-styragel columns (one 500 and two 100 A) and a tetrahydrofuran mobile phase were found to adequately separate the C-ether degradation products. The micro-oxidation tests yielded degradation results qualitatively similar to those observed from the bearing tests. Micro-oxidation tests conducted in air yielded more degradation than did tests in nitrogen. No great differences were observed between the thermal-oxidative stabilities of the two C-ether formulations or between the catalytic degradation activities of silver and M-50 steel. C-ether formulation I did yield more degradation than did formulation II in 111- and 25-hour bearing tests, respectively.

  17. A focused fragment library targeting the antibiotic resistance enzyme - Oxacillinase-48: Synthesis, structural evaluation and inhibitor design.

    Science.gov (United States)

    Akhter, Sundus; Lund, Bjarte Aarmo; Ismael, Aya; Langer, Manuel; Isaksson, Johan; Christopeit, Tony; Leiros, Hanna-Kirsti S; Bayer, Annette

    2018-02-10

    β-Lactam antibiotics are of utmost importance when treating bacterial infections in the medical community. However, currently their utility is threatened by the emergence and spread of β-lactam resistance. The most prevalent resistance mechanism to β-lactam antibiotics is expression of β-lactamase enzymes. One way to overcome resistance caused by β-lactamases, is the development of β-lactamase inhibitors and today several β-lactamase inhibitors e.g. avibactam, are approved in the clinic. Our focus is the oxacillinase-48 (OXA-48), an enzyme reported to spread rapidly across the world and commonly identified in Escherichia coli and Klebsiella pneumoniae. To guide inhibitor design, we used diversely substituted 3-aryl and 3-heteroaryl benzoic acids to probe the active site of OXA-48 for useful enzyme-inhibitor interactions. In the presented study, a focused fragment library containing 49 3-substituted benzoic acid derivatives were synthesised and biochemically characterized. Based on crystallographic data from 33 fragment-enzyme complexes, the fragments could be classified into R 1 or R 2 binders by their overall binding conformation in relation to the binding of the R 1 and R 2 side groups of imipenem. Moreover, binding interactions attractive for future inhibitor design were found and their usefulness explored by the rational design and evaluation of merged inhibitors from orthogonally binding fragments. The best inhibitors among the resulting 3,5-disubstituted benzoic acids showed inhibitory potential in the low micromolar range (IC 50  = 2.9 μM). For these inhibitors, the complex X-ray structures revealed non-covalent binding to Arg250, Arg214 and Tyr211 in the active site and the interactions observed with the mono-substituted fragments were also identified in the merged structures. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

  18. Novel Synthesis and Anti-HIV-1 Activity of 2-Arylthio-6-benzyl-2,3-dihydro-1H-pyrimidin-4-ones (Aryl S-DABOs)

    DEFF Research Database (Denmark)

    Aly, Youssef L.; Pedersen, Erik Bjerreg.; La Colla, Paolo

    2007-01-01

    The synthesis and the anti-HIV-1 activity of a series of 2-arylthio-6-benzyl-2,3-dihydro-1H-pyrimidin-4-ones (aryl S-DABOs) are reported. These compounds were synthesized via a coupling reaction of the corresponding 6-benzyl-2-thiouracils with aryl iodides in the presence of neocuproine hydrate...

  19. Direct dimethyl ether fueling of a high temperature polymer fuel cell

    DEFF Research Database (Denmark)

    Jensen, Jens Oluf; Vassiliev, Anton; Olsen, M.I.

    2012-01-01

    Direct dimethyl ether (DME) fuel cells suffer from poor DME–water miscibility and so far peak powers of only 20–40 mW cm−2 have been reported. Based on available literature on solubility of dimethyl ether (DME) in water at ambient pressure it was estimated that the maximum concentration of DME at...

  20. Synthesis of Novel Bibrachial Lariat Ethers (BiBLEs) Containing [1,2 ...

    African Journals Online (AJOL)

    NICO

    A practical and regioselective method for the synthesis of cis-diastereomers of bibrachial lariat ethers (BiBLEs) bearing ester and amide groups is reported. The novel bibrachial lariat ethers (BiBLEs) 3a–d with neutral side chains were prepared by reaction of the corresponding aza-crown macrocycles 1a–b with ethyl ...

  1. Isothermal (vapor + liquid) equilibria and excess enthalpy data of {1-hexene + methyl butyl ether (MBE)} and {1-hexene + methyl tert-butyl ether (MTBE)} binary systems at several temperatures

    International Nuclear Information System (INIS)

    Hani, Rachida; Solimando, Roland; Negadi, Latifa; Jose, Jacques; Ait Kaci, Ahmed

    2012-01-01

    Highlights: ► Vapor pressures of (1-hexene + methyl butyl ether) or (1-hexene + methyl tert-butyl ether) are reported between (263 and 363) K. ► The two mixtures exhibit positive G E . ► Additionally, molar excess enthalpies, H E , for the two binary systems have been measured at 303.15. - Abstract: The vapor pressures of {1-hexene + methyl butyl ether (MBE)} and {1-hexene + methyl tert-butyl ether (MTBE)} binary mixtures and of the three pure components were measured by means of a static device at temperatures between (263 and 333) K. The data were correlated with the Antoine equation. From these data, excess Gibbs functions were calculated for several constant temperatures and fitted to a third-order Redlich–Kister equation using the Barker’s method. Additionally, molar excess enthalpies, H E , for the two binary systems have been measured at 303.15 K using an isothermal flow calorimeter.

  2. Metabolism of nitrodiphenyl ether herbicides by dioxin-degrading bacterium Sphingomonas wittichii RW1.

    Science.gov (United States)

    Keum, Young Soo; Lee, Young Ju; Kim, Jeong-Han

    2008-10-08

    Nitrodiphenyl ether herbicides, including chlomethoxyfen, nitrofen, and oxyfluorfen are potent herbicides. Some metabolites and parent compounds are considered as possible mutagens and endocrine disruptors. Both properties pose serious hygienic and environmental risks. Sphingomonas wittichii RW1 is a well-known degrader of polychlorinated dibenzo- p-dioxins, dibenzofurans, and diphenyl ethers. However, no detailed research of its metabolic activity has been performed against pesticides with a diphenyl ether scaffold. In this study, we report S. wittichii RW1 as a very potent diphenyl ether herbicide-metabolizing bacterium with broad substrate specificity. The structures of metabolites were determined by instrumental analysis and synthetic standards. Most pesticides were rapidly removed from the culture medium in the order of nitrofen > oxyfluorfen > chlomethoxyfen. In general, herbicides were degraded through the initial reduction and N-acetylation of nitro groups, followed by ether bond cleavage. Relatively low concentrations of phenolic and catecholic metabolites throughout the study suggested that these metabolites were rapidly metabolized and incorporated into primary metabolism. These results indicate that strain RW1 has very versatile metabolic activities over a wide range of environmental contaminants.

  3. Children's exposure to polybrominated diphenyl ethers.

    NARCIS (Netherlands)

    Zuurbier, M.; Leijs, M.; Schoeters, G.; Tusscher, G. Ten; Koppe, J.G.

    2006-01-01

    Background: Polybrominated biphenyl ethers (PBDEs), a class of brominated flame retardants, are frequently used in consumer products. PBDEs levels in environmental and human samples have increased in recent decades. Children are exposed to PBDEs through diet, mainly through fish, meat and milk.

  4. Mechanical properties and chemical stability of pivalolactone-based poly(ether ester)s

    NARCIS (Netherlands)

    Tijsma, E.J.; Tijsma, E.J.; van der Does, L.; Bantjes, A.; Bantjes, A.; Vulic, I.

    1994-01-01

    The processing, mechanical and chemical properties of poly(ether ester)s, prepared from pivalolactone (PVL), 1,4-butanediol (4G) and dimethyl terephthalate (DMT), were studied. The poly(ether ester)s could easily be processed by injection moulding, owing to their favourable rheological and thermal

  5. Synthesis and optical properties of new 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl-1,3,4-oxadiazoles

    Directory of Open Access Journals (Sweden)

    Anastasia S. Kostyuchenko

    2017-02-01

    Full Text Available New photoluminescent donor–acceptor–donor (DAD molecules, namely 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl-1,3,4-oxadiazoles were prepared by palladium-catalyzed coupling from readily available compounds such as ethyl 3-decyl-2,2'-bithiophene-5-carboxylate and aryl halides. The obtained compounds feature increasing bathochromic shifts in their emission spectra with increasing aryl-substituent size yielding blue to bluish-green emissions. At the same time, their absorption spectra are almost independent from the identity of the terminal substituent with λmax values ranging from 395 to 405 nm. The observed trends are perfectly predicted by quantum chemical DFT/TDDFT calculations carried out for these new molecules.

  6. Identification of 1-Aryl-1H-1,2,3-triazoles as Potential New Antiretroviral Agents.

    Science.gov (United States)

    Gonzaga, Daniel T G; Souza, Thiago M L; Andrade, Viviane M M; Ferreira, Vitor F; de C da Silva, Fernando

    2018-01-01

    Low molecular weight 1-Aryl-1H-1,2,3-triazoles are endowed with various types of biological activities, such as against cancer, HIV and bacteria. Despite the existence of six different classes of antiretroviral drugs in clinical use, HIV/AIDS continue to be an on growing public health problem. In the present study, we synthesized and evaluated thirty 1-Aryl-1H-1,2,3-triazoles against HIV replication. The compounds were prepared by Huisgen 1,3-dipolar cycloaddition protocol catalyzed by Cu(I) between aryl azides and propargylic alcohol followed by further esterification and etherification from a nucleophilic substitution with acid chlorides or alkyl bromides in good yields. The compounds were submitted to the inhibition of HIV replication and evaluation of their cytotoxicity. Initially, the compounds were screened at 10 µM and the most active were further evaluated in order to obtain some pharmacological parameters. Thirty molecules were evaluated, six were selected - because they inhibited more than 80% HIV replication. We further showed that two of these compounds are 8-times more potent, and less cytotoxic, than nevirapine, an antiretroviral drug in clinical use. We identified very simple triazoles with promissing antiretroviral activities that led to the development of new drugs against AIDS. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  7. Efficient Synthesis of β-Aryl-γ-lactams and Their Resolution with (S-Naproxen: Preparation of (R- and (S-Baclofen

    Directory of Open Access Journals (Sweden)

    Iris J. Montoya-Balbás

    2015-12-01

    Full Text Available An efficient synthesis of enantiomerically-pure β-aryl-γ-lactams is described. The principal feature of this synthesis is the practical resolution of β-aryl-γ-lactams with (S-Naproxen. The procedure is based on the Michael addition of nitromethane to benzylidenemalonates, which was easily obtained, followed by the reduction of the γ-nitroester in the presence of Raney nickel and the subsequent saponification/decarboxylation reaction. The utility of this methodology was highlighted by the preparation of enantiomerically-pure (R- and (S-Baclofen hydrochloride.

  8. Flourimetric and prototropic studies on the inclusion complexation of 2-amino and 4-aminodiphenyl ethers with {beta}-cyclodextrin: Unusual behavior of 4-aminodiphenyl ether

    Energy Technology Data Exchange (ETDEWEB)

    Enoch, Israel V. Muthu Vijayan [Department of Chemistry, Annamalai University, Annamalainagar 608 002, Tamil Nadu (India); Swaminathan, Meenakshisundaram [Department of Chemistry, Annamalai University, Annamalainagar 608 002, Tamil Nadu (India)], E-mail: chemsam@yahoo.com

    2007-12-15

    The fluorescence characteristics of diphenyl ether (DPE), 2-aminodiphenyl ether (2ADPE) and 4-aminodiphenyl ether (4ADPE) and prototropic behavior of 2ADPE and 4ADPE on inclusion complexation with {beta}-cyclodextrin have been investigated. DPE forms 1:1 complex whereas 2ADPE and 4ADPE form 1:2 complex with {beta}-CDx. The fluorimetric and prototropic behaviors of 4ADPE in {beta}-CDx are different from those in aqueous solution. The dual fluorescence of 4ADPE in {beta}-CDx is found to be due to twisted intramolecular charge transfer (TICT) character induced by inclusion complexation. The two equilibria viz. monocation{r_reversible}monocation solvent exciplex{r_reversible}neutral reported for 4ADPE in aqueous solution are not observed in presence of {beta}-CDx. The ground and excited state pK{sub a} values for monocation-neutral equilibrium of 2ADPE and 4ADPE have been reported.

  9. High Resolution Rotational Spectroscopy of a Flexible Cyclic Ether

    Science.gov (United States)

    Gámez, F.; Martínez-Haya, B.; Blanco, S.; López, J. C.; Alonso, J. L.

    2011-06-01

    Crown ethers stand as one cornerstone molecular class inhost-guest Supramolecular Chemistry and constitute building blocks for a broad range of modern materials. We report here the first high resolution rotational study of a crown ether: 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5 ether,15c5). Molecular beam Fourier transform microwave spectroscopy has been employed. The liquid sample of 15c5 has been vaporized using heating methods. The considerable size of 15c5 and the broad range of conformations allowed by the flexibility of its backbone pose important challenges to spectroscopy approaches. In fact, the ab-initio computational study for isolated 15c5, yields at least six stable conformers with relative free energies within 2 kJ Mol-1 (167 Cm-1). Nevertheless, in this investigation it has been possible to identify and characterize in detail one stable rotamer of the 15c5 molecule and to challenge different quantum methods for the accurate description of this system. The results pave the ground for an extensive description of the conformational landscape of 15c5 and related cyclic ethers in the near term. J. L. Alonso, F. J. Lorenzo, J. C. López, A. Lesarri, S. Mata and H. Dreizler, Chem. Phys., 218, 267 (1997) S. Blanco, J.C López, J.L. Alonso, P. Ottaviani, W. Caminati, J. Chem. Phys. 119, 880 (2003) S.E. Hill, D. Feller, Int. J. Mass Spectrom. 201, 41 (2000)

  10. Solvent Effects on Cesium Complexation with Crown Ethers from Liquid to Supercritical Fluids

    International Nuclear Information System (INIS)

    Wai, Chien M.; Rustenholtz, Anne; Wang, Shaofen; Lee, Su-Chen; Herman, Jamie; Porter, Richard A.

    2004-01-01

    Nuclear magnetic resonance (NMR) techniques were used to study crown ether-water interactions in solvents of low dielectric constants such as chloroform and carbon tetrachloride. Water forms a 1:1 complex with a number of crown ethers including 12-crown-4, 15-crown-5, 18-crown-6, dicyclohexano-18=crown-6, dicyclohexano-24-crown 8, and dibenzl-24-crown-8 in chloroform. Among these crown ethers, the 18-crown-6-H2 complex has the largest equilibrium constant (K=545) and 97% of the crown is complexed to water in chloroform. Addition of carbon tetrachloride to chloroform lowers the equilibrium constants of the crown-water complexes. The partition coefficients of crown ethers (D=crown in water/crown in solvent) between water and organic solvent also vary with solvent composition

  11. Carboxyl functionalization of carbon fibers via aryl diazonium reaction in molten urea to enhance interfacial shear strength

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yuwei [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Meng, Linghui [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Fan, Liquan [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Wu, Guangshun; Ma, Lichun; Zhao, Min [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Huang, Yudong, E-mail: ydhuang.hit1@yahoo.com.cn [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China)

    2016-01-30

    Graphical abstract: - Highlights: • Carbon fibers are functionalized with benzoic acid groups via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 66%. • Tensile strength of the carbon fibers is preserved after grafting reaction. • The treatment in molten urea can improve modification efficiency greatly. • Using molten urea as the reaction medium can avoid pollution from organic solvents. - Abstract: Using molten urea as the solvent, carbon fibers were functionalized with carboxylic acid groups via aryl diazonium reaction in 15 min to improve their interfacial bonding with epoxy resin. The surface functionalization was quantified by X-ray photoelectron spectroscopy, which showed that the relative surface coverage of carboxylic acid groups increased from an initial percentage of 3.17–10.41%. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 66%. Meanwhile, the technique did not adopt any pre-oxidation step to produce functional groups prior to grafting and was shown to maintain the tensile strength of the fibers. This methodology provided a rapid, facile and economically viable route to produce covalently functionalized carbon fibers in large quantities with an eco-friendly method.

  12. Carboxyl functionalization of carbon fibers via aryl diazonium reaction in molten urea to enhance interfacial shear strength

    International Nuclear Information System (INIS)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Wu, Guangshun; Ma, Lichun; Zhao, Min; Huang, Yudong

    2016-01-01

    Graphical abstract: - Highlights: • Carbon fibers are functionalized with benzoic acid groups via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 66%. • Tensile strength of the carbon fibers is preserved after grafting reaction. • The treatment in molten urea can improve modification efficiency greatly. • Using molten urea as the reaction medium can avoid pollution from organic solvents. - Abstract: Using molten urea as the solvent, carbon fibers were functionalized with carboxylic acid groups via aryl diazonium reaction in 15 min to improve their interfacial bonding with epoxy resin. The surface functionalization was quantified by X-ray photoelectron spectroscopy, which showed that the relative surface coverage of carboxylic acid groups increased from an initial percentage of 3.17–10.41%. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 66%. Meanwhile, the technique did not adopt any pre-oxidation step to produce functional groups prior to grafting and was shown to maintain the tensile strength of the fibers. This methodology provided a rapid, facile and economically viable route to produce covalently functionalized carbon fibers in large quantities with an eco-friendly method.

  13. Ligand-Enabled Reactivity and Selectivity in a Synthetically Versatile Aryl C–H Olefination*

    Science.gov (United States)

    Wang, Dong-Hui; Engle, Keary M.; Shi, Bing-Feng; Yu, Jin-Quan

    2010-01-01

    The Mizoroki–Heck reaction, which couples aryl halides with olefins, has been widely used to stitch together the carbogenic cores of numerous complex organic molecules. Given that the position-selective introduction of a halide onto an arene is not always straightforward, direct olefination of aryl C–H bonds would obviate the inefficiencies associated with generating halide precursors or their equivalents; however, methods for carrying out such a reaction have suffered from narrow substrate scope and low positional selectivity. Here we report an operationally simple, atom-economical, carboxylate-directed Pd(II)-catalyzed C–H olefination reaction with phenylacetic acid and 3-phenylpropionic acid substrates, using oxygen at atmospheric pressure as the oxidant. The positional selectivity can be tuned by introducing amino acid derivatives as ligands. We demonstrate the versatility of the method through direct elaboration of commercial drug scaffolds and efficient synthesis of 2-tetralone and naphthoic acid natural product cores. PMID:19965380

  14. New degradation compounds from lignocellulosic biomass pretreatment: routes for formation of potent oligophenolic enzyme inhibitors

    DEFF Research Database (Denmark)

    Rasmussen, H.; Tanner, David Ackland; Sørensen, H. R.

    2017-01-01

    -condensation reactions involving aldol condensations, 1,4 additions to α,β unsaturated carbonyl compounds, 3-keto acid decarboxylations and oxidations. Furthermore, pentose reactions with phenolic lignin components are suggested. The identification of the central role of xylose in the reaction routes for oligophenolic...... inhibitor formation led to the solution to protect the reactive anomeric center in xylose. It is shown that protection of the anomeric center in in situ generated xylose with ethylene glycol monobutyl ether, during pretreatment of wheat straw, reduces the level of oligophenols by 73%. The results pave...

  15. Radiation-induced glycoside bond breaking in cellulose methyl ethers

    International Nuclear Information System (INIS)

    Petryaev, E.P.; Boltromeyuk, V.V.; Kovalenko, N.I.; Shadyro, O.I.

    1988-01-01

    Radiation-induced destruction of cellulose methyl ethers of different degree of esterification in aqueous solutions with and without acceptors: (N 2 O, O 2 , H 2 O + , Co(2), Cu(2)) is investigated. It is established that OH radicals make main contribution into radiolytic transformations of cellulose ethers in aqueous solutions. Reactions of radicals with free valency on carbon atoms containing secondary nonsubstituted hydroxyl groups lead also to glycoside bond breaking besides the reaction of β-fragmentation and hydrolysis of radicals with an unpaired electron localized near C 1 , C 4 , C 5 aroms

  16. Amination of Aryl Halides and Esters Using Intensified Continuous Flow Processing

    Directory of Open Access Journals (Sweden)

    Thomas M. Kohl

    2015-09-01

    Full Text Available Significant process intensification of the amination reactions of aryl halides and esters has been demonstrated using continuous flow processing. Using this technology traditionally difficult amination reactions have been performed safely at elevated temperatures. These reactions were successfully conducted on laboratory scale coil reactor modules with 1 mm internal diameter (ID and on a preparatory scale tubular reactor with 6 mm ID containing static mixers.

  17. Direct C-H Arylation Meets Perovskite Solar Cells: Sn-Free Synthesis Shortcut to High Performance Hole-Transporting Materials.

    Science.gov (United States)

    Chang, Yu-Chieh; Lee, Kun-Mu; Lai, Chia-Hsin; Liu, Ching-Yuan

    2018-03-30

    In contrast to the traditional multistep synthesis, we demonstrate herein a two-step synthesis-shortcut to triphenylamine-based hole-transporting materials (HTMs) through sequential direct C-H arylations. These hole-transporting molecules are fabricated in perovskite-based solar cells (PSCs), exhibiting promising efficiencies up to 17.69%, which is comparable to PSCs utilizing the commercially available spiro-OMeTAD as HTM. This is the first report describing the use of step-saving C-H activations/arylations in the facile synthesis of small-molecule HTMs for perovskite solar cells. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Oxime Ethers of (E)-11-Isonitrosostrychnine as Highly Potent Glycine Receptor Antagonists

    DEFF Research Database (Denmark)

    Mohsen, Amal M Y; Mandour, Yasmine M; Sarukhanyan, Edita

    2016-01-01

    of the crystal structure of the α3 glycine receptor indicated the same orientation of the strychnine core for all analogues. For the most potent oxime ethers, the ether substituent was accommodated in a lipophilic receptor binding pocket. The findings identify the oxime hydroxy group as a suitable attachment...

  19. C-H Bond Functionalization via Hydride Transfer: Formation of α-Arylated Piperidines and 1,2,3,4-Tetrahydroisoquinolines via Stereoselective Intramolecular Amination of Benzylic C-H Bonds

    OpenAIRE

    Vadola, Paul A.; Carrera, Ignacio; Sames, Dalibor

    2012-01-01

    We here report a study of the intramolecular amination of sp3 C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl-aldehydes are subjected to N-toluenesulfonamide in the presence of BF3•OEt2 to effect imine formation and HT-cyclization, leading to 2-aryl-piperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexib...

  20. Nickel-catalyzed direct synthesis of dialkoxymethane ethers

    Indian Academy of Sciences (India)

    MURUGAN SUBARAMANIAN

    Nickel catalysis; alcohol; paraformaldehyde; ether; solvent-free condition. 1. Introduction ..... oxidation and Dopamine Release with Protective Effects. Against Central ... P, Ghosh A, Saha R and Saha B 2016 A Review on the. Advancement of ...

  1. Reproductive Effects of Two Polybrominated Diphenyl Ethers on the Rotifer Brachionus plicatilis.

    Science.gov (United States)

    Zhang, Jing; Wang, You; Zhou, Bin; Sun, Kai-Ming; Tang, Xuexi

    2016-08-01

    The effects of two polybrominated diphenyl ethers (PBDEs) on the reproduction of the rotifer Brachionus plicatilis were investigated. Results showed that sexual maturation was promoted by tetra-brominated diphenyl ether-47 (BDE-47) and deca-brominated diphenyl ether-209 (BDE-209), whereas fecundity was inhibited by BDE-47, but promoted by BDE-209. Additionally, both PBDEs affected the expression of two genes, vasa and nanos mRNA, related to rotifer reproduction. This suggests a possible regulatory molecular mechanism at the transcriptional level. Our research extends the current knowledge of the ecotoxicological mechanism induced by PBDEs and provides further essential information for assessing the risks of PBDE contamination in marine ecosystems.

  2. Amended final report on the safety assessment of PPG-40 butyl ether with an addendum to include PPG-2, -4, -5, -9, -12, -14, -15, -16, -17, -18, -20, -22, -24, -26, -30, -33, -52, and -53 butyl ethers.

    Science.gov (United States)

    Lanigan, R S

    2001-01-01

    The Polypropylene Glycol (PPG) Butyl Ethers function as skinand hair-conditioning agents in cosmetics. Intestinal absorption of the PPG Butyl Ethers was inversely proportional to the molecular weight. In general, the toxicity of the PPG Butyl Ethers decreased as the molecular weight increased. In acute studies, moderate intraperitoneal (IP) doses of various PPG Butyl Ethers caused convulsive seizures in mice and anesthetized dogs, and large oral doses caused decreased activity, anuria, renal tubular swelling and necrosis, and hepatic swelling and necrosis. PPG-2 Butyl Ether vapors were nontoxic by the inhalation route. PPG-2 Butyl Ether was nontoxic in short-term feeding and dermal exposure studies in rats. In animal irritation studies, PPG-2 Butyl Ether caused minor, transient erythema and desquamation; in addition, erythema, edema, ecchymosis, necrosis, and other changes were observed during an acute percutaneous study. PPG-2 Butyl Ether also caused minor to moderate conjunctival irritation and minor corneal injury. PPG-2 Butyl Ether when dermally applied was nontoxic to pregnant rats and was nonteratogenic at doses up to 1.0 ml/kg/day. PPG BE800 at concentrations of 0.001% to 0.26% in feed was noncarcinogenic to rats after 2 years of treatment. In clinical studies, PPG BE800 was nonirritating and nonsensitizing to the skin when tested using 200 subjects. PPG-40 Butyl Ether was neither an irritant nor a sensitizer in a repeat-insult patch test using 112 subjects. Although clinical testing did not indicate significant skin irritation is produced by these ingredients, the animal test data did indicate the potential that these ingredients can be irritating. Therefore, it was concluded that the PPG Butyl Ethers can be used safely in cosmetic products if they are formulated to avoid irritation. Data on the component ingredients, Propylene Glycol, PPG, and n-Butyl Alcohol, from previous cosmetic ingredient safety assessments were also considered and found to support

  3. Ether-Directed ortho-C–H Olefination with a PdII/MPAA Catalyst**

    Science.gov (United States)

    Li, Gang; Leow, Dasheng; Wan, Li; Yu, Jin-Quan

    2013-01-01

    Weak coordination is powerful! A PdII-catalyzed olefination of ortho-C–H bonds of arenes directed by weakly coordinating ethers is developed using mono-protected amino acid (MPAA) ligands. This finding provides a method for chemically modifying ethers, which are abundant in natural products and drug molecules. PMID:23239120

  4. Photolytic degradation of polybromodiphenyl ethers under UV-lamp and solar irradiations

    Energy Technology Data Exchange (ETDEWEB)

    Shih, Yang-hsin, E-mail: yhs@nchu.edu.tw [Department of Soil and Environmental Sciences, National Chung Hsing University, Taichung 402, Taiwan (China); Wang, Chun-Kang [Department of Soil and Environmental Sciences, National Chung Hsing University, Taichung 402, Taiwan (China)

    2009-06-15

    Polybromodiphenyl ethers (PBDEs) are widely used flame retardant additives and have been mainly used in polymers for many plastic and electronic products. PBDEs have been found to bioaccumulate in both aquatic and terrestrial ecosystems and even human bodies. The technical product with the highest use is decabrominated diphenyl ether (BDE-209). Therefore, we chose to examine the solar and UV-lamp degradation of BDE-209. A linear increase of the photodegradation rate constant for BDE-209 was observed with the solar light intensity. The degradation reactions follow the pseudo-first-order kinetics. The photodegradation of BDE-209 produced other less brominated diphenyl ethers under ultraviolet light exposure, suggesting that the photodegradation of BDE-209 is a sequential dehalogenation mechanism. BDE-209 underwent rapid reductive debromination in these photodecomposition experiments. The formation rate constants of three nonabromodiphenyl ethers increase with the order of BDE-206, BDE-207 and BDE-208, indicating debromination mainly occurred at para > meta > ortho positions. These findings of the process properties and reductive debromination mechanism of the photolytic degradation of PBDEs can facilitate the design of remediation processes and also aid in predicting their fate in the environment.

  5. Hydrolysis of strained bridgehead bicyclic vinyl ethers and sulfides

    International Nuclear Information System (INIS)

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

    1979-01-01

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

  6. Pentafluorophenylammonium triflate-CuCl2: A mild, efficient and ...

    Indian Academy of Sciences (India)

    aminobenzamide with aryl aldehydes in the presence of CuCl2 as co-catalyst in good to excellent yields under solvent-free conditions. The present ... silyl acetals with ketones and oxime ethers.28 However, to the best of our knowledge ... cooled to room temperature and then water was added. The precipitate was filtered off ...

  7. Microwave Assisted Solvent Free Synthesis of Azomethines from Aryl Aldehydes on Melamin Formaldehyde as Solid Support

    Directory of Open Access Journals (Sweden)

    Ramin Rezaei

    2011-01-01

    Full Text Available Various aryl aldehydes underwent prompt one pot conversion into the corresponding azomethines in high yields by reacting with hydroxylamine hydrochloride supported on melamine formaldehyde under microwave irradiation.

  8. [Visualisation methods for etheric formative forces].

    Science.gov (United States)

    Burkhard, B; Kittel, R

    2009-09-01

    Rudolf Steiner, the founder of anthroposophy, suggested the development of visualisation methods for "etheric formative forces". The essential methods, their "spiritual scientific" basis and indications are described and their claims critically tested. The methods are not validated, the key criteria for diagnostic tests (reproducibility, sensitivity, specifity) are not given.

  9. Biosynthesis of ether-phospholipids including plasmalogens, peroxisomes and human disease: new insights into an old problem

    NARCIS (Netherlands)

    Wanders, Ronald J. A.; Brites, Pedro

    2010-01-01

    Ether-phospholipids represent an important subclass of phospholipids in animal cell membranes characterized by the presence of an ether bond at the sn-I position and the enrichment of PUFAs at the sn-2 position. Of the different ether-phospholipids, plasmalogens are the most abundant form and their

  10. From gene to biorefinery: microbial β-etherases as promising biocatalysts for lignin valorization

    Directory of Open Access Journals (Sweden)

    Pere ePicart

    2015-09-01

    Full Text Available The set-up of biorefineries for the valorization of lignocellulosic biomass will be core in the future to reach sustainability targets. In this area, biomass-degrading enzymes are attracting significant research interest for their potential in the production of chemicals and biofuels from renewable feedstock. Gluthatione-dependent β-etherases are emerging enzymes for the biocatalytic depolymerization of lignin, a heterogeneous aromatic polymer abundant in Nature. They selectively catalyze the reductive cleavage of β-O-4 aryl-ether bonds which account for 45-60% of linkages present in lignin. Hence, application of β-etherases in lignin depolymerization would enable a specific lignin breakdown, selectively yielding (valuable low-molecular-mass aromatics. Albeit β-etherases have been biochemically known for decades, only very recently novel β-etherases have been identified and thoroughly characterized for lignin valorization, expanding the enzyme toolbox for efficient β-O-4 aryl-ether bond cleavage. Given their emerging importance and potential, this mini-review discusses recent developments in the field of β-etherase biocatalysis covering all aspects from enzyme identification to biocatalytic applications with real lignin samples.

  11. From gene to biorefinery: microbial β-etherases as promising biocatalysts for lignin valorization.

    Science.gov (United States)

    Picart, Pere; de María, Pablo Domínguez; Schallmey, Anett

    2015-01-01

    The set-up of biorefineries for the valorization of lignocellulosic biomass will be core in the future to reach sustainability targets. In this area, biomass-degrading enzymes are attracting significant research interest for their potential in the production of chemicals and biofuels from renewable feedstock. Glutathione-dependent β-etherases are emerging enzymes for the biocatalytic depolymerization of lignin, a heterogeneous aromatic polymer abundant in nature. They selectively catalyze the reductive cleavage of β-O-4 aryl-ether bonds which account for 45-60% of linkages present in lignin. Hence, application of β-etherases in lignin depolymerization would enable a specific lignin breakdown, selectively yielding (valuable) low-molecular-mass aromatics. Albeit β-etherases have been biochemically known for decades, only very recently novel β-etherases have been identified and thoroughly characterized for lignin valorization, expanding the enzyme toolbox for efficient β-O-4 aryl-ether bond cleavage. Given their emerging importance and potential, this mini-review discusses recent developments in the field of β-etherase biocatalysis covering all aspects from enzyme identification to biocatalytic applications with real lignin samples.

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

    NARCIS (Netherlands)

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

    1987-01-01

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

  13. Rhodium(III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes through C(sp²)-H/alkene functionalization.

    Science.gov (United States)

    Zhou, Ming-Bo; Pi, Rui; Hu, Ming; Yang, Yuan; Song, Ren-Jie; Xia, Yuanzhi; Li, Jin-Heng

    2014-10-13

    This study describes a new rhodium(III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes using a Cu(OAc)2 oxidant for building a spirocyclic ring system, which includes the functionalization of an aryl C(sp(2))-H bond and addition/protonolysis of an alkene C=C bond. This method is applicable to a wide range of 5-aryl-2,3-dihydro-1H-pyrroles and internal alkynes, and results in the assembly of the spiro[indene-1,2'-pyrrolidine] architectures in good yields with excellent regioselectivities. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Surface modified MXene Ti_3C_2 multilayers by aryl diazonium salts leading to large-scale delamination

    International Nuclear Information System (INIS)

    Wang, Hongbing; Zhang, Jianfeng; Wu, Yuping; Huang, Huajie; Li, Gaiye; Zhang, Xin; Wang, Zhuyin

    2016-01-01

    Highlights: • A novel and simple method to delaminate MXene Ti_3C_2 multilayers. • Surface modification using aryl diazonium salts induced swelling that conversely weakened the bonds between MXene layers. • The grafting of phenylsulfonic acid groups on MXene surfaces resulted in excellent water dispersibility. - Abstract: Herein we report a simple and facile method to delaminate MXene Ti_3C_2 multilayers by the assistance of surface modification using aryl diazonium salts. The basic strategy involved the preparation of layered MAX Ti_3AlC_2 and the exfoliation of Ti_3AlC_2 into Ti_3C_2 multilayers, followed by Na"+ intercalation and surface modification using sulfanilic acid diazonium salts. The resulting chemically grafted Ti_3C_2 flakes were characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. Ultraviolet-visible spectroscopy revealed that surface-modified MXene Ti_3C_2 sheets disperse well in water and the solutions obey Lambert–Beer’s law. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to demonstrate the morphology and structure of delaminating MXene Ti_3C_2 flakes. The results indicated that chemical modification for MXene multilayers by aryl diazonium salts induced swelling that conversely weakened the bonds between MX layers, hence leading to large-scale delamination of multilayered MXene Ti_3C_2via mild sonication. Advantages of the present approach rely not only on the simplicity and efficiency of the delamination procedure but also on the grafting of aryl groups to MXene surfaces, highly suitable for further applications of the newly discovered two-dimensional materials.

  15. A novel dihydropyridine with 3-aryl meta-hydroxyl substitution blocks L-type calcium channels in rat cardiomyocytes

    International Nuclear Information System (INIS)

    Galvis-Pareja, David; Zapata-Torres, Gerald; Hidalgo, Jorge; Ayala, Pedro

    2014-01-01

    Rationale: Dihydropyridines are widely used for the treatment of several cardiac diseases due to their blocking activity on L-type Ca 2+ channels and their renowned antioxidant properties. Methods: We synthesized six novel dihydropyridine molecules and performed docking studies on the binding site of the L-type Ca 2+ channel. We used biochemical techniques on isolated adult rat cardiomyocytes to assess the efficacy of these molecules on their Ca 2+ channel-blocking activity and antioxidant properties. The Ca 2+ channel-blocking activity was evaluated by confocal microscopy on fluo-3AM loaded cardiomyocytes, as well as using patch clamp experiments. Antioxidant properties were evaluated by flow cytometry using the ROS sensitive dye 1,2,3 DHR. Results: Our docking studies show that a novel compound with 3-OH substitution inserts into the active binding site of the L-type Ca 2+ channel previously described for nitrendipine. In biochemical assays, the novel meta-OH group in the aryl in C4 showed a high blocking effect on L-type Ca 2+ channel as opposed to para-substituted compounds. In the tests we performed, none of the molecules showed antioxidant properties. Conclusions: Only substitutions in C2, C3 and C5 of the aryl ring render dihydropyridine compounds with the capacity of blocking LTCC. Based on our docking studies, we postulate that the antioxidant activity requires a larger group than the meta-OH substitution in C2, C3 or C5 of the dihydropyridine ring. - Highlights: • Dihydropyridine (DHP) molecules are widely used in cardiovascular disease. • DHPs block Ca 2+ entry through LTCC—some DHPs have antioxidant activity as well. • We synthesized 6 new DHPs and tested their Ca 2+ blocking and antioxidant activities. • 3-Aryl meta-hydroxyl substitution strongly increases their Ca 2+ blocking activity. • 3-Aryl meta-hydroxyl substitution did not affect the antioxidant properties

  16. The surface modifications of multi-walled carbon nanotubes for multi-walled carbon nanotube/poly(ether ether ketone) composites

    International Nuclear Information System (INIS)

    Cao, Zongshuang; Qiu, Li; Yang, Yongzhen; Chen, Yongkang; Liu, Xuguang

    2015-01-01

    Graphical abstract: Multi-walled carbon nanotube/poly(ether ether ketone) (MWCNT/PEEK) composites incorporating surface modified multi-walled carbon nanotubes (MWCNTs) as fillers were fabricated in a solution blending method in order to explore the dynamic mechanical and tribological properties of MWCNT/PEEK composites systematically. It is evident that surface modifications of MWCNTs have a significant impact on dispersibility of MWCNTs in PEEK, dynamic mechanical and tribological properties of MWCNT/PEEK composites. Typically, a clear effect of surface modifications of MWCNTs on tribological properties of MWCNT/PEEK composites was observed. A significant reduction in frictional coefficient of MWCNT/PEEK composites with the MWCNTs modified with ethanolamine has been achieved and the self-lubricating film on their worn surfaces was also observed. - Highlights: • The dispersibility of surface modified MWCNTs in PEEK has been studied. • MWCNTs modified with ethanolamine have showed a good dispersion in PEEK. • Surface modifications of MWCNTs have a significant impact on both dynamic mechanical and tribological properties of MWCNT/PEEK composites. - Abstract: The effects of surface modifications of multi-walled carbon nanotubes (MWCNTs) on the morphology, dynamic mechanical and tribological properties of multi-walled carbon nanotube/poly(ether ether ketone) (MWCNT/PEEK) composites have been investigated. MWCNTs were treated with mixed acids to obtain acid-functionalized MWCNTs. Then the acid-functionalized MWCNTs were modified with ethanolamine (named e-MWCNTs). The MWCNT/PEEK composites were prepared by a solution-blending method. A more homogeneous distribution of e-MWCNTs within the composites was found with scanning electron microscopy. Dynamic mechanical analysis demonstrated a clear increase in the storage modulus of e-MWCNT/PEEK composites because of the improved interfacial adhesion strength between e-MWCNTs and PEEK. Furthermore, the presence of e

  17. The surface modifications of multi-walled carbon nanotubes for multi-walled carbon nanotube/poly(ether ether ketone) composites

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Zongshuang [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); Research Center of Advanced Material Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Qiu, Li [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Yang, Yongzhen, E-mail: yyztyut@126.com [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); Research Center of Advanced Material Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Chen, Yongkang, E-mail: y.k.chen@herts.ac.uk [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); University of Hertfordshire, School of Engineering and Technology, Hatfield, Hertfordshire AL10 9AB (United Kingdom); Liu, Xuguang [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China)

    2015-10-30

    Graphical abstract: Multi-walled carbon nanotube/poly(ether ether ketone) (MWCNT/PEEK) composites incorporating surface modified multi-walled carbon nanotubes (MWCNTs) as fillers were fabricated in a solution blending method in order to explore the dynamic mechanical and tribological properties of MWCNT/PEEK composites systematically. It is evident that surface modifications of MWCNTs have a significant impact on dispersibility of MWCNTs in PEEK, dynamic mechanical and tribological properties of MWCNT/PEEK composites. Typically, a clear effect of surface modifications of MWCNTs on tribological properties of MWCNT/PEEK composites was observed. A significant reduction in frictional coefficient of MWCNT/PEEK composites with the MWCNTs modified with ethanolamine has been achieved and the self-lubricating film on their worn surfaces was also observed. - Highlights: • The dispersibility of surface modified MWCNTs in PEEK has been studied. • MWCNTs modified with ethanolamine have showed a good dispersion in PEEK. • Surface modifications of MWCNTs have a significant impact on both dynamic mechanical and tribological properties of MWCNT/PEEK composites. - Abstract: The effects of surface modifications of multi-walled carbon nanotubes (MWCNTs) on the morphology, dynamic mechanical and tribological properties of multi-walled carbon nanotube/poly(ether ether ketone) (MWCNT/PEEK) composites have been investigated. MWCNTs were treated with mixed acids to obtain acid-functionalized MWCNTs. Then the acid-functionalized MWCNTs were modified with ethanolamine (named e-MWCNTs). The MWCNT/PEEK composites were prepared by a solution-blending method. A more homogeneous distribution of e-MWCNTs within the composites was found with scanning electron microscopy. Dynamic mechanical analysis demonstrated a clear increase in the storage modulus of e-MWCNT/PEEK composites because of the improved interfacial adhesion strength between e-MWCNTs and PEEK. Furthermore, the presence of e

  18. Influence of some anti-inflammatory drugs on the activity of aryl hydrocarbon hydroxylase and the cytochrome P450 content

    Energy Technology Data Exchange (ETDEWEB)

    Mostafa, M.H.; Sheweita, S.A.; Abdel-Moneam, N.M. (Alexandria Univ. (Egypt))

    1990-06-01

    The metabolism of benzo({alpha})pyrene is mediated by the mixed function oxidase system including the cytochrome P450-dependent aryl hydrocarbon hydroxylase. The data of the present study revealed the ability of various commonly used anti-inflammatory drugs to alter the activity of this enzyme system, where all the tested drugs, namely phenyl butazone, ketoprofen, piroxicam, and acetaminophen, caused an increase in both the activity of aryl hydrocarbon hydroxylase and the cytochrome P450 content whether administered as a single dose or as a repeated dose for 6 consecutive days. The percentage of change for all drugs except phenyl butazone was proportional to the duration of drug administration. On the other hand, pyrazole which is chemically related to phenyl butazone, had no significant effect when administered as a single dose but caused a decrease in both studied parameters when administered as a repeated dose for 6 consecutive days. The mechanisms by which these commonly used drugs modify the aryl hydrocarbon hydroxylase activity and the cytochrome p450 content are discussed in the text.

  19. Glycerol tertiary butyl ethers via etherification of glycerol with isobutene

    Energy Technology Data Exchange (ETDEWEB)

    Behr, A. [Dortmund Univ. (Germany). Chair of Chemical Process Development/Technical Chemistry A

    2007-07-01

    Glycerol and isobutene can react to a mixture of glycerol tertiary butyl ethers (GTBE) which can be used as additives for gasoline, diesel or biodiesel. This reaction was investigated in lab scale yielding a proposal for a process flow diagram containing reaction, extraction, flash and rectification units. This process has the advantages that only the suitable higher ethers are formed and that both glycerol and isobutene are fully converted. The homogeneous acid catalyst is low-priced and can be completely recycled. (orig.)

  20. Biofilm behavior on sulfonated poly(ether-ether-ketone) (sPEEK)

    Energy Technology Data Exchange (ETDEWEB)

    Montero, Juan F.D. [Center for Research on Dental Implants (CEPID), School of Dentistry (ODT), Federal University of Santa Catarina - UFSC, Florianópolis, SC 88040-900 (Brazil); Tajiri, Henrique A.; Barra, Guilherme M.O.; Fredel, Márcio C. [Department of Mechanical Engineering (EMC), Federal University of Santa Catarina (UFSC), Florianópolis, SC 88040-900 (Brazil); Benfatti, Cesar A.M.; Magini, Ricardo S. [Center for Research on Dental Implants (CEPID), School of Dentistry (ODT), Federal University of Santa Catarina - UFSC, Florianópolis, SC 88040-900 (Brazil); Pimenta, Andréa L. [Integrated Laboratories Technologies (InteLAB), Dept. Chemical Engineering (EQA), Federal University of Santa Catarina - UFSC, Florianópolis, SC 88040-970 (Brazil); Department of Biologie, Université de Cergy Pontoise, 2, Av. Adolphe Chauvin, 95302 Cergy Pontoise (France); Souza, Júlio C.M., E-mail: julio.c.m.souza@ufsc.br [Center for Research on Dental Implants (CEPID), School of Dentistry (ODT), Federal University of Santa Catarina - UFSC, Florianópolis, SC 88040-900 (Brazil); Center for Microelectromechanical Systems (CMEMS), Dept. Mechanical Engineering (DEM), Campus Azurém, 4800-058 Guimarães (Portugal)

    2017-01-01

    Poly(ether-ether-ketone) (PEEK) has also shown to be very attractive for incorporating therapeutic compounds thanks to a sulfonation process which modifies the material structure resulting in a sulfonated-PEEK (sPEEK). Concerning biomedical applications, the objective of this work was to evaluate the influence of different sulfonation degree of sPEEK on the biofilm growth. PEEK samples were functionalized by using sulphuric acid (98%) and then dissolved into dimethyl-sulfoxide. A dip coating technique was used to synthesize sPEEK thin films. The sulfonation degree of the materials was analyzed by FT-IR, H NMR, TG and IEC. The surfaces were characterized by scanning electron microscopy, profilometry and contact angle analyses. Subsequently, the biofilm formation on sulfonated-PEEK based on Streptococcus mutans and Enterococcus faecalis was measured by spectrophotometry, colony forming units (CFU mL{sup −1}) and SEM. Results obtained from thermal and chemical analyses showed an intensification in sulfonation degree for sPEEK at 2 and 2.5 h. The E. faecalis or S. mutans biofilm growth revealed statistically significant differences (p < 0.05) between 2 and 3 h sulfonation groups. A significant decrease (p < 0.05) in CFU mL{sup −1} was recorded for S. mutans or E. faecalis biofilm grown on 2.5 or 3 h sPEEK. Regarding the thermal-chemical and microbiologic analyses, the sulfonation degree of sPEEK ranging from 2 up to 3 h was successful capable to decrease the biofilm growth. That revealed an alternative strategy to embed anti-biofilm and therapeutic compounds into PEEK avoiding infections in biomedical applications. - Highlights: • PEEK can be dissolved to incorporate therapeutic compounds. • High sulfonation degree on sPEEK affected the biofilm growth. • The sulfonation degree must be controlled to maintain the properties of sPEEK.

  1. Biofilm behavior on sulfonated poly(ether-ether-ketone) (sPEEK)

    International Nuclear Information System (INIS)

    Montero, Juan F.D.; Tajiri, Henrique A.; Barra, Guilherme M.O.; Fredel, Márcio C.; Benfatti, Cesar A.M.; Magini, Ricardo S.; Pimenta, Andréa L.; Souza, Júlio C.M.

    2017-01-01

    Poly(ether-ether-ketone) (PEEK) has also shown to be very attractive for incorporating therapeutic compounds thanks to a sulfonation process which modifies the material structure resulting in a sulfonated-PEEK (sPEEK). Concerning biomedical applications, the objective of this work was to evaluate the influence of different sulfonation degree of sPEEK on the biofilm growth. PEEK samples were functionalized by using sulphuric acid (98%) and then dissolved into dimethyl-sulfoxide. A dip coating technique was used to synthesize sPEEK thin films. The sulfonation degree of the materials was analyzed by FT-IR, H NMR, TG and IEC. The surfaces were characterized by scanning electron microscopy, profilometry and contact angle analyses. Subsequently, the biofilm formation on sulfonated-PEEK based on Streptococcus mutans and Enterococcus faecalis was measured by spectrophotometry, colony forming units (CFU mL −1 ) and SEM. Results obtained from thermal and chemical analyses showed an intensification in sulfonation degree for sPEEK at 2 and 2.5 h. The E. faecalis or S. mutans biofilm growth revealed statistically significant differences (p < 0.05) between 2 and 3 h sulfonation groups. A significant decrease (p < 0.05) in CFU mL −1 was recorded for S. mutans or E. faecalis biofilm grown on 2.5 or 3 h sPEEK. Regarding the thermal-chemical and microbiologic analyses, the sulfonation degree of sPEEK ranging from 2 up to 3 h was successful capable to decrease the biofilm growth. That revealed an alternative strategy to embed anti-biofilm and therapeutic compounds into PEEK avoiding infections in biomedical applications. - Highlights: • PEEK can be dissolved to incorporate therapeutic compounds. • High sulfonation degree on sPEEK affected the biofilm growth. • The sulfonation degree must be controlled to maintain the properties of sPEEK.

  2. Radium separation through complexation by aqueous crown ethers and ion exchange or solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Chiarizia, R.; Dietz, M.L.; Horwitz, E.P. [Argonne National Lab., IL (United States). Chemistry Div.; Burnett, W.C. [Florida State Univ., Tallahassee, FL (United States). Dept. of Oceanography

    1997-11-01

    The effect of three water-soluble, unsubstituted crown ethers (15-crown-5 (15C5), 18-crown-6 (18C6) and 21-crown-7 (21C7)) on the uptake of Ca, Sr, Ba and Ra cations by a sulfonic acid cation exchange resin, and on the extraction of the same cations by xylene solutions of dinonylnaphthalenesulfonic acid (HDNNS) from aqueous hydrochloric acid solutions has been investigated. The crown ethers enhance the sorption of the larger cations by the ion exchange resin, thereby improving the resin selectivity over calcium, a result of a synergistic interaction between the crown ether and the ionic functional groups of the resin. Similarly, the extraction of the larger alkaline earth cations into xylene by HDNNS is strongly synergized by the presence of the crown ethers in the aqueous phase. Promising results for intra-Group IIa cation separations have been obtained using each of the three crown ethers as the aqueous ligands and the sulfonic acid cation exchange resin. Even greater separation factors for the radium-calcium couple have been measured with the crown-ethers and HDNNS solutions in the solvent extraction mode. The application of the uptake and extraction results to the development of radium separation schemes is discussed and a possible flowchart for the determination of {sup 226}Ra/{sup 228}Ra in natural waters is presented.

  3. Binding of the 9-O-N-aryl/arylalkyl amino carbonyl methyl substituted berberine analogs to tRNA(phe..

    Directory of Open Access Journals (Sweden)

    Anirban Basu

    Full Text Available BACKGROUND: Three new analogs of berberine with aryl/ arylalkyl amino carbonyl methyl substituent at the 9-position of the isoquinoline chromophore along with berberrubine were studied for their binding to tRNA(phe by wide variety of biophysical techniques like spectrophotometry, spectrofluorimetry, circular dichroism, thermal melting, viscosity and isothermal titration calorimetry. METHODOLOGY/ PRINCIPAL FINDINGS: Scatchard binding isotherms revealed that the cooperative binding mode of berberine was propagated in the analogs also. Thermal melting studies showed that all the 9-O-N-aryl/arylalkyl amino carbonyl methyl substituted berberine analogs stabilized the tRNA(phe more in comparison to berberine. Circular dichroism studies showed that these analogs perturbed the structure of tRNA(phe more in comparison to berberine. Ferrocyanide quenching studies and viscosity results proved the intercalative binding mode of these analogs into the helical organization of tRNA(phe. The binding was entropy driven for the analogs in sharp contrast to the enthalpy driven binding of berberine. The introduction of the aryl/arylalkyl amino carbonyl methyl substituent at the 9-position thus switched the enthalpy driven binding of berberine to entropy dominated binding. Salt and temperature dependent calorimetric studies established the involvement of multiple weak noncovalent interactions in the binding process. CONCLUSIONS/ SIGNIFICANCE: The results showed that 9-O-N-aryl/arylalkyl amino carbonyl methyl substituted berberine analogs exhibited almost ten folds higher binding affinity to tRNA(phe compared to berberine whereas the binding of berberrubine was dramatically reduced by about twenty fold in comparison to berberine. The spacer length of the substitution at the 9-position of the isoquinoline chromophore appears to be critical in modulating the binding affinities towards tRNA(phe.

  4. Rhodium-catalyzed triarylphosphine synthesis via cross-coupling of aryl iodides and acylphosphines

    Directory of Open Access Journals (Sweden)

    Jiefang Yang

    2018-01-01

    Full Text Available Rhodium(I-catalyzed C–P cross-coupling reaction with aryl iodides and acylphosphines was disclosed for a straight forward synthesis of triarylphosphines. The acylphosphines were successfully employed as both the phosphorus source and the ligand to the Rh(I catalyst. The triarylphosphines could be afforded in a yield up to 98% with good toleration of wide functional groups.

  5. [Ether Day--no laughing matter. The birth of modern anaesthesia].

    Science.gov (United States)

    Goerig, Michael; Wulf, Hinnerk

    2013-10-01

    Since centuries the first public demonstration of the anaesthetic properties of ether by William Thomas Green Morton at the Massachusetts General Hospital in Boston on October 16th 1846 is celebrated as "Ether Day" world-wide. The news of the beneficial effects, primarily disposed as a "Yankee Invention", spread over all continents quickly. This was the result of an article, published in the Boston Medical and Surgical Journal on November 18th, 1846. It is mentioning worth that this article was written when Morton had disclosed that the used "preparation", later named as "Nostrum" or "Letheon", was sulphuric ether. The important discovery later became a patent case and was overshadowed by a long lasting priority claim. Nevertheless the readers of the New England Journal of Medicine voted in a survey that this article was the most important publication in the 200 years journals history ever. © Georg Thieme Verlag Stuttgart · New York.

  6. Towards a fragment-based approach in gelator design: halogen effects leading to thixotropic, mouldable and self-healing systems in aryl-triazolyl amino acid-based gelators!

    Science.gov (United States)

    Srivastava, Bhartendu K; Manheri, Muraleedharan K

    2017-04-18

    A simple replacement of a H atom by Br transformed non-gelating aryl triazolyl amino acid benzyl ester into a versatile gelator, which formed shape-persistent, self-healing and mouldable gels. The 'bromo-aryl benzyl ester' fragment was then transplanted into another framework, which resulted in similar solvent preference and gelation efficiency.

  7. Designing of molecular architecture, synthesis and properties of the next generation of state-of-the-art high-performance thermoplastic fluoro-poly(ether amide)s, (6F-PEA), fluoro-poly(ether amide-imide)s (6F-PEAI), and their co-polymers

    International Nuclear Information System (INIS)

    Vora, Rohitkumar H.

    2010-01-01

    Graphical abstract: Molecular architectures of next generation of high-performance advanced heat stable thermoplastic polymer compositions of fluoro-poly(ether amide) (6F-PA) and fluoro-poly(ether amide-imide) (6F-PEAI) having di-ether diamines moieties were designed based on fluoro-polyimide (6F-PI) chemistry, and polymers were synthesized using two novel state-of-the-art 2-(3,4'-carboxy anhydrophenyl-2(4-carboxyphenyl) hexafluoropropane (6FTMA) and 2,2'-bis(4-carboxyphenyl) hexafluropropane (6F-DAc) monomers. Their copolymers: fluoro-copoly(ether amide-(ether imide))s (6F-co(PEA-PEI)), fluoro-copoly(ether amide-(ether amide-imide))s (6F-co(PEA-PEAI)) and fluoro-copoly(ether amide-imide-(ether imide))s (6F-co(PEAI-PEI)) were also designed and synthesized using 2,2'-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydrides (6FDA) for the advanced aerospace, defense and industrial engineering applications. -- Abstract: A new generation of high-performance polymers for the advanced industrial, aerospace and defense engineering applications are being investigated in the academic and industrial research institutions throughout the world. Fluoro-polyimides (6F-PI) are one such sub-class of high-performance polyimide polymers. In the last 25 years a number of fluoro-polyimides have been reported but only a handful of them have been commercialized. This paper describes the 6F-polyimide chemistry-based designed molecular architectures and synthesis of two series of next generation of heat stable thermoplastic polymer compositions having di-ether diamines moieties, such as fluoro-poly(ether amide) (6F-PA) and fluoro-poly(ether amide-imide) (6F-PEAI) using the novel state-of-the-art 2-(3,4'-carboxy anhydrophenyl-2(4-carboxyphenyl) hexafluoropropane (6F-TMA) and 2,2'-bis(4-carboxyphenyl) hexafluoropropane (6F-DAc) monomers. Their co-polymers: fluoro-copoly(ether amide-(ether imide))s (6F-co(PEA-PEI)), fluoro-copoly(ether amide-(ether amide-imide))s (6F-co(PEA-PEAI)) and fluoro-copoly(ether

  8. Mechanistic evidence for a ring-opening pathway in the Pd-catalyzed direct arylation of benzoxazoles

    DEFF Research Database (Denmark)

    Sanchez, R.S.; Zhuravlev, Fedor

    2007-01-01

    The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent with the r......The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent...... with the rate-limiting electrophilic or concerted palladation. A mechanism, proposed on the basis of kinetic and computational studies, includes generation of isocyanophenolate as the key step. The DFT calculations suggest that the overall catalytic cycle is facile and is largely controlled by the C-H acidity...

  9. Deciphering the Origin, Evolution, and Physiological Function of the Subtelomeric Aryl-Alcohol Dehydrogenase Gene Family in the Yeast Saccharomyces cerevisiae.

    Science.gov (United States)

    Yang, Dong-Dong; de Billerbeck, Gustavo M; Zhang, Jin-Jing; Rosenzweig, Frank; Francois, Jean-Marie

    2018-01-01

    Homology searches indicate that Saccharomyces cerevisiae strain BY4741 contains seven redundant genes that encode putative aryl-alcohol dehydrogenases (AAD). Yeast AAD genes are located in subtelomeric regions of different chromosomes, and their functional role(s) remain enigmatic. Here, we show that two of these genes, AAD4 and AAD14 , encode functional enzymes that reduce aliphatic and aryl-aldehydes concomitant with the oxidation of cofactor NADPH, and that Aad4p and Aad14p exhibit different substrate preference patterns. Other yeast AAD genes are undergoing pseudogenization. The 5' sequence of AAD15 has been deleted from the genome. Repair of an AAD3 missense mutation at the catalytically essential Tyr 73 residue did not result in a functional enzyme. However, ancestral-state reconstruction by fusing Aad6 with Aad16 and by N-terminal repair of Aad10 restores NADPH-dependent aryl-alcohol dehydrogenase activities. Phylogenetic analysis indicates that AAD genes are narrowly distributed in wood-saprophyte fungi and in yeast that occupy lignocellulosic niches. Because yeast AAD genes exhibit activity on veratraldehyde, cinnamaldehyde, and vanillin, they could serve to detoxify aryl-aldehydes released during lignin degradation. However, none of these compounds induce yeast AAD gene expression, and Aad activities do not relieve aryl-aldehyde growth inhibition. Our data suggest an ancestral role for AAD genes in lignin degradation that is degenerating as a result of yeast's domestication and use in brewing, baking, and other industrial applications. IMPORTANCE Functional characterization of hypothetical genes remains one of the chief tasks of the postgenomic era. Although the first Saccharomyces cerevisiae genome sequence was published over 20 years ago, 22% of its estimated 6,603 open reading frames (ORFs) remain unverified. One outstanding example of this category of genes is the enigmatic seven-member AAD family. Here, we demonstrate that proteins encoded by two

  10. Modeling of a Reaction-Distillation-Recycle System to Produce Dimethyl Ether through Methanol Dehydration

    Science.gov (United States)

    Muharam, Y.; Zulkarnain, L. M.; Wirya, A. S.

    2018-03-01

    The increase in the dimethyl ether yield through methanol dehydration due to a recycle integration to a reaction-distillation system was studied in this research. A one-dimensional phenomenological model of a methanol dehydration reactor and a shortcut model of distillation columns were used to achieve the aim. Simulation results show that 10.7 moles/s of dimethyl ether is produced in a reaction-distillation system with the reactor length being 4 m, the reactor inlet pressure being 18 atm, the reactor inlet temperature being 533 K, the reactor inlet velocity being 0.408 m/s, and the distillation pressure being 8 atm. The methanol conversion is 90% and the dimethyl ether yield is 48%. The integration of the recycle stream to the system increases the dimethyl ether yield by 8%.

  11. Stepwise radical cation Diels-Alder reaction via multiple pathways.

    Science.gov (United States)

    Shimizu, Ryo; Okada, Yohei; Chiba, Kazuhiro

    2018-01-01

    Herein we disclose the radical cation Diels-Alder reaction of aryl vinyl ethers by electrocatalysis, which is triggered by an oxidative SET process. The reaction clearly proceeds in a stepwise fashion, which is a rare mechanism in this class. We also found that two distinctive pathways, including "direct" and "indirect", are possible to construct the Diels-Alder adduct.

  12. Ionic core–shell dendrimers with a polycationic core: structural aspects and host–guest binding properties

    NARCIS (Netherlands)

    van de Coevering, R.; Bruijnincx, P.C.A.; Lutz, M.; Spek, A.L.; van Koten, G.; Klein Gebbink, R.J.M.

    2007-01-01

    The structural aspects and host–guest binding properties of ionic core–shell dendrimers [1]Br8 and [2]Br4, which bear a polycationic core and a neutral shell of Fréchet-type poly(benzyl aryl ether) dendrons, have been investigated by means of dendritic wedges [3]Br2 and [4]Br, that resemble one of

  13. New ' Bucky- ligands'. Potentially Monoanionic Terdentate Diamino Aryl Pincer Ligands Anchored to C60

    NARCIS (Netherlands)

    Koten, G. van; Meijer, M.D.; Gossage, R.A.; Jastrzebski, J.T.B.H.

    1998-01-01

    Two new methanofullerenes have been prepared by the reaction of C{6}{0} with diazo substituted, potentially monoanionic, terdentate diamino aryl ligands, yielding a mixture of the open valence [5, 6]- and closed valence [6,6]-isomers. Single isomers of the pure [6,6]-methanofullerenes were obtained

  14. 40 CFR 721.6980 - Dimer acids, polymer with polyalkylene glycol, bisphenol A-diglycidyl ether, and alky-lenepolyols...

    Science.gov (United States)

    2010-07-01

    ... reporting. (1) The chemical substance dimer acids, polymer with polyalkylene glycol, bisphenol A-diglycidyl... glycol, bisphenol A-diglycidyl ether, and alky-lenepolyols polyglycidyl ethers (generic name). 721.6980... Substances § 721.6980 Dimer acids, polymer with polyalkylene glycol, bisphenol A-diglycidyl ether, and alky...

  15. Assessment of ether and alcohol fuels from coal. Volume 2. Technical report

    Energy Technology Data Exchange (ETDEWEB)

    1983-03-01

    A unique route for the indirect liquefaction of coal to produce transportation fuel has been evaluated. The resultant fuel includes alkyl tertiary alkyl ethers and higher alcohols, all in the gasoline boiling range. When blended into gasoline, the ether fuel provides several advantages over the lower alcohols: (1) lower chemical oxygen content, (2) less-severe water-separation problems, and (3) reduced front-end volatility effects. The ether fuel also has high-octane quality. Further, it can be utilized as a gasoline substitute in all proportions. Production of ether fuel combines several steps, all of which are or have been practiced on an industrial scale: (1) coal gasification, (2) gas cleanup and shift to desired H/sub 2/:CO ratio, (3) conversion of synthesis gas to isobutanol, methanol, and higher alcohols, (4) separation of alcohols, (5) chemical dehydration of isobutanol to isobutylene, and (6) etherification of isobutylene with methanol. A pilot-plant investigation of the isobutanol synthesis step was performed. Estimates of ether-fuel manufacturing costs indicate this process route is significantly more costly than synthesis of methanol. However, the fuel performance features provide incentive for developing the necessary process and catalyst improvements. Co-production of higher-molecular-weight co-solvent alcohols represents a less-drastic form of methanol modification to achieve improvement in the performance of methanol-gasoline blends. Costs were estimated for producing several proportions of methanol plus higher alcohols from coal. Estimated fuel selling price increases regularly but modestly with higher alcohol content.

  16. SYNTHESIS OF ALLYL PHENYL ETHER AND CLAISEN REARRANGEMENT

    Directory of Open Access Journals (Sweden)

    Gagik Torosyan

    2011-12-01

    Full Text Available It has been established the possibility for phenol allylation on natural zeolites and them analogs. Here is demonstrated the synthesis of allyl phenol, which has wide industrial applications. The offered method in comparison with the traditional methods has more advantages – higher selectivity, smaller material and power resources consumption. It has been obtained the mixture of allylating phenols (30% in general with allyl phenyl ether (1 with 80% yields. At 600 K is obtained allylphenyl ether, at 700 K beginning the formation of allyl phenols, which is the result of direct C-allylation of the aromatic ring. It has been investigated the possibility of Claisen rearrangement in the same conditions. All of that are established by gas-liquid chromatography and liquid chromatography data.

  17. Ether in Kant and akasa in Prasastapada: Philosophy in comparative perspective

    Directory of Open Access Journals (Sweden)

    Fernando Tola

    2015-02-01

    Full Text Available The study of Indian and Western systems of Philosophy reveals many points of thematic and methodological coincidences between them. We have collected a good number of these coincidences in our recent books, where we have included many philosophical texts in Sanskrit and in European languages which contain the expression of astonishing similar ideas and theses. In the present article we add a new instance of coincidence between Indian and Western thought in relation to akasa in India (limited to the Indian philosophical system Vaisesika and ether (Aether or Äther in German in the Opus postumum of Kant. The inexistence of both akasa and ether has been established by Modern Science. Akasa and ether in India and the West, respectively, constitute a notorious example of asrayasiddha, the well-known logical defect considered by Indian Logic.

  18. Electrodeposited Organic Layers Formed from Aryl Diazonium Salts for Inhibition of Copper Corrosion

    Directory of Open Access Journals (Sweden)

    Ana Chira

    2017-02-01

    Full Text Available Copper substrates deposed on a gold screen-printed electrode were covered with different aryl diazonium salts by electrodeposition at 0.25 mA for 30 or 300 s. Seven compounds were investigated: 4-aminophenylacetic acid, 4-aminophenethyl alcohol, 4-fluoroaniline, 4-(heptadecafluorooctylaniline, 4-aminoantipyrine, 4-(4-aminophenylbutyric acid and 3,4,5-trimethoxyaniline. Quantitative monitoring of the electrodeposition process was carried out by electrogravimetry using quartz crystal microbalance (QCM. The electrodeposited mass varies between 26 ng/cm2 for 4-fluoroaniline formed during 30 s to 442 ng/cm2 for 4-phenylbutyric acid formed during 300 s. The corrosion inhibition properties of aryl-modified layers have been studied in buffer citrate with pH = 3 or 3.5% NaCl solutions using electrochemical noise (ECN and Tafel potentiodynamic polarization measurements. A corrosion inhibiting efficiency up to 90% was found. The highest corrosion inhibition was obtained for 4-(4-aminophenylbutyric acid and the lowest for 4-fluoroaniline. A relation between the inhibition efficiency and the chemical nature of the substituents in the protective layer was found.

  19. Electrodeposited Organic Layers Formed from Aryl Diazonium Salts for Inhibition of Copper Corrosion.

    Science.gov (United States)

    Chira, Ana; Bucur, Bogdan; Radu, Gabriel-Lucian

    2017-02-28

    Copper substrates deposed on a gold screen-printed electrode were covered with different aryl diazonium salts by electrodeposition at 0.25 mA for 30 or 300 s. Seven compounds were investigated: 4-aminophenylacetic acid, 4-aminophenethyl alcohol, 4-fluoroaniline, 4-(heptadecafluorooctyl)aniline, 4-aminoantipyrine, 4-(4-aminophenyl)butyric acid and 3,4,5-trimethoxyaniline. Quantitative monitoring of the electrodeposition process was carried out by electrogravimetry using quartz crystal microbalance (QCM). The electrodeposited mass varies between 26 ng/cm² for 4-fluoroaniline formed during 30 s to 442 ng/cm² for 4-phenylbutyric acid formed during 300 s. The corrosion inhibition properties of aryl-modified layers have been studied in buffer citrate with pH = 3 or 3.5% NaCl solutions using electrochemical noise (ECN) and Tafel potentiodynamic polarization measurements. A corrosion inhibiting efficiency up to 90% was found. The highest corrosion inhibition was obtained for 4-(4-aminophenyl)butyric acid and the lowest for 4-fluoroaniline. A relation between the inhibition efficiency and the chemical nature of the substituents in the protective layer was found.

  20. Selective crystallization of cations with crown ethers; Selektive Kristallisation von Kationen mit Kronenethern

    Energy Technology Data Exchange (ETDEWEB)

    Heffels, Dennis Egidius

    2014-07-04

    The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The