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Sample records for aryl bromides bearing

  1. Palladium-catalyzed direct α-arylation of methyl sulfones with aryl bromides.

    PubMed

    Zheng, Bing; Jia, Tiezheng; Walsh, Patrick J

    2013-04-01

    A direct and efficient approach for palladium-catalyzed arylation of aryl and alkyl methyl sulfones with aryl bromides has been developed. The catalytic system affords arylated sulfones in good to excellent yields (73-90%). PMID:23517309

  2. Palladium-Catalyzed α-Arylation of Aryl Acetic Acid Derivatives via Dienolate Intermediates with Aryl Chlorides and Bromides

    PubMed Central

    2016-01-01

    To date, examples of α-arylation of carboxylic acids remain scarce. Using a deprotonative cross-coupling process (DCCP), a method for palladium-catalyzed γ-arylation of aryl acetic acids with aryl halides has been developed. This protocol is applicable to a wide range of aryl bromides and chlorides. A procedure for the palladium-catalyzed α-arylation of styryl acetic acids is also described. PMID:25582024

  3. Aryl bromides as inexpensive starting materials in the catalytic enantioselective arylation of aryl aldehydes: the additive TMEDA enhances the enantioselectivity.

    PubMed

    Yang, Yong-Xin; Liu, Yue; Zhang, Lei; Jia, Yan-E; Wang, Pei; Zhuo, Fang-Fang; An, Xian-Tao; Da, Chao-Shan

    2014-11-01

    We used aryl bromides as inexpensive starting materials to enantioselectively arylate aldehydes in one pot. Aryl bromides readily transfer aryls to aryllithiums with n-butyllithium, successively to triarylaluminums with aluminum chloride, and then to aryltitaniums with titanium isopropoxide. Finally aryltitaniums arylate aldehydes catalyzed by (S)-H8-BINOL-Ti(Oi-Pr)2 in excellent yields and enantioselectivities. The additive TMEDA evidently suppresses the racemic background reaction promoted by LiCl generated from salt metathesis. This procedure represents a cost-effective and operationally convenient method for enantioenriched diarylmethanols. PMID:25279967

  4. Versatile Route to Arylated Fluoroalkyl Bromide Building Blocks.

    PubMed

    Kaplan, Peter T; Vicic, David A

    2016-02-19

    New difunctionalized and fluoroalkylated silyl reagents have been prepared that react with silver and copper salts to afford active catalysts that can be used to synthesize arylated fluoroalkyl bromide building blocks. It has been shown that the [(phen)Ag(CF2)nBr] intermediates are capable of transferring both the phenanthroline ligand and the fluoroalkyl bromide chain to copper iodide, eliminating the need for a preligated copper salt precursor. The methodology is compatible with various chain lengths of the fluoroalkyl halide functionality. PMID:26820388

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

    NASA Astrophysics Data System (ADS)

    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

  6. Multimetallic Catalysis Enabled Cross-Coupling of Aryl Bromides with Aryl Triflates

    PubMed Central

    Ackerman, Laura K.G.; Lovell, Matthew M.

    2015-01-01

    Transition metal-catalyzed strategies for the formation of new C-C bonds have revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules.1–3 In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation4 of two distinct catalysts – multimetallic catalysis – can be employed instead. Many important reactions rely on multimetallic catalysis,5 including the Wacker oxidation of olefins6–8 and the Sonogashira coupling of alkynes with aryl halides.9–10 However, the application of this strategy, even in recently developed methods11, has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing an oxidative addition.12 In this manuscript, we demonstrate that cooperativity between two d10 metal catalysts, (bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium, enables a general cross-Ullman reaction.13–15 Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple C–H bonds that is required for many C–H activation methods.16–17 The selectivity does not require an excess of either substrate and originates from the orthogonal activity of the two catalysts and the relative stability of the two arylmetal intermediates. While (dppp)Pd reacts preferentially with aryl triflates to afford a persistent intermediate, (bpy)Ni reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5% cross product in isolation, together they are able to achieve up to 94% yield. Our results reveal a new, general method for the synthesis of biaryls, heteroaryls, and dienes, as well as a new mechanism for selective transmetalation between two catalysts. We anticipate that this reaction will simplify the synthesis of

  7. Copper-catalyzed conversion of aryl and heteroaryl bromides into the corresponding chlorides.

    PubMed

    Feng, Xiujuan; Qu, Yiping; Han, Yanlei; Yu, Xiaoqiang; Bao, Ming; Yamamoto, Yoshinori

    2012-10-01

    An efficient method for the synthesis of aryl and heteroaryl chlorides is described. The reactions of aryl and heteroaryl bromides with tetramethylammonium chloride proceeded smoothly in the presence of a copper catalyst under mild reaction conditions to produce the corresponding chlorides in satisfactory to excellent yields. PMID:22895409

  8. Nickel-Catalyzed Reductive Cross-Coupling of Aryl Bromides with Alkyl Bromides: Et3N as the Terminal Reductant.

    PubMed

    Duan, Zhengli; Li, Wu; Lei, Aiwen

    2016-08-19

    Reductive cross-coupling has emerged as a direct method for the construction of carbon-carbon bonds. Most cobalt-, nickel-, and palladium-catalyzed reductive cross-coupling reactions to date are limited to stoichiometric Mn(0) or Zn(0) as the reductant. One nickel-catalyzed cross-coupling paradigm using Et3N as the terminal reductant is reported. By using this photoredox catalysis and nickel catalysis approach, a direct Csp(2)-Csp(3) reductive cross-coupling of aryl bromides with alkyl bromides is achieved under mild conditions without stoichiometric metal reductants. PMID:27472556

  9. Palladium-catalyzed carbonylative synthesis of quinazolinones from 2-aminobenzamide and aryl bromides.

    PubMed

    Wu, Xiao-Feng; He, Lin; Neumann, Helfried; Beller, Matthias

    2013-09-16

    C from CO! A straightforward procedure for the carbonylative synthesis of quinazolinones from readily available 2-aminobenzamide and aryl bromides has been developed. In the presence of a palladium catalyst, various quinazolinones were produced in moderate to excellent yields. Remarkably, no chromatography was needed for purification (see scheme). PMID:24175339

  10. Mild Pd-Catalyzed Aminocarbonylation of (Hetero)Aryl Bromides with a Palladacycle Precatalyst

    PubMed Central

    2015-01-01

    A palladacyclic precatalyst is employed to cleanly generate a highly active XantPhos-ligated Pd-catalyst. Its use in low temperature aminocarbonylations of (hetero)aryl bromides provides access to a range of challenging products in good to excellent yields with low catalyst loading and only a slight excess of CO. Some products are unattainable by traditional carbonylative coupling. PMID:25090373

  11. Efficient Stille cross-coupling reaction using aryl chlorides or bromides in water.

    PubMed

    Wolf, Christian; Lerebours, Rachel

    2003-09-19

    An efficient Stille cross-coupling reaction using a variety of aryl halides in neat water has been developed. Employing palladium-phosphinous acid catalyst [(t-Bu)(2)P(OH)](2)PdCl(2) allows formation of biaryls from aryl chlorides and bromides in good to high yields. Functional groups such as ketones and nitriles are tolerated, and organic cosolvents are not required. The air stability and solubility in water of the palladium complexes used in this study facilitate operation of the coupling reaction and product isolation. The feasibility of catalyst recycling has also been demonstrated. PMID:12968920

  12. Reductive Cross-Coupling of Conjugated Arylalkenes and Aryl Bromides with Hydrosilanes by Cooperative Palladium/Copper Catalysis.

    PubMed

    Semba, Kazuhiko; Ariyama, Kenta; Zheng, Hong; Kameyama, Ryohei; Sakaki, Shigeyoshi; Nakao, Yoshiaki

    2016-05-17

    A method for the reductive cross-coupling of conjugated arylalkenes and aryl bromides with hydrosilanes by cooperative palladium/copper catalysis was developed, thus resulting in the highly regioselective formation of various 1,1-diarylalkanes, including a biologically active molecule. Under the applied reaction conditions, high levels of functional-group tolerance were observed, and the reductive cross-coupling of internal alkynes with aryl bromides afforded trisubstituted alkenes. PMID:27080165

  13. Carbonylative Suzuki Couplings of Aryl Bromides with Boronic Acid Derivatives under Base-Free Conditions

    PubMed Central

    2015-01-01

    The carbonylative Suzuki–Miyaura reaction between aryl bromides and arylboronic acid equivalents is herein reported, using base-free conditions and a limited excess of carbon monoxide generated ex situ from stable CO-precursors. Under these conditions, unsymmetrical biaryl ketones were obtained in modest to excellent yields. This method was adapted to the synthesis of the triglyceride and cholesterol regulator drug, fenofibrate, and its 13C-labeled derivative in good yields from the appropriate CO-precursor. PMID:24635142

  14. A Fluorinated Ligand Enables Room-Temperature and Regioselective Pd-Catalyzed Fluorination of Aryl Triflates and Bromides.

    PubMed

    Sather, Aaron C; Lee, Hong Geun; De La Rosa, Valentina Y; Yang, Yang; Müller, Peter; Buchwald, Stephen L

    2015-10-21

    A new biaryl monophosphine ligand (AlPhos, L1) allows for the room-temperature Pd-catalyzed fluorination of a variety of activated (hetero)aryl triflates. Furthermore, aryl triflates and bromides that are prone to give mixtures of regioisomeric aryl fluorides with Pd-catalysis can now be converted to the desired aryl fluorides with high regioselectivity. Analysis of the solid-state structures of several Pd(II) complexes, as well as density functional theory (DFT) calculations, shed light on the origin of the enhanced reactivity observed with L1. PMID:26413908

  15. An Efficient and General Method for Formylation of Aryl Bromides with CO2 and Poly(methylhydrosiloxane).

    PubMed

    Yu, Bo; Yang, Zhenzhen; Zhao, Yanfei; Hao, Leiduan; Zhang, Hongye; Gao, Xiang; Han, Buxing; Liu, Zhimin

    2016-01-18

    The formylation of aryl halides with CO2 to generate aryl aldehydes is challenging. Herein, we report a novel synthesis of aryl aldehydes by formylation of aryl bromides with CO2 and a waste silane, poly(methylhydrosiloxane) (PMHS). It has been discovered that a simple combination of 1,3-bis(diphenyphosphino)propane (DPPP)-chelated Pd catalyst, Pd(DPPP)Cl2 , with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is able to effectively catalyze the reaction, leading to aryl aldehydes in moderate to excellent yields, and without any by-products in most cases. Moreover, this route could be extended to the formylation of aryl iodides with high efficiency. This approach is simple, less costly, and environmentally friendly, and also widens the applications of CO2 to form value-added chemicals by the construction of new C-C bonds. PMID:26663139

  16. Cooperative dual palladium/silver catalyst for direct difluoromethylation of aryl bromides and iodides.

    PubMed

    Gu, Yang; Leng, Xuebing; Shen, Qilong

    2014-01-01

    Difluoromethylated arenes are one of the privileged structural motifs that are important for fine tuning the biological properties of drug molecules. No general catalytic method exists for the formation of difluoromethylarenes. Previous methods for the preparation of difluoromethylarenes typically required harsh conditions, multiple steps or stoichiometric amount of catalysts. Here we report a cooperative dual palladium/silver catalyst system for direct difluoromethylation of aryl bromides and iodides under mild conditions. We develop the system by initial preparation of the putative intermediates in the dual-catalytic cycles, followed by studying the elemental steps to demonstrate the viability of the proposed cooperative catalytic cycle. The reaction is compatible with a variety of functional groups such as ester, amide, protected phenoxide, protected ketone, cyclopropyl, bromide and heteroaryl subunits such as pyrrole, benzothiazole, carbazole or pyridine. PMID:25377759

  17. Copper-catalyzed coupling of triaryl- and trialkylindium reagents with aryl iodides and bromides through consecutive transmetalations.

    PubMed

    Thapa, Surendra; Gurung, Santosh K; Dickie, Diane A; Giri, Ramesh

    2014-10-20

    An efficient copper(I)-catalyzed coupling of triaryl and trialkylindium reagents with aryl iodides and bromides is reported. The reaction proceeds at low catalyst loadings (2 mol%) and generally only requires 0.33 equivalents of the triorganoindium reagent with respect to the aryl halide as all three organic nucleophilic moieties of the reagent are transferred to the products through consecutive transmetalations. The reaction tolerates a variety of functional groups and sterically hindered substrates. Furthermore, preliminary mechanistic studies that entailed the synthesis and characterization of potential reaction intermediates offered a glimpse of the elementary steps that constitute the catalytic cycle. PMID:25213151

  18. Highly Reactive, General and Long-Lived Catalysts for Palladium-Catalyzed Amination of Heteroaryl and Aryl Chlorides, Bromides and Iodides: Scope and Structure-Activity Relationships

    PubMed Central

    Shen, Qilong; Ogata, Tokutaro; Hartwig, John F.

    2010-01-01

    We describe a systematic study of the scope and relationship between ligand structure and activity for a highly efficient and selective class of catalysts for the amination of heteroaryl and aryl chlorides, bromides and iodides containing sterically hindered chelating alkylphosphines. In the presence of this catalyst, aryl and heteroaryl chlorides, bromides and iodides react with many primary amines in high yields with part-per-million quantities of palladium precursor and ligand. Many reactions of primary amines with both heteroaryl and aryl chlorides, bromides and iodides occur to completion with 0.0005-0.05 mol % catalysts. A comparison of the reactivity of this catalyst for coupling of primary amines at these loadings is made with catalysts generated from hindered monophosphines and carbenes, and these data illustrate the benefits of chelation. Thus, these complexes constitute a fourth-generation catalyst for the amination of aryl halides, whose activity complements catalysts based on monophosphines and carbenes. PMID:18444639

  19. Environmentally-Safe Conditions for a Palladium-Catalyzed Direct C3-Arylation with High Turn Over Frequency of Imidazo[1,2-b]pyridazines Using Aryl Bromides and Chlorides.

    PubMed

    Chikhi, Sabah; Djebbar, Safia; Soulé, Jean-François; Doucet, Henri

    2016-09-01

    Pd(OAc)2 was found to catalyze very efficiently the direct arylation of imidazo[1,2-b]pyridazine at C3-position under a very low catalyst loading and phosphine-free conditions. The reaction can be performed in very high TOFs and TONs employing as little as 0.1-0.05 mol % catalyst using a wide range of aryl bromides. In addition, some electron-deficient aryl chlorides were also found to be suitable substrates. Moreover, 31 examples of the cross couplings were reported using green, safe, and renewable solvents, such as pentan-1-ol, diethylcarbonate or cyclopentyl methyl ether, without loss of efficiency. PMID:27380613

  20. A Well-Defined {[(PhCH₂O)₂P(CH₃)₂CHNCH(CH₃)₂]₂PdCl₂} Complex Catalyzed Hiyama Coupling of Aryl Bromides with Arylsilanes.

    PubMed

    Guo, Mengping; Fu, Leiqing; Li, Jiamin; Zhou, Lanjiang; Kang, Yanping

    2016-01-01

    A palladium (II) complex {[(PhCH₂O)₂P(CH₃)₂CHNCH(CH₃)₂]₂PdCl₂} catalyzed Hiyama cross-coupling reaction between aryl bromides and arylsilanes has been developed. The substituted biaryls were produced in moderate to high yields, regardless of electron-withdrawing or electron-donating. PMID:27483226

  1. Rapid synthesis of an electron-deficient t-BuPHOX ligand: cross-coupling of aryl bromides with secondary phosphine oxides.

    PubMed

    McDougal, Nolan T; Streuff, Jan; Mukherjee, Herschel; Virgil, Scott C; Stoltz, Brian M

    2010-10-20

    Herein an efficient and direct copper-catalyzed coupling of oxazoline-containing aryl bromides with electron-deficient secondary phosphine oxides is reported. The resulting tertiary phosphine oxides can be reduced to prepare a range of PHOX ligands. The presented strategy is a useful alternative to known methods for constructing PHOX derivatives. PMID:21076623

  2. Synthesis and antibacterial activities of acylide derivatives bearing an aryl-tetrazolyl chain

    PubMed Central

    Shan, Ling-Xing; Sun, Ping-Hua; Guo, Bao-Qin; Xu, Xing-Jun; Li, Zhi-Qiang; Sun, Jia-Zhi; Zhou, Shu-Feng; Chen, Wei-Min

    2014-01-01

    Seventeen acylides bearing an aryl-tetrazolyl alkyl-substituted side chain were synthesized, starting from clarithromycin, via several reactions including hydrolysis, acetylating, esterification, carbamylation, and Michael addition. The structures of all new compounds were confirmed by 1H nuclear magnetic resonance spectroscopy, 13C nuclear magnetic resonance spectroscopy, and mass spectrometry. All these synthesized acylides were evaluated for in vitro antimicrobial activities against gram-positive pathogens (Staphylococcus aureus, Staphylococcus epidermidis) and gram-negative pathogens (Pseudomonas aeruginosa, Escherichia coli), using the broth microdilution method. Results showed that compounds 10e, 10f, 10g, 10 h, 10o have good antibacterial activities. PMID:25284984

  3. Organozinc Chemistry Enabled by Micellar Catalysis. Palladium-Catalyzed Cross-Couplings between Alkyl and Aryl Bromides in Water at Room Temperature

    PubMed Central

    Duplais, Christophe; Krasovskiy, Arkady; Lipshutz, Bruce H.

    2012-01-01

    Negishi-like cross-couplings between (functionalized) alkyl and aryl bromides are described. Despite the fact that organozinc reagents are intolerant of water, their formation as well as their use in an aqueous micellar environment is discussed herein. Each component of this complex series of events leading up to C–C bond formation has an important role which has been determined insofar as the type of zinc, amine ligand, surfactant, and palladium catalyst are concerned. In particular, the nature of the surfactant has been found to be crucial in order to obtain synthetically useful results involving highly reactive, moisture-sensitive organometallics. Neither organic solvent nor heat is required for these cross-couplings to occur; just add water. PMID:23539206

  4. Comparative analysis of the conformations of symmetrically and asymmetrically deca- and undecasubstituted porphyrins bearing meso-alkyl or -aryl groups

    SciTech Connect

    Senge, M.O.; Medforth, C.J.; Forsyth, T.P.

    1997-03-12

    Conformational analysis of highly substituted porphyrins, has potential implications for modeling the behavior of macrocycles in tetrapyrrole-containing protein complexes and during catalytic reactions. In order to study the influence of different substituent patterns of the conformation of the porphyrin macrocycle, a series of metal free and nickel(II) decasubstituted porphyrins bearing aryl or ethyl groups at opposite meso positions and alkyl groups at the pyrrole positions have been synthesized and characterized by X-ray crystallography. Crystal structures of the free-base porphyrins with 5,15-diaryl substituents showed negligible out-of-plane distortion but a large amount of in-plane distortion along the 5,15-axis accompanied by large bond angle changes similar to those previously seen for related porphyrins with 5,15-dialkyl substituents. Nickel(II) complexes of the 5,15-diaryl-substituted porphyrins show planar or modestly nonplanar conformations, suggesting that these complexes are not intrinsically nonplanar, whereas a complex with 5,15-diethyl substituents has a very ruffled conformation similar to those observed for related complexes with other metals. The nickel(II) complexes are also elongated along the 5,15-axis in a qualitatively similar but less dramatic fashion than are the free-base porphyrins. Spectroscopic studies ({sup 1}H NMR, optical, and resonance Raman spectroscopy) suggest that conformations similar to those determined by X-ray crystallography are present in solution for the 5,15-disubstituted porphyrins containing both aryl and alkyl mesosubstituents were also investigated. Metal-free 5,15-dialkyl- and 5,15-diaryl-substituted porphyrins. Several asymmetric nickel(II) and metal-free deca- and undecasubstituted porphyrins containing both aryl and alkyl mesosubstituents were also investigated.

  5. A Mild Synthesis of New Aryl Vinyl Ethers and Diethyl 1-[(Alkyl)(cyano)methyl]vinylphosphonates via the Substitution of a 2,3-Difunctional Allyl Bromide

    PubMed Central

    Ben Kraïem, Jihène; Arfaoui, Aïcha; Amri, Hassen

    2014-01-01

    A novel class of aryl vinyl ethers 3 and diethyl 3-cyano-3-alkylprop-1-en-2-ylphosphonates 4 has been prepared, respectively, from coupling reaction of diethyl 1-(bromomethyl)-2-cyanovinylphosphonate 2 with phenols and Gilman reagents. PMID:24688373

  6. Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides

    PubMed Central

    2016-01-01

    Although the ruthenium-catalyzed C–H arylation of arenes bearing directing groups with haloarenes is well-known, this process has never been achieved in the absence of directing groups. We report the first example of such a process and show that unexpectedly the reaction only takes place in the presence of catalytic amounts of a benzoic acid. Furthermore, contrary to other transition metals, the arylation site selectivity is governed by both electronic and steric factors. Stoichiometric and NMR mechanistic studies support a catalytic cycle that involves a well-defined η6-arene-ligand-free Ru(II) catalyst. Indeed, upon initial pivalate-assisted C–H activation, the aryl-Ru(II) intermediate generated is able to react with an aryl bromide coupling partner only in the presence of a benzoate additive. In contrast, directing-group-containing substrates (such as 2-phenylpyridine) do not require a benzoate additive. Deuterium labeling and kinetic isotope effect experiments indicate that C–H activation is both reversible and kinetically significant. Computational studies support a concerted metalation–deprotonation (CMD)-type ruthenation mode and shed light on the unusual arylation regioselectivity. PMID:26942551

  7. Ru-Catalyzed C-H Arylation of Fluoroarenes with Aryl Halides.

    PubMed

    Simonetti, Marco; Perry, Gregory J P; Cambeiro, Xacobe C; Juliá-Hernández, Francisco; Arokianathar, Jude N; Larrosa, Igor

    2016-03-16

    Although the ruthenium-catalyzed C-H arylation of arenes bearing directing groups with haloarenes is well-known, this process has never been achieved in the absence of directing groups. We report the first example of such a process and show that unexpectedly the reaction only takes place in the presence of catalytic amounts of a benzoic acid. Furthermore, contrary to other transition metals, the arylation site selectivity is governed by both electronic and steric factors. Stoichiometric and NMR mechanistic studies support a catalytic cycle that involves a well-defined η(6)-arene-ligand-free Ru(II) catalyst. Indeed, upon initial pivalate-assisted C-H activation, the aryl-Ru(II) intermediate generated is able to react with an aryl bromide coupling partner only in the presence of a benzoate additive. In contrast, directing-group-containing substrates (such as 2-phenylpyridine) do not require a benzoate additive. Deuterium labeling and kinetic isotope effect experiments indicate that C-H activation is both reversible and kinetically significant. Computational studies support a concerted metalation-deprotonation (CMD)-type ruthenation mode and shed light on the unusual arylation regioselectivity. PMID:26942551

  8. Evaluation of 1-aryl-2,5-dithiohydrazodicarbonamides as EP additives on bearing balls of different composition in a four ball machine

    SciTech Connect

    Bhattacharya, A.; Verma, V.K.; Prasad, N. )

    1992-08-01

    A number of 1-aryl-2,5-dithiohydrazodicarbonamides are synthesized, and their friction and wear properties are evaluated on a four-ball machine using paraffin oil as a base oil. The additive, 1-p-Cl-phenyl-2,5-dithiohydrazodicarbonamide, is found to be equally effective on steel bearing balls of different compositions. The shape and elemental composition of the wear-scars were investigated by SEM and by Auger Electron Spectroscopy, respectively. 15 refs.

  9. Efficient cross-coupling of aryl Grignard reagents with alkyl halides by recyclable ionic iron(III) complexes bearing a bis(phenol)-functionalized benzimidazolium cation.

    PubMed

    Xia, Chong-Liang; Xie, Cun-Fei; Wu, Yu-Feng; Sun, Hong-Mei; Shen, Qi; Zhang, Yong

    2013-12-14

    A novel bis(phenol)-functionalized benzimidazolium salt, 1,3-bis(3,5-di-tert-butyl-2-hydroxybenzyl)benzimidazolium chloride (H3LCl, 1), was designed and used to prepare ionic iron(III) complexes of the type [H3L][FeX4] (X = Cl, 2; X = Br, 3). Both 2 and 3 were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The catalytic performances of 2 and 3 in cross-coupling reactions using aryl Grignard reagents with primary and secondary alkyl halides bearing β-hydrogens were studied. This analysis shows that complex 2 has good potential for alkyl chloride-mediated coupling. In comparison, complex 3 showed slightly lower catalytic activity. After decanting the product contained in the ethereal layer, complex 2 could be recycled at least eight times without significant loss of catalytic activity. PMID:24145602

  10. Construction of Cyclic Sulfamidates Bearing Two gem-Diaryl Stereocenters through a Rhodium-Catalyzed Stepwise Asymmetric Arylation Protocol.

    PubMed

    Zhang, Yu-Fang; Chen, Diao; Chen, Wen-Wen; Xu, Ming-Hua

    2016-06-01

    A rhodium-catalyzed stepwise asymmetric 1,4- and 1,2-addition of arylboronic acids to α,β-unsaturated cyclic N-sulfonyl ketimines has been developed, providing a wide range of gem-diaryl-substituted chiral benzosulfamidates with high optical purities. C1-Symmetric chiral diene and branched chiral sulfur-olefin ligands were sequentially utilized in this double-arylation process for high stereocontrol. Further synthetic utility offers new opportunities for the facile construction of otherwise difficult to access polycyclic heterocycles. PMID:27184663

  11. Practical Direct α-Arylation of Cyclopentanones by Palladium/Enamine Cooperative Catalysis.

    PubMed

    Xu, Yan; Su, Tianshun; Huang, Zhongxing; Dong, Guangbin

    2016-02-12

    Direct arylation of cyclopentanones has been a long-standing challenge because of competitive self-aldol condensation and multiple arylations. Reported herein is a direct mono-α-C-H arylation of cyclopentanones with aryl bromides which is enabled by palladium/amine cooperative catalysis. This method is scalable and chemoselective with broad functional-group tolerance. Application to controlled sequential arylation of cyclopentanones has been also demonstrated. PMID:26840218

  12. Palladium-Catalyzed α-Arylation of Zinc Enolates of Esters: Reaction Conditions and Substrate Scope

    PubMed Central

    Hama, Takuo; Ge, Shaozhong; Hartwig, John F.

    2013-01-01

    The intermolecular α-arylation of esters by palladium-catalyzed coupling of aryl bromides with zinc enolates of esters is reported. Reactions of three different types of zinc enolates have been developed. α-Arylation of esters occurs in high yields with isolated Reformatsky reagents, with Reformatsky reagents generated from α-bromo esters and activated zinc, and with zinc enolates generated by quenching lithium enolates of esters with zinc chloride. The use of zinc enolates, instead of alkali metal enolates, greatly expands the scope of the arylation of esters. The reactions occur at room temperature or at 70 °C with bromoarenes containing cyano, nitro, ester, keto, fluoro, enolizable hydrogen, hydroxyl or amino functionality and with bromopyridines. The scope of esters encompasses acyclic acetates, propionates, and isobutyrates, α-alkoxyesters, and lactones. The arylation of zinc enolates of esters was conducted with catalysts bearing the hindered pentaphenylferrocenyl di-tert-butylphosphine (Q-phos) or the highly reactive dimeric Pd(I) complex {[P(t-Bu)3]PdBr}2. PMID:23931445

  13. Synthesis, Density Functional Theory (DFT), Urease Inhibition and Antimicrobial Activities of 5-Aryl Thiophenes Bearing Sulphonylacetamide Moieties.

    PubMed

    Noreen, Mnaza; Rasool, Nasir; Gull, Yasmeen; Zubair, Muhammad; Mahmood, Tariq; Ayub, Khurshid; Nasim, Faiz-Ul-Hassan; Yaqoob, Asma; Zia-Ul-Haq, Muhammad; de Feo, Vincenzo

    2015-01-01

    A variety of novel 5-aryl thiophenes 4a-g containing sulphonylacetamide (sulfacetamide) groups were synthesized in appreciable yields via Pd[0] Suzuki cross coupling reactions. The structures of these newly synthesized compounds were determined using spectral data and elemental analysis. Density functional theory (DFT) studies were performed using the B3LYP/6-31G (d, p) basis set to gain insight into their structural properties. Frontier molecular orbital (FMOs) analysis of all compounds 4a-g was computed at the same level of theory to get an idea about their kinetic stability. The molecular electrostatic potential (MEP) mapping over the entire stabilized geometries of the molecules indicated the reactive sites. First hyperpolarizability analysis (nonlinear optical response) were simulated at the B3LYP/6-31G (d, p) level of theory as well. The compounds were further evaluated for their promising antibacterial and anti-urease activities. In this case, the antibacterial activities were estimated by the agar well diffusion method, whereas the anti-urease activities of these compounds were determined using the indophenol method by quantifying the evolved ammonia produced. The results revealed that all the sulfacetamide derivatives displayed antibacterial activity against Bacillus subtiles, Escherichia coli, Staphylococcus aureus, Shigella dysenteriae, Salmonella typhae, Pseudomonas aeruginosa at various concentrations. Furthermore, the compound 4g N-((5-(4-chlorophenyl)thiophen-2-yl)sulfonyl) acetamide showed excellent urease inhibition with percentage inhibition activity ~46.23 ± 0.11 at 15 µg/mL with IC50 17.1 µg/mL. Moreover, some other compounds 4a-f also exhibited very good inhibition against urease enzyme. PMID:26556326

  14. Palladium-Catalyzed Negishi Cross-Coupling Reaction of Aryl Halides with (Difluoromethyl)zinc Reagent.

    PubMed

    Aikawa, Kohsuke; Serizawa, Hiroki; Ishii, Koki; Mikami, Koichi

    2016-08-01

    The palladium-catalyzed Negishi cross-coupling reaction of aryl iodides and bromides with (difluoromethyl)zinc reagent bearing a diamine such as TMEDA is achieved to provide the difluoromethylated aromatic compounds in good to excellent yields. The advantages of (difluoromethyl)zinc reagent are that (1) the derivatives, which possess different stability and reactivity, can be readily prepared via ligand screening and (2) transmetalation of a difluoromethyl group from the zinc reagent to palladium catalyst efficiently proceeds without an activator. PMID:27442347

  15. Direct Intermolecular Aniline ortho-Arylation via Benzyne Intermediates

    PubMed Central

    Truong, Thanh

    2012-01-01

    A method for direct, transition-metal-free ortho-arylation of anilines by aryl chlorides, bromides, fluorides, and triflates has been developed. This methodology provides the most direct approach to 2-arylanilines since no protecting or directing groups on nitrogen are required. The arylation is functional-group tolerant, with alkene, ether, trifluoromethyl, dimethylamino, carbonyl, chloro, and cyano functionalities tolerated. Phenylation of enantiopure binaphthyldiamine affords a product with >99% ee. PMID:23148679

  16. Palladium-Catalyzed Benzylic Arylation of Pyridylmethyl Silyl Ethers: One-Pot Synthesis of Aryl(pyridyl)methanols.

    PubMed

    Rivero, Alexandra R; Kim, Byeong-Seon; Walsh, Patrick J

    2016-04-01

    An efficient palladium-catalyzed direct arylation of pyridylmethyl silyl ethers with aryl bromides is described. A Pd(OAc)2/NIXANTPHOS-based catalyst provides aryl(pyridyl)methyl alcohol derivatives in good to excellent yields (33 examples, 57-100% yield). This protocol is compatible with different silyl ether protecting groups, affording either the protected or the free alcohols in an effective one-pot process. The scalability of the reaction is demonstrated. PMID:27004592

  17. Cyanogen bromide

    Integrated Risk Information System (IRIS)

    Cyanogen bromide ; CASRN 506 - 68 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  18. Vinyl bromide

    Integrated Risk Information System (IRIS)

    Vinyl bromide ; CASRN 593 - 60 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Eff

  19. Palladium-catalyzed β-C(sp(3))-H arylation of phthaloyl alanine with hindered aryl iodides: synthesis of complex β-aryl α-amino acids.

    PubMed

    Zhang, Xuekai; He, Gang; Chen, Gong

    2016-06-28

    An efficient protocol for palladium-catalyzed β-C(sp(3))-H arylation of aliphatic carboxamides equipped with a 2-(2-pyridyl) ethylamine (PE) auxiliary was developed. The PE auxiliary is uniquely effective at facilitating the arylation of primary C(sp(3))-H bonds with sterically hindered aryl iodides. A variety of aryl iodides bearing alkoxyl, carbonyl, nitro and halogen groups on the ortho position can react with the PE-coupled phthaloyl alanine substrate in moderate to excellent yield. These reactions offer a useful solution for preparing complex β-aryl α-amino acid products from readily accessible starting materials. PMID:26781005

  20. Amination of aryl halides with aqueous ammonia catalyzed by green recyclable poly(4-vinylpyridine)-supported copper iodide nanoparticles catalyst.

    PubMed

    Albadi, Jalal; Shiran, Jafar Abbasi; Mansournezhad, Azam

    2014-01-01

    In this research efficient procedure for the amination of aryl halides with aqueous ammonia in the presence of poly(4-vinylpyridine)-supported copper iodide nanoparticles catalyst is reported. A wide range of aryl halides including aryl iodides and aryl bromides are converted into the corresponding aniline derivatives. The experimental procedure with poly(4-vinylpyridine)-supported copper iodide nanoparticles catalyst is quite straightforward and it is recycled up to 3 consecutive runs by simple filtration. PMID:25551733

  1. Copper-Catalyzed Carboxylation of Aryl Iodides with Carbon Dioxide.

    PubMed

    Tran-Vu, Hung; Daugulis, Olafs

    2013-10-01

    A method for carboxylation of aryl iodides with carbon dioxide has been developed. The reaction employs low loadings of copper iodide/TMEDA or DMEDA catalyst, 1 atm of CO2, DMSO or DMA solvent, and proceeds at 25-70 °C. Good functional group tolerance is observed, with ester, bromide, chloride, fluoride, ether, hydroxy, amino, and ketone functionalities tolerated. Additionally, hindered aryl iodides such as iodomesitylene can also be carboxylated. PMID:24288654

  2. Copper-catalyzed arylation of biguanide derivatives via C-N cross-coupling reactions.

    PubMed

    Zhang, Chen; Huang, Bo; Bao, Ai-Qing; Li, Xiao; Guo, Shunna; Zhang, Jin-Quan; Xu, Jun-Zhi; Zhang, Rihao; Cui, Dong-Mei

    2015-12-21

    An efficient copper-catalyzed cross-coupling reaction of biguanide hydrochloride derivatives with both aryl iodides and bromides under mild conditions has been developed. The reaction occurred in good yields and tolerated aryl halides containing functionalities such as nitriles, sulfonamides, ethers, and halogens. Alkyl and cyclic substituted biguanidines were also well tolerated. PMID:26444146

  3. Nickel-Catalyzed Decarboxylative Cross-Coupling of Perfluorobenzoates with Aryl Halides and Sulfonates

    PubMed Central

    2016-01-01

    A Ni-catalyzed method for the coupling of perfluorobenzoates with aryl halides and pseudohalides is described. Aryl iodides, bromides, chlorides, triflates, and tosylates participate in these transformations to afford the products in good yields. Penta-, tetra-, and trifluorinated biaryl compounds are obtained using these newly developed Ni-catalyzed decarboxylative cross-coupling reactions. PMID:25700128

  4. Ullmann coupling reaction of aryl chlorides on Au(111) using dosed Cu as a catalyst and the programmed growth of 2D covalent organic frameworks.

    PubMed

    Shi, Ke Ji; Zhang, Xin; Shu, Chen Hui; Li, Deng Yuan; Wu, Xin Yan; Liu, Pei Nian

    2016-07-01

    The efficiency of Ullmann reaction of aryl chlorides on an Au(111) surface has been substantially increased by using dosed Cu as a catalyst. The different reactivity of aryl bromides and aryl chlorides has been exploited to design a programmed, on-surface synthesis to form 2D covalent organic frameworks. PMID:27334002

  5. Palladium-catalyzed cross-coupling reactions of aryl boronic acids with aryl halides in water.

    PubMed

    Wang, Shaoyan; Zhang, Zhiqiang; Hu, Zhizhi; Wang, Yue; Lei, Peng; Chi, Haijun

    2009-01-01

    An efficient Suzuki cross-coupling reaction using a variety of aryl halides in neat water was developed. The Pd-catalyzed reaction between aryl bromides or chlorides and phenyl boronic acids was compatible with various functional groups and affords biphenyls in good to excellent yields without requirement of organic cosolvents. The air stability and solubility in water of the palladium-phosphinous acid complexes were considered to facilitate operation of the coupling reaction and product isolation. The reaction conditions including Pd catalyst selection, temperature, base and catalyst recoverability were also investigated. PMID:25084408

  6. Palladium-Catalyzed α-Arylation of Benzylic Phosphonates

    PubMed Central

    2015-01-01

    A new synthetic route to access diarylmethyl phosphonates is presented. The transformation enables the introduction of aromatic groups on benzylic phosphonates via a deprotonative cross-coupling process (DCCP). The Pd(OAc)2/CataCXium A-based catalyst afforded a reaction between benzyl diisopropyl phosphonate derivatives and aryl bromides in good to excellent isolated yields (64–92%). PMID:24520897

  7. Hauser-Heck: Efficient Synthesis of γ-Aryl-β-ketoesters en Route to Substituted Naphthalenes.

    PubMed

    Wagner, Frederic; Harms, Klaus; Koert, Ulrich

    2015-11-20

    γ-Aryl-β-ketoesters can be prepared in one step from aryl bromides and bis(trimethylsilyl) enol ethers using catalytic amounts of Pd(dba)2/t-Bu3P and stoichiometric amounts of Bu3SnF. The wide range of γ-(hetero)aryl-β-ketoesters that can be obtained illustrate the scope and limitations of this novel Hauser-Heck combination. γ-Aryl-β-ketoesters with a 1,3-dioxane acetal in the ortho position can easily be transformed into the hydroxy naphthoate in very good yield. Aqueous formic acid at 65 °C provides optimal conditions for this deprotective aromatization. PMID:26536142

  8. Reversed-Polarity Synthesis of Diaryl Ketones through Palladium-Catalyzed Direct Arylation of 2-Aryl-1,3-dithianes

    PubMed Central

    Yucel, Baris; Walsh, Patrick J.

    2015-01-01

    An umpolung approach to the synthesis of diaryl ketones has been developed based on in situ generation of acyl anion equivalents and their catalytic arylation. This method entails the base promoted palladium catalyzed direct C–H arylation of 2 The resulting 2,2-diaryl-1,3-dithianes with aryl bromides. Use of MN(SiMe3)2 (M=Li, Na) base results in reversible deprotonation of the weakly acidic dithiane. In the presence of a Pd(NiXantphos)-based catalyst and aryl bromide, cross-coupling of the metallated 2-aryl-1,3-dithiane takes place under mild conditions (2 h at rt) with yields as high as 96%. The resulting 2,2-diaryl-1,3-dithianes were converted into diaryl ketones by either molecular iodine, N-bromo succinimide (NBS) or Selectfluor in the presence of water. The dithiane arylation/hydrolysis can be performed in a one-pot procedure to yield a good to excellent yields. This method is suitable for rapid and large-scale synthesis of diaryl ketones. A one-pot preparation of anti-cholesterol drug fenofibrate (TriCor®) has been achieved on 10.0 mmol scale in 86% yield. PMID:26185491

  9. Short Synthesis of Sulfur Analogues of Polyaromatic Hydrocarbons through Three Palladium-Catalyzed C-H Bond Arylations.

    PubMed

    Hagui, Wided; Besbes, Néji; Srasra, Ezzeddine; Roisnel, Thierry; Soulé, Jean-François; Doucet, Henri

    2016-09-01

    An expeditious synthesis of a wide range of phenanthro[9,10-b]thiophene derivatives, which are a class of polyaromatic hydrocarbon (PAH) containing a sulfur atom, is reported. The synthetic scheme involves only two operations from commercially available thiophenes, 2-bromobenzenesulfonyl chlorides and aryl bromides. In the first step, palladium-catalyzed desulfitative arylation using 2-bromobenzenesulfonyl chlorides allows the synthesis of thiophene derivatives, which are substituted at the C4 position by an aryl group containing an ortho-bromo substituent. Then, a palladium-catalyzed one-pot cascade intermolecular C5-arylation of thiophene using aryl bromides followed by intramolecular arylation led to the corresponding phenanthro[9,10-b]thiophenes in a single operation. In addition, PAHs containing two or three sulfur atoms, as well as both sulfur and nitrogen atoms, were also designed by this strategy. PMID:27550151

  10. Trifluoromethylation of aryl and heteroaryl halides with fluoroform-derived CuCF3: scope, limitations, and mechanistic features.

    PubMed

    Lishchynskyi, Anton; Novikov, Maxim A; Martin, Eddy; Escudero-Adán, Eduardo C; Novák, Petr; Grushin, Vladimir V

    2013-11-15

    Fluoroform-derived CuCF3 recently discovered in our group exhibits remarkably high reactivity toward aryl and heteroaryl halides, performing best in the absence of extra ligands. A broad variety of iodoarenes undergo smooth trifluoromethylation with the "ligandless" CuCF3 at 23-50 °C to give the corresponding benzotrifluorides in nearly quantitative yield. A number of much less reactive aromatic bromides also have been trifluoromethylated, including pyridine, pyrimidine, pyrazine, and thiazole derivatives as well as aryl bromides bearing electron-withdrawing groups and/or ortho substituents. Only the most electrophilic chloroarenes can be trifluoromethylated, e.g., 2-chloronicotinic acid. Exceptionally high chemoselectivity of the reactions (no side-formation of arenes, biaryls, and C2F5 derivatives) has allowed for the isolation of a large number of trifluoromethylated products in high yield on a gram scale (up to 20 mmol). The CuCF3 reagent is destabilized by CuX coproduced in the reaction, the magnitude of the effect paralleling the Lewis acidity of CuX: CuCl > CuBr > CuI. While S(N)Ar and S(RN)1 mechanisms are not operational, there is a well-pronounced ortho effect, i.e., the enhanced reactivity of ortho-substituted aryl halides 2-RC6H4X toward CuCF3. Intriguingly, this ortho-effect is observed for R = NO2, COOH, CHO, COOEt, COCH3, OCH3, and even CH3, but not for R = CN. The fluoroform-derived CuCF3 reagent and its reactions with haloarenes provide an unmatched combination of reactivity, selectivity, and low cost. PMID:23964731

  11. A general and efficient approach to aryl thiols: CuI-catalyzed coupling of aryl iodides with sulfur and subsequent reduction.

    PubMed

    Jiang, Yongwen; Qin, Yuxia; Xie, Siwei; Zhang, Xiaojing; Dong, Jinhua; Ma, Dawei

    2009-11-19

    A CuI-catalyzed coupling reaction of aryl iodides and sulfur powder takes place in the presence of K(2)CO(3) at 90 degrees C. The coupling mixture is directly treated with NaBH(4) or triphenylphosphine to afford aryl thiols in good to excellent yields. A wide range of substituted aryl thiols that bear methoxy, hydroxyl, carboxylate, amido, keto, bromo, and fluoro groups can be assembled through this procedure. PMID:19835369

  12. Efficient Synthesis of 3H-Indoles Enabled by the Lead-Mediated α-Arylation of β-Ketoesters or γ-Lactams Using Aryl Azides

    PubMed Central

    2015-01-01

    The development of a lead-mediated α-arylation reaction between aryl azides and β-ketoesters or γ-lactams that facilitates the formation of 3H-indoles is disclosed. Twenty-five examples are included which demonstrate the generality of this reaction to access aryl azides bearing tetrasubstituted o-alkyl substituents. When paired with a Staudinger reduction, this reaction streamlines the synthesis of functionalized 3H-indoles. PMID:24865180

  13. A cooperative Pd-Cu system for direct C-H bond arylation.

    PubMed

    Lesieur, Mathieu; Lazreg, Faïma; Cazin, Catherine S J

    2014-08-18

    A novel and efficient method for C-H arylation using well-defined Pd- and Cu-NHC systems has been developed. This process promotes the challenging construction of C-C bonds from arenes or heteroarenes using aryl bromides and chlorides. Mechanistic studies show that [Cu(OH)(NHC)] plays a key role in the C-H activation and is involved in the transmetallation with the Pd-NHC co-catalyst. PMID:24976025

  14. Methyl Bromide Poisoning

    PubMed Central

    Rathus, E. M.; Landy, P. J.

    1961-01-01

    Seven cases of methyl bromide poisoning which occurred amongst workers engaged on a fumigation project are described. The methods adopted for investigation of the environmental situation are discussed and the measurement of blood bromide levels on random samples of workers is suggested as an index of the effectiveness of equipment and working methods. PMID:13739738

  15. Reductions of aryl bromides in water at room temperature

    PubMed Central

    Fennewald, James C.; Landstrom, Evan B.; Lipshutz, Bruce H.

    2015-01-01

    Micellar nanoreactors derived from commercially available ‘Nok’ (SPGS-550-M), in the presence of Fu’s catalyst and a mild hydride source (NaBH4), are useful for facile debromination of functionalized aromatic derivatives. This mild and environemntally responsible process is utlized in water at room temperature, and the reaction mixtures can be smoothly recycled. PMID:26273116

  16. Enantioselective cross-coupling of meso-epoxides with aryl halides.

    PubMed

    Zhao, Yang; Weix, Daniel J

    2015-03-11

    The first enantioselective cross-electrophile coupling of aryl bromides with meso-epoxides to form trans-β-arylcycloalkanols is presented. The reaction is catalyzed by a combination of (bpy)NiCl2 and a chiral titanocene under reducing conditions. Yields range from 57 to 99% with 78-95% enantiomeric excess. The 30 examples include a variety of functional groups (ether, ester, ketone, nitrile, ketal, trifluoromethyl, sulfonamide, sulfonate ester), both aryl and vinyl halides, and five- to seven-membered rings. The intermediacy of a carbon radical is strongly suggested by the conversion of cyclooctene monoxide to an aryl [3.3.0]bicyclooctanol. PMID:25716775

  17. Palladium-Catalyzed Arylation of Fluoroalkylamines

    PubMed Central

    Brusoe, Andrew T.; Hartwig, John F.

    2015-01-01

    We report the synthesis of fluorinated anilines by palladium-catalyzed coupling of fluoroalkylamines with aryl bromides and aryl chlorides. The products of these reactions are valuable because anilines typically require the presence of an electron-withdrawing substituent on nitrogen to suppress aerobic or metabolic oxidation, and the fluoroalkyl groups have steric properties and polarity distinct from those of more common electron-withdrawing amide and sulfonamide units. The fluoroalkylaniline products are unstable under typical conditions for C–N coupling reactions (heat and strong base). However, the reactions conducted with the weaker base KOPh, which has rarely been used in cross-coupling to form C–N bonds, occurred in high yield in the presence of a catalyst derived from commercially available AdBippyPhos and [Pd(allyl)Cl]2. Under these conditions, the reactions occur with low catalyst loadings (<0.50 mol % for most substrates) and tolerate the presence of various functional groups that react with the strong bases that are typically used in Pd-catalyzed C–N cross-coupling reactions of aryl halides. The resting state of the catalyst is the phenoxide complex, (BippyPhosPd(Ar)OPh); due to the electron-withdrawing property of the fluoroalkyl substituent, the turnover-limiting step of the reaction is reductive elimination to form the C–N bond. PMID:26065341

  18. Formation of ArF from LPdAr(F): catalytic conversion of aryl triflates to aryl fluorides.

    PubMed

    Watson, Donald A; Su, Mingjuan; Teverovskiy, Georgiy; Zhang, Yong; García-Fortanet, Jorge; Kinzel, Tom; Buchwald, Stephen L

    2009-09-25

    Despite increasing pharmaceutical importance, fluorinated aromatic organic molecules remain difficult to synthesize. Present methods require either harsh reaction conditions or highly specialized reagents, making the preparation of complex fluoroarenes challenging. Thus, the development of general methods for their preparation that overcome the limitations of those techniques currently in use is of great interest. We have prepared [LPd(II)Ar(F)] complexes, where L is a biaryl monophosphine ligand and Ar is an aryl group, and identified conditions under which reductive elimination occurs to form an Ar-F bond. On the basis of these results, we have developed a catalytic process that converts aryl bromides and aryl triflates into the corresponding fluorinated arenes by using simple fluoride salts. We expect this method to allow the introduction of fluorine atoms into advanced, highly functionalized intermediates. PMID:19679769

  19. Copper-catalyzed Green and Expeditious N-Arylation of Sulfoximines using Diaryliodonium Salts

    EPA Science Inventory

    An ultrasound-accelerated green route for an expeditious N-arylation of NH-sulfoximines is described that involves the use of benign diaryliodonium salts in aqueous polyethylene glycol-400 and copper(I) bromide as catalyst at room temperature. The high yields of the products and...

  20. Cross-Coupling of Aromatic Bromides with Allylic Silanolate Salts

    PubMed Central

    Denmark, Scott E; Werner, Nathan S.

    2009-01-01

    The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85 °C in DME with allylpalladium chloride dimer (2.5 mol %) to afford 7–95% yields of the allylation products. Both electron-rich and sterically-hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (γ-substitution product). A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 4–83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous E-silanolates gave slightly higher γ-selectivity than the pure Z-silanolates. A unified mechanistic picture involving initial γ-transmetalation followed by direct reductive elimination or σ–π isomerization can rationalize all of the observed trends. PMID:18998687

  1. Proposal for halogen atom transfer mechanism for Ullmann O-arylation of phenols with aryl halides.

    PubMed

    Zhang, Songlin; Zhu, Zhenzhong; Ding, Yuqiang

    2012-12-01

    A systematic theoretical study on reaction mechanisms for copper(I)-catalyzed C-O coupling of phenols with aryl bromides is reported herein. Through evaluation of the relative concentrations of possible copper species in reaction solution and reactivity study of these copper species with aryl halides in the context of several commonly proposed mechanisms for copper(I)-catalyzed Ullmann reactions, we propose that the active copper catalyst should be a neutral (L)Cu(I)-OAr (L denotes an ancillary ligand; OAr denotes an aryloxide ligand) species in nonpolar solvent and Cu(OAr)(2)(-) anion in highly polar solvent. In the reaction solution, these two kinds of copper species should be in equilibrium, the direction of which is highly dependent on the polarity of the solvent. For both kinds of copper species, a halogen atom transfer mechanism is favored where an initial halogen atom transfer from phenyl bromide to the Cu(I) center occurs, resulting in the formation of Cu(II)(OAr)(Br) and a phenyl radical. Subsequent rapid attack of this phenyl radical to the aryloxide ligand bound to copper(II) would yield the coupling product and Cu(I)(Br) species, which can be readily converted to the active Cu(I)-OAr species in the presence of phenols and base. Other mechanisms such as oxidative addition, single electron transfer and σ-bond metathesis mechanisms all possess activation barriers which are too high, rendering them kinetically unfavorable. Electronic effects on phenol rings reveal that electron-donating substituents accelerate the coupling of (phen)Cu(I)(OAr) with aryl halides whereas electron-withdrawing substituents lead to much higher activation barriers, which is consistent with experimental findings and thus lends further support for such a halogen atom transfer mechanism. In view of the widely accepted oxidative addition/reductive elimination mechanism for analogous copper(I)-catalyzed coupling of N-nucleophiles with aryl halides, our results here highlight that the

  2. General and modular synthesis of isomeric 5-substituted pyridin-2-yl and 6-substituted pyridin-3-yl C-ribonucleosides bearing diverse alkyl, aryl, hetaryl, amino, carbamoyl, and hydroxy groups.

    PubMed

    Štefko, Martin; Slavětínská, Lenka; Klepetářová, Blanka; Hocek, Michal

    2011-08-19

    A general modular and practical methodology for preparation of diverse 5-substituted pyridin-2-yl and 6-substituted pyridin-3-yl C-ribonucleosides was developed. Regioselective lithiation of 2,5-dibromopyridine proceeded at position 5 or 2 depending on the solvent, and the resulting bromopyridyl lithium species underwent additions to TBS-protected ribonolactone and follow-up transformations to corresponding acetylated hemiketal intermediates 7 and 10 that were diastereoselectively reduced to give either 5-bromopyridin-2-yl or 6-bromopyridin-3-yl silyl-protected C-ribonucleosides 8 or 11 in 68% and 77% overall yields as pure β-anomers. These bromopyridyl C-nucleoside intermediates were then subjected to a series of palladium-catalyzed cross-coupling reactions, aminations, aminocarbonylations, and hydroxylations to give a series of protected 1β-(5-alkyl-, 5-aryl-, 5-amino-, 5-carbamoyl-, and 5-hydroxypyridin-2-yl)-C-ribonucleosides 13a-i and β-(6-alkyl-, 6-aryl-, 6-amino-, 6-carbamoyl-, and 6-hydroxypyridin-3-yl)-C-ribonucleosides 15a-i. Deprotection of silylated nucleosides by Et(3)N·3HF, TBAF, or TFA gave a series of free C-nucleosides 14a-i and 16a-i. PMID:21739971

  3. Synthesis of (18) F-Difluoromethylarenes from Aryl (Pseudo) Halides.

    PubMed

    Shi, Hang; Braun, Augustin; Wang, Lu; Liang, Steven H; Vasdev, Neil; Ritter, Tobias

    2016-08-26

    A general method for the synthesis of [(18) F]difluoromethylarenes from [(18) F]fluoride for radiopharmaceutical discovery is reported. The method is practical, operationally simple, tolerates a wide scope of functional groups, and enables the labeling of a variety of arenes and heteroarenes with radiochemical yields (RCYs, not decay-corrected) from 10 to 60 %. The (18) F-fluorination precursors are readily prepared from aryl chlorides, bromides, iodides, and triflates. Seven (18) F-difluoromethylarene drug analogues and radiopharmaceuticals including Claritin, fluoxetine (Prozac), and [(18) F]DAA1106 were synthesized to show the potential of the method for applications in PET radiopharmaceutical design. PMID:27491349

  4. Copper-Catalyzed 2,2,2-Trifluoroethylthiolation of Aryl Halides.

    PubMed

    Chen, Shouxiong; Zhang, Mengjia; Liao, Xuebin; Weng, Zhiqiang

    2016-09-01

    Herein, a copper-catalyzed 2,2,2-trifluoroethylthiolation reaction of aryl bromides and iodides with elemental sulfur, and 1,1,1-trifluoro-2-iodoethane is described. The reaction showed excellent functional group tolerance and allowed the synthesis of various substituted aryl 2,2,2-trifluoroethyl thioethers with good to excellent yields. This transformation constitutes a one-pot synthesis of 2,2,2-trifluoroethylthiolated compounds from inexpensive, readily available starting materials. Utility of the protocol was further demonstrated in the late-stage synthesis of the pirfenidone derivative. The copper thiolate species were prepared and proposed as key intermediates in the catalytic cycle. PMID:27477255

  5. Modular isoquinoline synthesis using catalytic enolate arylation and in situ functionalization.

    PubMed

    Pilgrim, Ben S; Gatland, Alice E; McTernan, Charlie T; Procopiou, Panayiotis A; Donohoe, Timothy J

    2013-12-20

    A methyl ketone, an aryl bromide, an electrophile, and ammonium chloride were combined in a four-component, three-step, and one-pot coupling procedure to furnish substituted isoquinolines in overall yields of up to 80%. This protocol utilizes the palladium catalyzed α-arylation reaction of an enolate, followed by in situ trapping with an electrophile, and aromatization with ammonium chloride. tert-Butyl cyanoacetate participated in a similar protocol; after functionalization and decarboxylation, 3-amino-4-alkyl isoquinolines were prepared in high yield. PMID:24251885

  6. Bromide affecting drinking water mutagenicity.

    PubMed

    Myllykangas, T; Nissinen, T K; Mäki-Paakkanen, J; Hirvonen, A; Vartiainen, T

    2003-11-01

    The effect of bromide on the mutagenicity of artificially recharged groundwater and purified artificially recharged groundwater after chlorine, ozone, hydrogen peroxide, permanganate, and UV treatments alone and in various combinations was studied. The highest mutagenicity was observed after chlorination, while hydrogen peroxide-ozone-chlorine treatment produced the lowest value for both waters. Chlorinated waters, which were spiked with bromide, had up to 3.7 times more mutagenic activity than waters without bromide after every preoxidation method. 3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) was found to correspond as much as 76% of the overall mutagenicity in the waters not spiked with bromide. MX formation was found to be lower when the treated water contained bromide, implicating the formation of brominated MX analogues. Trihalomethane formation increased when the treated water contained bromide. PMID:13129514

  7. Mild Pd-catalyzed N-arylation of methanesulfonamide and related nucleophiles: avoiding potentially genotoxic reagents and byproducts.

    PubMed

    Rosen, Brandon R; Ruble, J Craig; Beauchamp, Thomas J; Navarro, Antonio

    2011-05-20

    A convenient, general, and high yielding Pd-catalyzed cross-coupling of methanesulfonamide with aryl bromides and chlorides is reported. The use of this method eliminates concern over genotoxic impurities that can arise when an aniline is reacted with methanesulfonyl chloride. The application of this method to the synthesis of dofetilide is also reported. PMID:21510692

  8. The Development of Versatile Methods for Palladium-Catalyzed Coupling Reactions of Aryl Electrophiles Through the Use of P(t-Bu)3 and PCy3 as Ligands

    PubMed Central

    FU, GREGORY C.

    2009-01-01

    CONSPECTUS Metal-catalyzed coupling reactions of aryl electrophiles with organometallics and with olefins serve as unusually effective tools for forming new carbon-carbon bonds. By 1998, researchers had developed catalysts that achieved reactions of aryl iodides, bromides, and triflates. Nevertheless, many noteworthy challenges remained, among them: couplings of aryl iodides, bromides, and triflates under mild conditions (at room temperature, for example); couplings of hindered reaction partners; and, couplings of inexpensive aryl chlorides. This Account highlights some of the progress that has been made over the past decade, largely through the appropriate choice of ligand, in achieving these synthetic objectives. In particular, we have established that palladium in combination with a bulky trialkylphosphine accomplishes a broad spectrum of coupling processes, including Suzuki, Stille, Negishi, and Heck reactions. These methods have been applied in a wide array of settings, such as natural-product synthesis, materials science, and bioorganic chemistry. PMID:18947239

  9. Iron-catalyzed arylation of α-aryl-α-diazoesters.

    PubMed

    Yang, Ji-Min; Cai, Yan; Zhu, Shou-Fei; Zhou, Qi-Lin

    2016-06-28

    An iron-catalyzed arylation of α-aryl-α-diazoesters with electron-rich benzene rings was developed, which provides an efficient method for the preparation of 1,1-diarylacetates with high yields and excellent chemo- and regio-selectivities. PMID:26805776

  10. Convergent Synthesis of 2-Aryl-Substituted Quinolines by Gold-Catalyzed Cascade Reaction.

    PubMed

    Ueda, Hirofumi; Yamaguchi, Minami; Tokuyama, Hidetoshi

    2016-01-01

    Gold-catalyzed auto-tandem catalysis has been developed for synthesizing 2-aryl-substituted quinolines. The reaction of an aniline bearing an acetal moiety with an aryl alkyne proceeded via formal [4+2]-cycloaddition, which involved the addition of gold acetylide to an oxonium ion to give amino alkyne intermediate and sequential 6-endo-dig cyclization of amino alkyne intermediate by attacking of nitrogen to alkyne moiety activated by gold catalyst. The cationic gold catalyst promoted two different processes by enhancing the nucleophilicity and electrophilicity of alkyne. This convergent synthetic methodology enabled the synthesis of a variety of 2-aryl-substituted quinolines. PMID:27373638

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

    SciTech Connect

    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. Aqueous Zinc Bromide Waste Solidification

    SciTech Connect

    Langton, C.A.

    2002-07-23

    The goal of this study was to select one or more commercially available aqueous sorbents to solidify the zinc bromide solution stored in C-Area, identify the polymer to zinc bromide solution ratio (waste loading) for the selected sorbents, and identify processing issues that require further testing in pilot-scale testing.

  13. Tiotropium Bromide: An Update

    PubMed Central

    Heredia, Josep Lluis

    2009-01-01

    Tiotropium bromide is a once-daily inhaled anticholinergic bronchodilator. It works by blocking the muscarinic receptors in airway smooth muscle. Tiotropium has a wide therapeutic margin, due to its poor gastrointestinal absorption and its very low systemic bioavailability. The drug is mainly indicated in COPD patients. Clinically relevant outcomes such as significant improvements in spirometry, hyperinflation, dyspnea, heath status, acute exacerbations and mortality have been consistently observed in tiotropium clinical trials, and the drug has been shown to reduce the risk of mortality due to cardiac-vascular disease and respiratory failure. The main side effect reported is dryness of the mouth. Some subgroups of asthmatics also seem to respond to anticholinergic drugs: among them, those with the Arg/Arg genotype for the β2-adrenergic receptor and those with a high percentage of neutrophils in sputum. PMID:19461900

  14. 1,2-shifts of hydrogen atoms in aryl radicals

    SciTech Connect

    Brooks, M.A.; Scott, L.T.

    1999-06-16

    An energy barrier on the order of 60 kcal/mol is predicted for the 1,2-shift of hydrogen atoms in aryl radicals. Such rearrangements are, therefore, not expected to occur under ordinary laboratory conditions, but they should be prevalent in the aryl radicals formed during combustion, flash vacuum pyrolysis, and other high-temperature gas-phase processes. As a demonstration of this rearrangement, the 2-benzo[c]phenanthryl radical (1) was generated by flash vacuum pyrolysis of the corresponding aryl bromide. A 1,2-shift of hydrogen out of the sterically congested cover region of 1, followed by cyclization and rearomatization of the resulting radical, is proposed to explain the observation of benzo[ghi]fluoranthene as the dominant monomeric product formed. Under the same conditions, [1,3,4,5-{sup 2}H{sub 4}]-2-bromobenzo[c]phenanthrene gives [1,2,3,4-{sup 2}H{sub 4}]-benzo[ghi]fluoranthene as the dominant monomeric product, in accord with the expectation of a deuterium atom 1,2-shift.

  15. NiXantphos: A Deprotonatable Ligand for Room-Temperature Palladium-Catalyzed Cross-Couplings of Aryl Chlorides

    PubMed Central

    2015-01-01

    Although the past 15 years have witnessed the development of sterically bulky and electron-rich alkylphosphine ligands for palladium-catalyzed cross-couplings with aryl chlorides, examples of palladium catalysts based on either triarylphosphine or bidentate phosphine ligands for efficient room temperature cross-coupling reactions with unactivated aryl chlorides are rare. Herein we report a palladium catalyst based on NiXantphos, a deprotonatable chelating aryldiphosphine ligand, to oxidatively add unactivated aryl chlorides at room temperature. Surprisingly, comparison of an extensive array of ligands revealed that under the basic reaction conditions the resultant heterobimetallic Pd–NiXantphos catalyst system outperformed all the other mono- and bidentate ligands in a deprotonative cross-coupling process (DCCP) with aryl chlorides. The DCCP with aryl chlorides affords a variety of triarylmethane products, a class of compounds with various applications and interesting biological activity. Additionally, the DCCP exhibits remarkable chemoselectivity in the presence of aryl chloride substrates bearing heteroaryl groups and sensitive functional groups that are known to undergo 1,2-addition, aldol reaction, and O-, N-, enolate-α-, and C(sp2)–H arylations. The advantages and importance of the Pd–NiXantphos catalyst system outlined herein make it a valuable contribution for applications in Pd-catalyzed arylation reactions with aryl chlorides. PMID:24745758

  16. Aryl substitution of pentacenes

    PubMed Central

    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

  17. Rh(I)-Catalyzed Direct Arylation of Pyridines and Quinolines

    SciTech Connect

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

    2008-07-29

    additive proved even more effective, with the yield of 1a improving to 61% (entry 2). Further enhancement in yield was not observed upon the inclusion of other additives such as MgO (entry 3), various organic bases (entries 4, 5), or a protic acid source (entry 6). Absolute concentration proved very important, with the best results being obtained at relatively high concentrations of the aryl bromide (compare entries 7 and 8). A marginal improvement was observed upon running the reaction with 6 equivalents of 2-methyl pyridine (entry 9). The reaction temperature could also be increased to 175 or 190 C while maintaining reaction yield, to enable the reaction time to be reduced to 24 h (entries 10 and 11). In summary, we have developed a Rh(I)-catalyzed strategy for the direct arylation of pyridines and quinolines. The heterocycle is used without the need for prefunctionalization, and all reaction components are inexpensive and readily available. The strategy represents an expeditious route to an important class of bis(hetero)aryls and should be of broad utility.

  18. Radical Hydrodeiodination of Aryl, Alkenyl, Alkynyl, and Alkyl Iodides with an Alcoholate as Organic Chain Reductant through Electron Catalysis.

    PubMed

    Dewanji, Abhishek; Mück-Lichtenfeld, Christian; Studer, Armido

    2016-06-01

    A simple and efficient method for radical hydrodeiodination is reported. The novel approach uses electron catalysis. In situ generated Na-alcoholates are introduced as radical chain reducing reagents and reactions work with O2 as cheap initiator. Hydrodeiodination works on aryl, alkenyl, alkynyl iodides and a tert-alkyl iodide also gets reduced applying the method. Albeit less general, the method is also applicable to the reduction of aryl bromides. The novel reagent is successfully used to conduct typical reductive radical cyclization reactions and mechanistic studies are reported. PMID:27101530

  19. Palladium-Catalyzed Room-Temperature Acylative Suzuki Coupling of High-Order Aryl Borons with Carboxylic Acids.

    PubMed

    Si, Shufen; Wang, Chen; Zhang, Nan; Zou, Gang

    2016-05-20

    This note describes a dimethyl dicarbonate-assisted, Pd(OAc)2/PPh3-catalyzed acylative Suzuki coupling of carboxylic acids with diarylborinic acids or tetraarylboronates for practical and efficient synthesis of sterically undemanding aryl ketones at room temperature. More than just cost-effective alternatives to aryl boronic acids, diarylborinic acids and tetraarylboronates displayed higher reactivity in the acylative Suzuki coupling. A variety of alkyl aryl ketones, including those bearing a hydroxy, bromo, or carbonyl group, could be readily obtained in modest to excellent yields. PMID:27100118

  20. Rhodium-catalyzed silylation and intramolecular arylation of nitriles via the silicon-assisted cleavage of carbon-cyano bonds.

    PubMed

    Tobisu, Mamoru; Kita, Yusuke; Ano, Yusuke; Chatani, Naoto

    2008-11-26

    A rhodium-catalyzed silylation reaction of carbon-cyano bonds using disilane has been developed. Under these catalytic conditions, carbon-cyano bonds in aryl, alkenyl, allyl, and benzyl cyanides bearing a variety of functional groups can be silylated. The observation of an enamine side product in the silylation of benzyl cyanides and related stoichiometric studies indicate that the carbon-cyano bond cleavage proceeds through the deinsertion of silyl isocyanide from eta(2)-iminoacyl complex B. Knowledge gained from these studies has led to the development of a new intramolecular biaryl coupling reaction in which aryl cyanides and aryl chlorides are cross-coupled. PMID:18975946

  1. Suzuki-Miyaura Cross-Coupling of Potassium Alkoxyethyltri-fluoroborates: Access to Aryl/Heteroarylethyloxy Motifs

    PubMed Central

    Fleury-Brégeot, Nicolas; Presset, Marc; Beaumard, Floriane; Colombel, Virginie; Oehlrich, Daniel; Rombouts, Frederik; Molander, Gary A.

    2012-01-01

    The introduction of an alkoxyethyl moiety onto aromatic substructures has remained a long-standing challenge for synthetic organic chemists. The main reasons are the inherent instability of alkoxyethylmetallic species and the lack of general procedures to access them. A new method utilizing a cross-coupling strategy based on the exceptional properties of organotrifluoroborates has been developed, and the method allows an easy and efficient installation of this unit on a broad range of aryl and heteroaryl bromides. PMID:23131122

  2. Bromide Adsorption by Reference Minerals and Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bromide, Br-, adsorption behavior was investigated on amorphous Al and Fe oxide, montmorillonite, kaolinite, and temperate and tropical soils. Bromide adsorption decreased with increasing solution pH with minimal adsorption occurring above pH 7. Bromide adsorption was higher for amorphous oxides t...

  3. Cross-Couplings Using Aryl Ethers via C-O Bond Activation Enabled by Nickel Catalysts.

    PubMed

    Tobisu, Mamoru; Chatani, Naoto

    2015-06-16

    Arene synthesis has been revolutionized by the invention of catalytic cross-coupling reactions, wherein aryl halides can be coupled with organometallic and organic nucleophiles. Although the replacement of aryl halides with phenol derivatives would lead to more economical and ecological methods, success has been primarily limited to activated phenol derivatives such as triflates. Aryl ethers arguably represent one of the most ideal substrates in terms of availability, cost, safety, and atom efficiency. However, the robust nature of the C(aryl)-O bonds of aryl ethers renders it extremely difficult to use them in catalytic reactions among the phenol derivatives. In 1979, Wenkert reported a seminal work on the nickel-catalyzed cross-coupling of aryl ethers with Grignard reagents. However, it was not until 2004 that the unique ability of a low-valent nickel species to activate otherwise unreactive C(aryl)-O bonds was appreciated with Dankwardt's identification of the Ni(0)/PCy3 system, which significantly expanded the efficiency of the Wenkert reaction. Application of the nickel catalyst to cross-couplings with other nucleophiles was first accomplished in 2008 by our group using organoboron reagents. Later on, several other nucleophiles, including organozinc reagents, amines, hydrosilane, and hydrogen were shown to be coupled with aryl ethers under nickel catalysis. Despite these advances, progress in this field is relatively slow because of the low reactivity of benzene derivatives (e.g., anisole) compared with polyaromatic substrates (e.g., methoxynaphthalene), particularly when less reactive and synthetically useful nucleophiles are used. The "naphthalene problem" has been overcome by the use of N-heterocyclic carbene (NHC) ligands bearing bulky N-alkyl substituents, which enables a wide range of aryl ethers to be coupled with organoboron nucleophiles. Moreover, the use of N-alkyl-substituted NHC ligands allows the use of alkynylmagnesium reagents, thereby realizing

  4. Bearing system

    DOEpatents

    Kapich, Davorin D.

    1987-01-01

    A bearing system includes backup bearings for supporting a rotating shaft upon failure of primary bearings. In the preferred embodiment, the backup bearings are rolling element bearings having their rolling elements disposed out of contact with their associated respective inner races during normal functioning of the primary bearings. Displacement detection sensors are provided for detecting displacement of the shaft upon failure of the primary bearings. Upon detection of the failure of the primary bearings, the rolling elements and inner races of the backup bearings are brought into mutual contact by axial displacement of the shaft.

  5. Nucleophilic arylation with tetraarylphosphonium salts

    PubMed Central

    Deng, Zuyong; Lin, Jin-Hong; Xiao, Ji-Chang

    2016-01-01

    Organic phosphonium salts have served as important intermediates in synthetic chemistry. But the use of a substituent on the positive phosphorus as a nucleophile to construct C–C bond remains a significant challenge. Here we report an efficient transition-metal-free protocol for the direct nucleophilic arylation of carbonyls and imines with tetraarylphosphonium salts in the presence of caesium carbonate. The aryl nucleophile generated from phosphonium salt shows low basicity and good nucleophilicity, as evidenced by the successful conversion of enolizable aldehydes and ketones. The reaction is not particularly sensitive to water, shows wide substrate scope, and is compatible with a variety of functional groups including cyano and ester groups. Compared with the arylmetallic reagents that are usually moisture sensitive, the phosphonium salts are shelf-stable and can be easily handled. PMID:26822205

  6. BippyPhos: a single ligand with unprecedented scope in the Buchwald-Hartwig amination of (hetero)aryl chlorides.

    PubMed

    Crawford, Sarah M; Lavery, Christopher B; Stradiotto, Mark

    2013-12-01

    Over the past two decades, considerable attention has been given to the development of new ligands for the palladium-catalyzed arylation of amines and related NH-containing substrates (i.e., Buchwald-Hartwig amination). The generation of structurally diverse ligands, by research groups in both academia and industry, has facilitated the accommodation of sterically and electronically divergent substrates including ammonia, hydrazine, amines, amides, and NH heterocycles. Despite these achievements, problems with catalyst generality persist and access to multiple ligands is necessary to accommodate all of these NH-containing substrates. In our quest to address this significant limitation we identified the BippyPhos/[Pd(cinnamyl)Cl]2 catalyst system as being capable of catalyzing the amination of a variety of functionalized (hetero)aryl chlorides, as well as bromides and tosylates, at moderate to low catalyst loadings. The successful transformations described herein include primary and secondary amines, NH heterocycles, amides, ammonia and hydrazine, thus demonstrating the largest scope in the NH-containing coupling partner reported for a single Pd/ligand catalyst system. We also established BippyPhos/[Pd(cinnamyl)Cl]2 as exhibiting the broadest demonstrated substrate scope for metal-catalyzed cross-coupling of (hetero)aryl chlorides with NH indoles. Furthermore, the remarkable ability of BippyPhos/[Pd(cinnamyl)Cl]2 to catalyze both the selective monoarylation of ammonia and the N-arylation of indoles was exploited in the development of a new one-pot, two-step synthesis of N-aryl heterocycles from ammonia, ortho-alkynylhalo(hetero)arenes and (hetero) aryl halides through tandem N-arylation/hydroamination reactions. Although the scope in the NH-containing coupling partner is broad, BippyPhos/[Pd(cinnamyl)Cl]2 also displays a marked selectivity profile that was exploited in the chemoselective monoarylation of substrates featuring two chemically distinct NH

  7. Lanthanum Bromide Detectors for Safeguards Measurements

    SciTech Connect

    Wright, J.

    2011-05-25

    Lanthanum bromide has advantages over other popular inorganic scintillator detectors. Lanthanum bromide offers superior resolution, and good efficiency when compared to sodium iodide and lanthanum chloride. It is a good alternative to high purity germanium detectors for some safeguards applications. This paper offers an initial look at lanthanum bromide detectors. Resolution of lanthanum bromide will be compared lanthanum chloride and sodium-iodide detectors through check source measurements. Relative efficiency and angular dependence will be looked at. Nuclear material spectra, to include plutonium and highly enriched uranium, will be compared between detector types.

  8. Visible Light Mediated Photoredox Catalytic Arylation Reactions.

    PubMed

    Ghosh, Indrajit; Marzo, Leyre; Das, Amrita; Shaikh, Rizwan; König, Burkhard

    2016-08-16

    Introducing aryl- and heteroaryl moieties into molecular scaffolds are often key steps in the syntheses of natural products, drugs, or functional materials. A variety of cross-coupling methods have been well established, mainly using transition metal mediated reactions between prefunctionalized substrates and arenes or C-H arylations with functionalization in only one coupling partner. Although highly developed, one drawback of the established sp2-sp2 arylations is the required transition metal catalyst, often in combination with specific ligands and additives. Therefore, photoredox mediated arylation methods have been developed as alternative over the past decade. We begin our survey with visible light photo-Meerwein arylation reactions, which allow C-H arylation of heteroarenes, enones, alkenes, and alkynes with organic dyes, such as eosin Y, as the photocatalyst. A good number of examples from different groups illustrate the broad application of the reaction in synthetic transformations. While initially only photo-Meerwein arylation-elimination processes were reported, the reaction was later extended to photo-Meerwein arylation-addition reactions giving access to the photoinduced three component synthesis of amides and esters from alkenes, aryl diazonium salts, nitriles or formamides, respectively. Other substrates with redox-active leaving groups have been explored in photocatalyzed arylation reactions, such as diaryliodonium and triarylsulfonium salts, and arylsulfonyl chlorides. We discus some examples with their scope and limitations. The scope of arylation reagents for photoredox reactions was extended to aryl halides. The challenge here is the extremely negative reduction potential of aryl halides in the initial electron transfer step compared to, e.g., aryl diazonium or diaryliodonium salts. In order to reach reduction potentials over -2.0 V vs SCE two consecutive photoinduced electron transfer steps were used. The intermediary formed colored radical

  9. A mild and facile synthesis of aryl and alkenyl sulfides via copper-catalyzed deborylthiolation of organoborons with thiosulfonates.

    PubMed

    Yoshida, Suguru; Sugimura, Yasuyuki; Hazama, Yuki; Nishiyama, Yoshitake; Yano, Takahisa; Shimizu, Shigeomi; Hosoya, Takamitsu

    2015-12-01

    An efficient deborylthiolation of aryl- and alkenylborons with thiosulfonates has been achieved under mild conditions using a copper catalyst. All steps of the experimental process were free from unpleasant odors. The mild reaction conditions as well as ready availability of boron compounds and thiosulfonates enabled easy access to an array of sulfides, including those bearing sensitive functional groups. PMID:26447905

  10. Measuring methyl bromide emissions from fields

    SciTech Connect

    Yates, S.R.; Gan, J.; Ernst, F.F.; Yates, M.V.

    1995-12-31

    Methyl bromide is used extensively for pest control. Recent evidence suggests that methyl bromide may react with stratospheric ozone and, due to the Clean Air Act, is scheduled for phase-out within the next 5 to 10 years. As indicated in a recent report from The National Agricultural Pesticide Impact Assessment Program, there will be substantial economic impact on the agricultural community if the use of methyl bromide is restricted. There are several areas of uncertainty concerning the agricultural use of methyl bromide. Foremost is the quantification of mass emitted to the atmosphere from agricultural fields. To address this, two field experiments were conducted to directly measure methyl bromide emissions. In the first experiment, methyl bromide was injected at approximately 25 cm depth and the soil was covered with 1 mil high-density polyethylene plastic. The second experiment was similar except that methyl bromide was injected at approximately 68 cm depth and the soil was not covered. From these experiments, the emission rate into the atmosphere and the subsurface transport of methyl bromide was determined. Both experiments include a field-scale mass balance to verify the accuracy of the flux-measurement methods as well as to check data consistency. The volatilization rate and mass lost was determined from estimates of the degradation and from several atmospheric and chamber flux methods.

  11. 77 FR 35295 - Methyl Bromide; Pesticide Tolerances

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-06-13

    ... AGENCY 40 CFR Part 180 RIN 2070-ZA16 Methyl Bromide; Pesticide Tolerances AGENCY: Environmental... methyl bromide in or on cotton, undelinted seed under the Federal Food, Drug, and Cosmetic Act (FFDCA.... Background In the Federal Register of April 6, 2012 (77 FR 20752) (FRL-9345- 1), EPA issued a proposed...

  12. METHYL BROMIDE ALTERNATIVES FOR VINEYARD REPLANT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soil fumigation with methyl bromide is needed by grape growers in central California to control soilborne pests. However, use of methyl bromide is banned and soil fumigation with other chemicals subjects to strict regulations to protect human health and air quality. The objective was to determine,...

  13. Activation of Aryl Halides by Nickel(I) Pincer Complexes: Reaction Pathways of Stoichiometric and Catalytic Dehalogenations.

    PubMed

    Rettenmeier, Christoph A; Wenz, Jan; Wadepohl, Hubert; Gade, Lutz H

    2016-08-15

    Homolytic C-X bond cleavage of organohalides by the T-shaped nickel(I) complexes [LigNi(I)] 1 bearing the iso-PyrrMeBox ligand had been found previously to be the crucial activation step in the asymmetric hydrodehalogenation of geminal dihalides. Here, this mechanistic investigation is extended to aryl halides, which allowed a systematic study of the activation process by a combination of experimental data and density functional theory modeling. While the activation of both aryl chlorides and geminal dichlorides appears to proceed via an analogous transition state, the generation of a highly stabile nickel(II)aryl species in the reaction of the aryl chlorides for the former represents a major difference in the reactive behavior. This difference was found to have a crucial impact on the activity of these nickel pincer systems as catalysts in the dehalogenation of aryl chlorides compared to geminal dichlorides and highlights the importance of the regulatory pathways controlling the nickel(I) concentration throughout the catalysis. These results along with the identification and characterization of novel nickel(II)aryl species are presented. PMID:27483018

  14. N-Aryl Lactams by Regioselective Ozonation of N-Aryl Cyclic Amines

    PubMed Central

    Saliu, Francesco; Orlandi, Marco; Bruschi, Maurizio

    2012-01-01

    Ozonation of N-aryl-cyclic amines in organic solvents gave N-aryl-lactams regioselectively. In particular, 4-(4-aminophenyl)-morpolin-3-one, a key intermediate in the preparation of factor Xa inhibitors, was obtained in fair yields. The method represents an alternative approach for the lactamization of tertiary N-arylic substrates and is based on a “metal-free” introduction of the carbonyl function into the heterocyclic ring. PMID:24052840

  15. Nickel-catalyzed reductive arylation of activated alkynes with aryl iodides

    PubMed Central

    Dorn, Stephanie C. M.; Olsen, Andrew K; Kelemen, Rachel E.; Shrestha, Ruja; Weix, Daniel J.

    2015-01-01

    The direct, regioselective, and stereoselective arylation of activated alkynes with aryl iodides using a nickel catalyst and manganese reductant is described. The reaction conditions are mild (40 °C in MeOH, no acid or base) and an intermediate organomanganese reagent is unlikely. Functional groups tolerated include halides and pseudohalides, free and protected anilines, and a benzyl alcohol. Other activated alkynes including an amide and a ketone also reacted to form arylated products in good yields. PMID:26028781

  16. N-aryl lactams by regioselective ozonation of N-aryl cyclic amines.

    PubMed

    Saliu, Francesco; Orlandi, Marco; Bruschi, Maurizio

    2012-01-01

    Ozonation of N-aryl-cyclic amines in organic solvents gave N-aryl-lactams regioselectively. In particular, 4-(4-aminophenyl)-morpolin-3-one, a key intermediate in the preparation of factor Xa inhibitors, was obtained in fair yields. The method represents an alternative approach for the lactamization of tertiary N-arylic substrates and is based on a "metal-free" introduction of the carbonyl function into the heterocyclic ring. PMID:24052840

  17. THRUST BEARING

    DOEpatents

    Heller, P.R.

    1958-09-16

    A thrust bearing suitable for use with a rotor or blower that is to rotate about a vertical axis is descrihed. A centrifagal jack is provided so thnt the device may opernte on one hearing at starting and lower speeds, and transfer the load to another bearing at higher speeds. A low viscosity fluid is used to lubricate the higher speed operation bearing, in connection with broad hearing -surfaces, the ability to withstand great loads, and a relatively high friction loss, as contraated to the lower speed operatio;n bearing which will withstand only light thrust loads but is sufficiently frictionfree to avoid bearing seizure during slow speed or startup operation. An axially aligned shaft pin provides the bearing surface for low rotational speeds, but at higher speed, weights operating against spring tension withdraw nthe shaft pin into the bearing proper and the rotor shaft comes in contact with the large bearing surfaces.

  18. Neurological manifestation of methyl bromide intoxication.

    PubMed

    Suwanlaong, Kanokrat; Phanthumchinda, Kammant

    2008-03-01

    Methyl bromide is a highly toxic gas with poor olfactory warning properties. It is widely used as insecticidal fumigant for dry foodstuffs and can be toxic to central and peripheral nervous systems. Most neurological manifestations of methyl bromide intoxication occur from inhalation. Acute toxicity characterized by headache, dizziness, abdominal pain, nausea, vomiting and visual disturbances. Tremor, convulsion, unconsciousness and permanent brain damage may occur in severe poisoning. Chronic exposure can cause neuropathy, pyramidal and cerebellar dysfunction, as well as neuropsychiatric disturbances. The first case of methyl bromide intoxication in Thailand has been described. The patient was a 24-year-old man who worked in a warehouse of imported vegetables fumigated with methyl bromide. He presented with unstable gait, vertigo and paresthesia of both feet, for two weeks. He had a history of chronic exposure to methyl bromide for three years. His fourteen co-workers also developed the same symptoms but less in severity. Neurological examination revealed ataxic gait, decreased pain and vibratory sense on both feet, impaired cerebellar signs and hyperactive reflex in all extremities. The serum concentration of methyl bromide was 8.18 mg/dl. Electrophysilogical study was normal. Magnetic resonance imaging of the brain (MRI) revealed bilateral symmetrical lesion of abnormal hypersignal intensity on T2 and fluid-attenuation inversion recovery (FLAIR) sequences at bilateral dentate nuclei of cerebellum and periventricular area of the fourth ventricle. This incident stresses the need for improvement of worker education and safety precautions during all stages of methyl bromide fumigation. PMID:18575299

  19. Potassium bromide method of infrared sampling

    USGS Publications Warehouse

    Milkey, R.G.

    1958-01-01

    In the preparation of potassium bromide pressed windows for use in the infrared analysis of solids, severe grinding of the potassium bromide powder may produce strong absorption bands that could interfere seriously with the spectra of the sample. These absorption bands appear to be due to some crystal alteration of the potassium bromide as a result of the grinding process. They were less apt to occur when the coarser powder, which had received a relatively gentle grinding, was used. Window blanks prepared from the coarser powders showed smaller adsorbed water peaks and generally higher over-all transmittance readings than windows pressed from the very fine powders.

  20. Evaluation of O-alkyl and aryl sulfonyl aromatic and heteroaromatic amidoximes as novel potent DNA photo-cleavers.

    PubMed

    Papastergiou, A; Perontsis, S; Gritzapis, P; Koumbis, A E; Koffa, M; Psomas, G; Fylaktakidou, K C

    2016-03-01

    Several stable O-alkyl and aryl sulfonyl conjugated p-nitro-Ph and o-, m-, p-pyridine N'-hydroxy imidamides, were subjected to UV irradiation at 312 nm with supercoiled circular plasmid DNA pBluescript KS II. The generated amidinyl and sulfonyloxyl radicals led to effective DNA photo-cleavage. Both alkyl and aryl sulfonyl derivatives were active and the order p-pyridine > p-nitro-Ph > o-pyridine > m-pyridine was schematized for the N'-hydroxy imidamides moiety. Calf thymus-DNA affinity studies which comprised UV interactions, viscosity experiments and competitive studies with ethidium bromide showed good to excellent affinity of the compounds. These properties revealed sulfonyl amidoximes as novel effective DNA-photo-cleavers and may serve in the discovery of new leads for "on demand" biotechnological and medical applications. PMID:26959855

  1. Regioselective Radical Arylation of 3-Hydroxypyridines.

    PubMed

    Fürst, Michael C D; Bock, Leonard R; Heinrich, Markus R

    2016-07-01

    The titanium(III)-mediated radical arylation of 3-hydroxypyridines was found to proceed with high regioselectivity for the 2-position. Using aryldiazonium chlorides, which were prepared from the corresponding anilines, as aryl radical sources, a range of 3-hydroxy-2-phenylpyridines were obtained in moderate to good yields under simple reaction conditions. Reactions of ortho-carboxylic ester substituted phenyldiazonium salts directly provided tricyclic benzopyranopyridinones. PMID:27258367

  2. Journal bearing

    DOEpatents

    Menke, John R.; Boeker, Gilbert F.

    1976-05-11

    1. An improved journal bearing comprising in combination a non-rotatable cylindrical bearing member having a first bearing surface, a rotatable cylindrical bearing member having a confronting second bearing surface having a plurality of bearing elements, a source of lubricant adjacent said bearing elements for supplying lubricant thereto, each bearing element consisting of a pair of elongated relatively shallowly depressed surfaces lying in a cylindrical surface co-axial with the non-depressed surface and diverging from one another in the direction of rotation and obliquely arranged with respect to the axis of rotation of said rotatable member to cause a flow of lubricant longitudinally along said depressed surfaces from their distal ends toward their proximal ends as said bearing members are rotated relative to one another, each depressed surface subtending a radial angle of less than 360.degree., and means for rotating said rotatable bearing member to cause the lubricant to flow across and along said depressed surfaces, the flow of lubricant being impeded by the non-depressed portions of said second bearing surface to cause an increase in the lubricant pressure.

  3. Lithium choreography: intramolecular arylations of carbamate-stabilised carbanions and their mechanisms probed by in situ IR spectroscopy and DFT calculations.

    PubMed

    Fournier, Anne M; Nichols, Christopher J; Vincent, Mark A; Hillier, Ian H; Clayden, Jonathan

    2012-12-14

    Deprotonation of O-allyl, O-propargyl or O-benzyl carbamates in the presence of a lithium counterion leads to carbamate-stabilised organolithium compounds that may be quenched with electrophiles. We now report that when the allylic, propargylic or benzylic carbamate bears an N-aryl substituent, an aryl migration takes place, leading to stereochemical inversion and C-arylation of the carbamate α to oxygen. The aryl migration is an intramolecular S(N) Ar reaction, despite the lack of anion-stabilising aryl substituents. Our in situ IR studies reveal a number of intermediates along the rearrangement pathway, including a "pre-lithiation complex," the deprotonated carbamate, the rearranged anion, and the final arylated carbamate. No evidence was obtained for a dearomatised intermediate during the aryl migration. DFT calculations predict that during the reaction the solvated Li cation moves from the carbanion centre, thus freeing its lone pair for nucleophilic attack on the remote phenyl ring. This charge separation leads to several alternative conformations. The one having Li(+) bound to the carbamate oxygen gives rise to the lowest-energy transition structure, and also leads to inversion of the configuration. In agreement with the IR studies, the DFT calculations fail to locate a dearomatised intermediate. PMID:23097264

  4. Oligo(N-aryl glycines): a new twist on structured peptoids.

    PubMed

    Shah, Neel H; Butterfoss, Glenn L; Nguyen, Khanh; Yoo, Barney; Bonneau, Richard; Rabenstein, Dallas L; Kirshenbaum, Kent

    2008-12-10

    We explore strategies to enhance conformational ordering of N-substituted glycine peptoid oligomers. Peptoids bearing bulky N-alkyl side chains have previously been studied as important examples of biomimetic "foldamer" compounds, as they exhibit a capacity to populate helical structures featuring repeating cis-amide bonds. Substantial cis/trans amide bond isomerization, however, gives rise to conformational heterogeneity. Here, we report the use of N-aryl side chains as a tool to enforce the presence of trans-amide bonds, thereby engendering structural stability. Aniline derivatives and bromoacetic acid are used in the facile solid-phase synthesis of a diverse family of sequence-specific N-aryl glycine oligomers. Quantum mechanics calculations yield a detailed energy profile of the folding landscape and substantiate the hypothesis that the presence of anilide groups establishes a strong energetic preference for trans-amide bonds. X-ray crystallographic analysis and solution NMR studies verify this preference. Molecular modeling indicates that the linear oligomers can adopt helical structures resembling a polyproline type II helix. High resolution structures of macrocyclic oligomers incorporating both N-alkyl and N-aryl glycine units confirm the ability to direct the presence of trans-amide bonds specifically at N-aryl positions. These results are an important step in developing strategies for the rational de novo design of new structural motifs in biomimetic oligopeptoid systems. PMID:19049458

  5. Emission of methyl bromide from biomass burning

    SciTech Connect

    Manoe, S.; Andreae, M.O. )

    1994-03-04

    Bromine is, per atom, far more efficient than chlorine in destroying stratospheric ozone, and methyl bromide is the single largest source of stratospheric bromine. The two main previously known sources of this compound are emissions from the ocean and from the compound's use as an agricultural pesticide. Laboratory biomass combustion experiments showed that methyl bromide was emitted in the smoke from various fuels tested. Methyl bromide was also found in smoke plumes from wildfires in savannas, chaparral, and boreal forest. Global emissions of methyl bromide from biomass burning are estimated to be in the range of 10 to 50 gigagrams per year, which is comparable to the amount produced by ocean emission and pesticide use and represents a major contribution ([approximately]30 percent) to the stratospheric bromine budget.

  6. Growth and characterization of lead bromide crystals

    NASA Technical Reports Server (NTRS)

    Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Glicksman, M. E.; Coriell, S. R.; Santoro, G. J.; Duval, W. M. B.

    1992-01-01

    Lead(II) bromide was purified by a combination of directional freezing and zone-refining methods. Differential thermal analysis of the lead bromide showed that a destructive phase transformation occurs below the melting temperature. This transformation causes extensive cracking, making it very difficult to grow a large single crystal. Energy of phase transformation for pure lead bromide was determined to be 24.67 cal/g. To circumvent this limitation, crystals were doped by silver bromide which decreased the energy of phase transformation. The addition of silver helped in achieving the size, but enhanced the inhomogeneity in the crystal. The acoustic attenuation constant was almost identical for the pure and doped (below 3000 ppm) crystals.

  7. Investigation of drug interactions with pinaverium bromide.

    PubMed

    Devred, C; Godeau, P; Guerot, C; Librez, P; Mougeot, G; Orsetti, A; Segrestaa, J M

    1986-01-01

    A series of studies was carried out at 6 centres to investigate possible drug interaction between the spasmolytic, pinaverium bromide, and cardiac glycosides, anticoagulants and hypoglycaemic agents given to patients as part of the long-term treatment of their condition. The results of clinical and laboratory investigations did not show any evidence of pinaverium bromide interfering with the action or activity of any of the drugs studied. PMID:3084176

  8. Reductive carbonylation of aryl halides employing a two-chamber reactor: a protocol for the synthesis of aryl aldehydes including 13C- and D-isotope labeling.

    PubMed

    Korsager, Signe; Taaning, Rolf H; Lindhardt, Anders T; Skrydstrup, Troels

    2013-06-21

    A protocol has been developed for conducting the palladium-catalyzed reductive carbonylation of aryl iodides and bromides using 9-methylfluorene-9-carbonyl chloride (COgen) as a source of externally delivered carbon monoxide in a sealed two-chamber system (COware), and potassium formate as the in situ hydride source. The method is tolerant to a wide number of functional groups positioned on the aromatic ring, and it can be exploited for the isotope labeling of the aldehyde group. Hence, reductive carbonylations run with (13)COgen provide a facile access to (13)C-labeled aromatic aldehydes, whereas with DCO2K, the aldehyde is specifically labeled with deuterium. Two examples of double isotopic labeling are also demonstrated. Finally, the method was applied to the specific carbon-13 labeling of the β-amyloid binding compound, florbetaben. PMID:23692554

  9. Toward Optimization of the Second Aryl Substructure Common to Transthyretin Amyloidogenesis Inhibitors Using Biochemical and Structural Studies

    PubMed Central

    Johnson, Steven M.; Connelly, Stephen; Wilson, Ian A.; Kelly, Jeffery W.

    2009-01-01

    Transthyretin (TTR) amyloidogenesis inhibitors are typically composed of two aromatic rings and a linker. We have previously established optimal structures for one aromatic ring and the linker. Herein, we employ a suboptimal linker and an optimal aryl-X substructure to rank order the desirability of aryl-Z substructures–using a library of 56 N-(3,5-dibromo-4-hydroxyphenyl)benzamides. Co-consideration of amyloid inhibition potency and ex-vivo plasma TTR binding selectivity data reveal that 2,6; 2,5; 2; 3,4,5 and 3,5 aryls bearing small substituents generate the most potent and selective inhibitors, in descending order. These benzamides generally lack undesirable thyroid hormone receptor binding and COX-1 inhibition activity. Three high-resolution TTR•inhibitor crystal structures (1.31-1.35 Å) provide insight into why these inhibitors are potent and selective, enabling future structure-based design of TTR kinetic stabilizers. PMID:19191553

  10. Functionalization of 2H-1,2,3-Triazole C-Nucleoside Template via N(2) Selective Arylation.

    PubMed

    Lopes, Alexandra Basilio; Wagner, Patrick; de Souza, Rodrigo Octavio Mendonça Alves; Germain, Nadège Lubin; Uziel, Jacques; Bourguignon, Jean-Jacques; Schmitt, Martine; Miranda, Leandro S M

    2016-06-01

    C-Nucleosides are an underexplored and important class of nucleosides with antiviral and anticancer activity. In addition, triazole heterocycles are well employed as a strategy to modify nucleobase in nucleoside analogues, although rare examples were described for triazoyl C-nucleosides. N(2)-Aryl-1,2,3-triazole C-nucleoside compounds that could be obtained by selective 1,2,3-triazole heterocycle N(2) arylation in 1-β-d-ribofuranosyl-2H-1,2,3-triazole substrate were designed in this study. The optimized condition used AdBrettPhos/[PdCl(allyl)]2 as the catalyst system. This transformation was accomplished by aryl halides bearing an electron donor and withdrawing groups, as well as by heterocyclic halides in good to excellent yields. The transformation developed in this study represents a significant contribution to the nucleoside field, once it allows for the synthesis of unexplored scaffolds through selective functionalization of triazole nucleosides. PMID:27166644

  11. Ru-Catalysed C–H Arylation of Indoles and Pyrroles with Boronic Acids: Scope and Mechanistic Studies

    PubMed Central

    Sollert, Carina; Devaraj, Karthik; Orthaber, Andreas; Gates, Paul J; Pilarski, Lukasz T

    2015-01-01

    The Ru-catalysed C2–H arylation of indoles and pyrroles by using boronic acids under oxidative conditions is reported. This reaction can be applied to tryptophan derivatives and tolerates a wide range of functional groups on both coupling partners, including bromides and iodides, which can be further derivatised selectively. New indole-based ruthenacyclic complexes are described and investigated as possible intermediates in the reaction. Mechanistic studies suggest the on-cycle intermediates do not possess a para-cymene ligand and that the on-cycle metalation occurs through an electrophilic attack by the Ru centre. PMID:25689052

  12. A novel 4-aminoantipyrine-Pd(II) complex catalyzes Suzuki–Miyaura cross-coupling reactions of aryl halides

    PubMed Central

    Mendoza-Rayo, Darío; Rincón-Medina, José A; Chacón-García, Luis

    2014-01-01

    Summary A simple and efficient catalytic system based on a Pd complex of 4-aminoantipyrine, 4-AAP–Pd(II), was found to be highly active for Suzuki–Miyaura cross-coupling of aryl iodides and bromides with phenylboronic acids under mild reaction conditions. Good to excellent product yields from the cross-coupling reaction can be achieved when the reaction is carried out in ethanol, in the open air, using low loading of 4-AAP–Pd(II) as a precatalyst, and in the presence of aqueous K2CO3 as the base. A variety of functional groups are tolerated. PMID:25550748

  13. Ligand-Mediated and Copper-Catalyzed C(sp3)-H Bond Functionalization of Aryl Ketones with Sodium Sulfinates under Mild Conditions

    NASA Astrophysics Data System (ADS)

    Lan, Xing-Wang; Wang, Nai-Xing; Bai, Cui-Bing; Zhang, Wei; Xing, Yalan; Wen, Jia-Long; Wang, Yan-Jing; Li, Yi-He

    2015-12-01

    A novel and convenient copper (II) bromide and 1,8-diazabicyclo[5.4.1]undec-7-ene (DBU) or 1,10-phenanthroline catalysis protocol for the construction of α-alkyl-β-keto sulfones via C(sp3)-H bond functionalization followed by C(sp3)-S bond formation between aryl ketones and sodium sulfinates at room temperature has been developed. This method is applicable to a wide range of aryl ketones and sodium sulfinates. The electronic effects of aryl ketones and ligands effects of the copper salts are crucial for this transformation. Typically, substituted aryl ketones with electron-withdrawing group do not need any ligand to give a good to excellent yield, while substituted aryl ketones with electron-donating group and electron-rich heteroaromatic ketones offer a good to excellent yield only under the nitrogen-based ligands. The practical value of this transformation highlights the efficient and robust one-pot synthesis of α-alkyl-β-keto sulfones.

  14. Ligand-Mediated and Copper-Catalyzed C(sp3)-H Bond Functionalization of Aryl Ketones with Sodium Sulfinates under Mild Conditions

    PubMed Central

    Lan, Xing-Wang; Wang, Nai-Xing; Bai, Cui-Bing; Zhang, Wei; Xing, Yalan; Wen, Jia-Long; Wang, Yan-Jing; Li, Yi-He

    2015-01-01

    A novel and convenient copper (II) bromide and 1,8-diazabicyclo[5.4.1]undec-7-ene (DBU) or 1,10-phenanthroline catalysis protocol for the construction of α-alkyl-β-keto sulfones via C(sp3)-H bond functionalization followed by C(sp3)-S bond formation between aryl ketones and sodium sulfinates at room temperature has been developed. This method is applicable to a wide range of aryl ketones and sodium sulfinates. The electronic effects of aryl ketones and ligands effects of the copper salts are crucial for this transformation. Typically, substituted aryl ketones with electron-withdrawing group do not need any ligand to give a good to excellent yield, while substituted aryl ketones with electron-donating group and electron-rich heteroaromatic ketones offer a good to excellent yield only under the nitrogen-based ligands. The practical value of this transformation highlights the efficient and robust one-pot synthesis of α-alkyl-β-keto sulfones. PMID:26681470

  15. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations... bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. (a) Bromoacetone must...

  16. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations... bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. (a) Bromoacetone must...

  17. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations... bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. (a) Bromoacetone must...

  18. Grizzly bear

    USGS Publications Warehouse

    Schwartz, C.C.; Miller, S.D.; Haroldson, M.A.

    2003-01-01

    The grizzly bear inspires fear, awe, and respect in humans to a degree unmatched by any other North American wild mammal. Like other bear species, it can inflict serious injury and death on humans and sometimes does. Unlike the polar bear (Ursus maritimus) of the sparsely inhabited northern arctic, however, grizzly bears still live in areas visited by crowds of people, where presence of the grizzly remains physically real and emotionally dominant. A hike in the wilderness that includes grizzly bears is different from a stroll in a forest from which grizzly bears have been purged; nighttime conversations around the campfire and dreams in the tent reflect the presence of the great bear. Contributing to the aura of the grizzly bear is the mixture of myth and reality about its ferocity. unpredictable disposition, large size, strength, huge canines, long claws, keen senses, swiftness, and playfulness. They share characteristics with humans such as generalist life history strategies. extended periods of maternal care, and omnivorous diets. These factors capture the human imagination in ways distinct from other North American mammals. Precontact Native American legends reflected the same fascination with the grizzly bear as modern stories and legends (Rockwell 1991).

  19. The Remarkable Reactivity of Aryl Halides with Nucleophiles

    ERIC Educational Resources Information Center

    Bunnett, Joseph F.

    1974-01-01

    Discusses the reactivity of aryl halides with nucleophilic or basic reagents, including nucleophilic attacks on carbon, hydrogen, halogen, and arynes. Suggestions are made concerning revisions of the sections on aryl halide chemistry courses and the corresponding chapters in textbooks. (CC)

  20. Polar Bear

    USGS Publications Warehouse

    Amstrup, S.D.; DeMaster

    1988-01-01

    Polar bears are long-lived, late-maturing carnivores that have relatively low rates of reproduction and natural mortality. Their populations are susceptible to disturbance from human activities, such as the exploration and development of mineral resources or hunting. Polar bear populations have been an important renewable resource available to coastal communities throughout the Arctic for thousands of years.

  1. Human Skin Aryl Hydrocarbon Hydroxylase

    PubMed Central

    Bickers, David R.; Kappas, Attallah

    1978-01-01

    Coal tar products, which are widely used in treating dermatologic disease, contain numerous polycyclic aromatic hydrocarbons, including 3,4-benzo[a]pyrene (BP). BP is among the most potent environmental chemical carcinogens and is known to evoke tumors in the skin of experimental animals and perhaps also of man. In this study the effect of cutaneous application of coal tar solution (U. S. Pharmacopeia) on aryl hydrocarbon hydroxylase (AHH) activity in the skin of patients usually treated with this drug was investigated. AHH, a cytochrome P-450 dependent carcinogen-metabolizing enzyme appears to play an important role in the activation of polycyclic hydrocarbons into reactive moieties that can bind to DNA and that may directly induce cancer. Application of coal tar solution to human skin caused a two to five-fold induction of cutaneous AHH in nine subjects. In further studies, the incubation of human skin with coal tar solution in vitro also caused variable induction of cutaneous AHH. Maximum responses in both systems occurred after 24 h and enzyme activity in vitro was time- and tissue- and substrate-concentration dependent. Studies in experimental animals showed that topical application of coal tar solution caused induction of AHH in skin and, after percutaneous absorption, in liver as well. Assay of several defined constituents of coal tar for AHH induction showed that BP was the most potent inducer of AHH tested. These studies indicate that topical application of coal tar solution in doses ordinarily used in treating dermatologic disease causes induction of AHH in human skin and suggest that such induced enzymatic activity could relate to carcinogenic responses to this agent in skin or, after percutaneous absorption, in other tissues as well. PMID:711851

  2. Half-sandwich nickel(II) complexes bearing 1,3-di(cycloalkyl)imidazol-2-ylidene ligands

    PubMed Central

    Yau, Johnathon; Hunt, Kaarel E; McDougall, Laura; Kennedy, Alan R

    2015-01-01

    Summary Two new nickel catalysts have been prepared using a convenient procedure where nickelocene, the NHC·HBF4 salts, and [Et4N]Cl were heated in THF using microwave irradiation. The resulting [NiCl(Cp)(NHC)] complexes are air- and moisture stable in the solid state, and represent two new members of this valuable and practical class of nickel catalysts. The new species were fully characterised using methods including NMR spectroscopy and X-ray crystallography. When tested in model Suzuki–Miyaura cross-coupling reactions, these complexes were found to be active for the cross-coupling of aryl bromides and aryl chlorides. PMID:26664639

  3. Half-sandwich nickel(II) complexes bearing 1,3-di(cycloalkyl)imidazol-2-ylidene ligands.

    PubMed

    Yau, Johnathon; Hunt, Kaarel E; McDougall, Laura; Kennedy, Alan R; Nelson, David J

    2015-01-01

    Two new nickel catalysts have been prepared using a convenient procedure where nickelocene, the NHC·HBF4 salts, and [Et4N]Cl were heated in THF using microwave irradiation. The resulting [NiCl(Cp)(NHC)] complexes are air- and moisture stable in the solid state, and represent two new members of this valuable and practical class of nickel catalysts. The new species were fully characterised using methods including NMR spectroscopy and X-ray crystallography. When tested in model Suzuki-Miyaura cross-coupling reactions, these complexes were found to be active for the cross-coupling of aryl bromides and aryl chlorides. PMID:26664639

  4. [The clinical pharmacological profile of pinaverium bromide].

    PubMed

    Guslandi, M

    1994-04-01

    Pinaverium bromide is a locally acting spasmolytic agent of the digestive tract. Its mechanism of action relies upon inhibition of calcium ion entrance into smooth muscle cells (calcium-antagonist effect). In humans pinaverium facilitates gastric emptying and decreases intestinal transit time in patients with constipation. Pinaverium is very effective in improving symptoms of irritable bowel syndrome (abdominal pain, gas, diarrhea or constipation). In this respect the drug proved to be significantly superior to placebo, at least as effective as trimebutine and on the whole more active than otilonium and prifinium bromide, being always extremely well tolerated. PMID:8028745

  5. Effects of pinaverium bromide on Oddi's sphincter.

    PubMed

    DiSomma, C; Reboa, G; Patrone, M G; Mortola, G P; Sala, G; Ciampini, M

    1986-01-01

    Twelve to 15 days after cholecystectomy, endocholedochal pressure was measured in ten patients before and one hour after oral administration of 15 mg of pinaverium bromide (six patients) or placebo. The mean endocholedochal pressure was 7.1 +/- 0.25 mmHg before and 3.1 +/- 0.2 mmHg after pinaverium (P less than 0.01), and 7.0 +/- 0.2 and 6.8 +/- 1.2 mmHg in the placebo-treated patients. The results suggest that pinaverium bromide has a specific effect on the common bile duct and probably on Oddi's sphincter. PMID:3815457

  6. Magnetic Bearing

    NASA Technical Reports Server (NTRS)

    1996-01-01

    AVCON, Inc. produces advanced magnetic bearing systems for industrial use, offering a unique technological approach based on contract work done at Marshall Space Flight Center and Lewis Research Center. Designed for the turbopump of the Space Shuttle main engine, they are now used in applications such as electric power generation, petroleum refining, machine tool operation and natural gas pipelines. Magnetic bearings support moving machinery without physical contact; AVCON's homopolar approach is a hybrid of permanent and electromagnets which are one-third the weight, smaller and more power- efficient than previous magnetic bearings.

  7. Iridium-catalysed dehydrocoupling of aryl phosphine-borane adducts: synthesis and characterisation of high molecular weight poly(phosphinoboranes).

    PubMed

    Paul, Ursula S D; Braunschweig, Holger; Radius, Udo

    2016-06-30

    The thermal dehydrogenative coupling of aryl phosphine-borane adducts with iridium complexes bearing a bis(phosphinite) pincer ligand is reported. This catalysis produces high molecular weight poly(phosphinoboranes) [ArPH-BH2]n (Ar = Ph, (p)Tol, Mes). Furthermore, we investigated the reactivity of these pincer complexes towards primary phosphines and their respective borane adducts on a stoichiometric scale. PMID:27320239

  8. Foil bearings

    NASA Technical Reports Server (NTRS)

    Elrod, David A.

    1993-01-01

    The rolling element bearings (REB's) which support many turbomachinery rotors offer high load capacity, low power requirements, and durability. Two disadvantages of REB's are: (1) rolling or sliding contact within the bearing has life-limiting consequences; and (2) REB's provide essentially no damping. The REB's in the Space Shuttle Main Engine (SSME) turbopumps must sustain high static and dynamic loads, at high speeds, with a cryogenic fluid as lubricant and coolant. The pump end ball bearings limit the life of the SSME high pressure oxygen turbopump (HPOTP). Compliant foil bearing (CFB) manufacturers have proposed replacing turbopump REB's with CFB's CFB's work well in aircraft air cycle machines, auxiliary power units, and refrigeration compressors. In a CFB, the rotor only contracts the foil support structure during start up and shut down. CFB damping is higher than REB damping. However, the load capacity of the CFB is low, compared to a REB. Furthermore, little stiffness and damping data exists for the CFB. A rotordynamic analysis for turbomachinery critical speeds and stability requires the input of bearing stiffness and damping coefficients. The two basic types of CFB are the tension-dominated bearing and the bending-dominated bearing. Many investigators have analyzed and measured characteristics of tension-dominated foil bearings, which are applied principally in magnetic tape recording. The bending-dominated CFB is used more in rotating machinery. This report describes the first phase of a structural analysis of a bending-dominated, multileaf CFB. A brief discussion of CFB literature is followed by a description and results of the present analysis.

  9. Base-Free Conditions for Rhodium-Catalyzed Asymmetric Arylation To Produce Stereochemically Labile α-Aryl Ketones.

    PubMed

    Dou, Xiaowei; Lu, Yixin; Hayashi, Tamio

    2016-06-01

    The asymmetric arylation of 2,2-dialkyl cyclopent-4-ene-1,3-diones with aryl boronic acids was found to be efficiently catalyzed by a chiral diene-rhodium μ-chloro dimer, [{RhCl((R)-diene*)}2 ], in the absence of bases in toluene/H2 O to give 2,2-dialkyl 4-aryl cyclopentane-1,3-diones in high yields with high enantioselectivity. Such compounds can not be obtained with high enantiomeric purity under the standard basic conditions used for rhodium-catalyzed asymmetric arylation because the α-aryl ketone products undergo racemization under the basic conditions. PMID:27100902

  10. Methyl Bromide Alternatives for Vineyard Replant

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The project is part of the USDA-ARS Pacific Area-Wide Pest Management Program for Methyl Bromide Alternatives. This is the first year of a three-year project. The research was initiated in summer 2007 with a field study planned for October 2007 at the USDA-ARS San Joaquin Valley Agricultural Scienc...

  11. METHYL BROMIDE ALTERNATIVES FOR CALIFORNIA STRAWBERRY NURSERIES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effects of methyl bromide (MB) alternative fumigants on soil pests, plant productivity in nursery and fruiting fields, as well as production costs, were evaluated in California strawberry nurseries by an interdisciplinary team. Our trials followed nursery stock through low and high elevation ph...

  12. Zinc Bromide Waste Solution Treatment Options

    SciTech Connect

    Langston, C.A.

    2001-01-16

    The objective of this effort was to identify treatment options for 20,000 gallons of low-level radioactively contaminated zinc bromide solution currently stored in C-Area. These options will be relevant when the solutions are declared waste.

  13. Challenges in Weed Management Without Methyl Bromide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide has been used for several decades for pre-plant soil fumigation in high value agricultural and horticultural crops because it can provide broad-spectrum control of insects, nematodes, pathogens, and weeds. However, MeBr has been identified as a powerful ozone-depleting chemical and i...

  14. Methyl bromide emissions from tarped fields

    SciTech Connect

    Cicerone, R.J.; Williams, J.; Wang, N.Y.

    1995-12-31

    Once in the stratosphere, bromine atoms can destroy ozone effectively. Because of this potential effect, certain organobromine compounds including methyl bromide (MeBr) are being controlled or eliminated by national and international regulations. It would be valuable to determine the fraction of MeBr used in soil fumigations that subsequently enters the atmosphere to better assess the need for, and value of, strong regulations. We have designed and conducted several experiments accompanying field fumigations with MeBr/chloropicrin mixtures. In each of three field-fumigation experiments new Irvine, CA in which the fumigated field was covered immediately with plastic tarping, we have deployed static flux chambers on top of the tarping and measured escape fluxes of MeBr. After tarp removal, the same chambers were replaced on the bare soil to continue the measurements. We have also measured soil bromide contents before and after the fumigation. One experiment yielded an escape fraction of 80 to 87% (with 19% remaining as bromide) while the other two experiments yielded escape fractions of 30 to 35% (with about 70% remaining as bromide). This paper will summarize stratospheric bromine chemistry, describe the field experiments and discuss factors that influence emissions, including soil pH, moisture and organic content and injection technique. We acknowledge TriCal, Inc. for many helpful discussions and for professional field applications of MeBr.

  15. Can Georgia growers replace methyl bromide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The price and availability of methyl bromide is limiting its use on Georgia farms; the need for an alternative is essential for sustainable vegetable production in GA. Three alternatives were evaluated in on-farm trials in the spring 2007 in Tift, Colquitt and Echols Counties. Treatments were replic...

  16. Synthesis of fluorescent (benzyloxycarbonylamino)(aryl)methylphosphonates.

    PubMed

    Górniak, Michał Górny Vel; Czernicka, Anna; Młynarz, Piotr; Balcerzak, Waldemar; Kafarski, Paweł

    2014-01-01

    The synthesis of a library of structurally variable aromatic esters of (benzyloxycarbonylamino)(aryl)methylphosphonic acids is described by means of the Oleksyszyn reaction. The library was enlarged by the application of a Suzuki-Miayra approach and by preparation of mixed esters. PMID:24778727

  17. Arylation and Heteroarylation of Thienylsulfonamides with Organotrifluoroborates

    PubMed Central

    2015-01-01

    A mild, practical protocol has been developed for the Suzuki cross-coupling of unprotected thienylsulfonamides from air- and bench-stable organotrifluoroborates in the absence of a protecting group on the sulfonamide nitrogen. The developed synthetic method can be applied to the preparation of various arylated and heteroarylated thienylsulfonamides under conditions that are tolerant of a broad range of functional groups. PMID:25019222

  18. Alkyl and aryl sulfonyl p-pyridine ethanone oximes are efficient DNA photo-cleavage agents.

    PubMed

    Andreou, Nicolaos-Panagiotis; Dafnopoulos, Konstantinos; Tortopidis, Christos; Koumbis, Alexandros E; Koffa, Maria; Psomas, George; Fylaktakidou, Konstantina C

    2016-05-01

    Sulfonyloxyl radicals, readily generated upon UV irradiation of p-pyridine sulfonyl ethanone oxime derivatives, effectively cleave DNA, in a pH independent manner, and under either aerobic or anaerobic conditions. p-Pyridine sulfonyl ethanone oxime derivatives were synthesized from the reaction of p-pyridine ethanone oxime with the corresponding sulfonyl chlorides in good to excellent yields. All compounds, at a concentration of 100μM, were irradiated at 312nm for 15min, after incubation with supercoiled circular pBluescript KS II DNA and resulted in extended single- and double- strand cleavages. The cleavage ability was found to be concentration dependent, with some derivatives exhibiting activity even at nanomolar levels. Besides that, p-pyridine sulfonyl ethanone oxime derivatives showed good affinity to DNA, as it was observed with UV interaction and viscosity experiments with CT DNA and competitive studies with ethidium bromide. The compounds interact to CT DNA probably by non-classical intercalation (i.e. groove-binding) and at a second step they may intercalate within the DNA base pairs. The fluorescence emission spectra of pre-treated EB-DNA exhibited a significant or moderate quenching. Comparing with the known aryl carbonyloxyl radicals the sulfonyloxyl ones are more powerful, with both aryl and alkyl sulfonyl substituted derivatives to exhibit DNA photo-cleaving ability, in significantly lower concentrations. These properties may serve in the discovery of new leads for "on demand" biotechnological and medical applications. PMID:26945644

  19. Crystal structures of five 1-alkyl-4-aryl-1,2,4-triazol-1-ium halide salts.

    PubMed

    Guino-O, Marites A; Talbot, Meghan O; Slitts, Michael M; Pham, Theresa N; Audi, Maya C; Janzen, Daron E

    2015-06-01

    The asymmetric units for the salts 4-(4-fluoro-phen-yl)-1-isopropyl-1,2,4-triazol-1-ium iodide, C11H13FN3 (+)·I(-), (1), 1-isopropyl-4-(4-methyl-phen-yl)-1,2,4-triazol-1-ium iodide, C12H16N3 (+)·I(-), (2), 1-isopropyl-4-phenyl-1,2,4-triazol-1-ium iodide, C11H14N3 (+)·I(-), (3), and 1-methyl-4-phenyl-1,2,4-triazol-1-ium iodide, C9H10N3 (+)·I(-), (4), contain one cation and one iodide ion, whereas in 1-benzyl-4-phenyl-1,2,4-triazol-1-ium bromide monohydrate, C15H14N3 (+)·Br(-)·H2O, (5), there is an additional single water mol-ecule. There is a predominant C-H⋯X(halide) inter-action for all salts, resulting in a two-dimensional extended sheet network between the triazolium cation and the halide ions. For salts with para-substitution on the aryl ring, there is an additional π-anion inter-action between a triazolium carbon and iodide displayed by the layers. For salts without the para-substitution on the aryl ring, the π-π inter-actions are between the triazolium and aryl rings. The melting points of these salts agree with the predicted substituent inductive effects. PMID:26090137

  20. A comparison of the action of otilonium bromide and pinaverium bromide: study conducted under clinical control.

    PubMed

    Defrance, P; Casini, A

    1991-11-01

    We studied 40 patients with irritable bowel syndrome (IBS) which received in a simple-blind fashion otilonium and pinaverium bromide (15 days each drug). During each 15-day period we evaluated: number of pain episodes, intensity of pain, number of bowel movements, side effects. Otilonium bromide, (OB), compared with pinaverium bromide was able to significantly (p less than 0.05) reduce the number of pain attacks, whereas no significant differences were found between the 2 groups as regards the other parameters. The occurrence of side effects was similar in the two treatment courses. We can conclude that the two types of treatment were similarly useful in IBS, although OB seems more effective than pinaverium bromide. PMID:1756286

  1. Seismic bearing

    NASA Astrophysics Data System (ADS)

    Power, Dennis

    2009-05-01

    Textron Systems (Textron) has been using geophones for target detection for many years. This sensing capability was utilized for detection and classification purposes only. Recently Textron has been evaluating multiaxis geophones to calculate bearings and track targets more specifically personnel. This capability will not only aid the system in locating personnel in bearing space or cartesian space but also enhance detection and reduce false alarms. Textron has been involved in the testing and evaluation of several sensors at multiple sites. One of the challenges of calculating seismic bearing is an adequate signal to noise ratio. The sensor signal to noise ratio is a function of sensor coupling to the ground, seismic propagation and range to target. The goals of testing at multiple sites are to gain a good understanding of the maximum and minimum ranges for bearing and detection and to exploit that information to tailor sensor system emplacement to achieve desired performance. Test sites include 10A Site Devens, MA, McKenna Airfield Ft. Benning, GA and Yuma Proving Ground Yuma, AZ. Geophone sensors evaluated include a 28 Hz triax spike, a 15 Hz triax spike and a hybrid triax spike consisting of a 10 Hz vertical geophone and two 28 Hz horizontal geophones. The algorithm uses raw seismic data to calculate the bearings. All evaluated sensors have triaxial geophone configuration mounted to a spike housing/fixture. The suite of sensors also compares various types of geophones to evaluate benefits in lower bandwidth. The data products of these tests include raw geophone signals, seismic features, seismic bearings, seismic detection and GPS position truth data. The analyses produce Probability of Detection vs range, bearing accuracy vs range, and seismic feature level vs range. These analysis products are compared across test sites and sensor types.

  2. Reactions of nitroxides XIII: Synthesis of the Morita–Baylis–Hillman adducts bearing a nitroxyl moiety using 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a starting compound, and DABCO and quinuclidine as catalysts

    PubMed Central

    2012-01-01

    Summary The Morita–Baylis–Hillman adducts bearing a nitroxyl moiety were synthesized from 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl and aliphatic, aryl and heterocyclic aldehydes. PMID:23019486

  3. Cu(I)-catalyzed N,N’-diarylation of natural diamines and polyamines with aryl iodides

    PubMed Central

    Panchenko, Svetlana Petrovna; Averin, Alexei Dmitrievich; Anokhin, Maksim Viktorovich; Maloshitskaya, Olga Aleksandrovna

    2015-01-01

    Summary The Cu(I)-catalyzed N,N’-diarylation of natural diamines and polyamines such as putrescine, cadaverine, spermine, spermidine and their homologues is described. Aryl iodides bearing electron-donating and electron-withdrawing groups have been employed in the study. The CuI/2-(isobutyryl)cyclohexanone/DMF catalytic system has found to be more efficient in the diarylation of diamines and spermine while the CuI/L-proline/EtCN system proved to be preferable for the diarylation of other tri- and tetraamines like spermidine, norspermidine and norspermine. PMID:26734078

  4. EVALUATION OF PROPARGYL BROMIDE AS A SOIL FUMIGANT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The cut flower and bulb industry has relied heavily upon the use of methyl bromide as a key soil treatment for soilborne pest control. Due to the phase-out of methyl bromide it is important to develop alternatives to manage pests now managed by methyl bromide. The emphasis of this work was to eval...

  5. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  6. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  7. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  8. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  9. WEED CONTROL IN THE LIFE AFTER METHYL BROMIDE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable growers are losing the soil fumigant methyl bromide. Efforts are on-going to extend the deadline for using methyl bromide until suitable alternatives are developed. Regardless of whether the deadline is extended or not, growers need to begin to study alternatives to methyl bromide and be...

  10. 75 FR 5582 - Methyl Bromide; Amendments to Terminate Uses

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-03

    ... AGENCY Methyl Bromide; Amendments to Terminate Uses AGENCY: Environmental Protection Agency (EPA). ACTION... requested by the registrants and accepted by the Agency, of products containing the pesticide methyl bromide... Requests from the registrants listed in Table 2 to amend to terminate post-harvest methyl bromide uses...

  11. 40 CFR 180.124 - Methyl bromide; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Methyl bromide; tolerances for... § 180.124 Methyl bromide; tolerances for residues. (a) General. A tolerance is established for residues of the fumigant methyl bromide, including metabolites and degradates, in or on the commodity in...

  12. 7 CFR 305.6 - Methyl bromide fumigation treatment schedules.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 5 2010-01-01 2010-01-01 false Methyl bromide fumigation treatment schedules. 305.6..., fumigation with methyl bromide for sapote fruit fly. Regulated citrus fruits originating inside an area... equal concentrations of methyl bromide throughout the chamber, a fan should be placed near the point...

  13. Catalytic Enantioselective Conjugate Alkynylation of β-Aryl-β-trifluoromethyl Enones Constructing Propargylic All-Carbon Quaternary Stereogenic Centers.

    PubMed

    Sanz-Marco, Amparo; Blay, Gonzalo; Vila, Carlos; Pedro, José R

    2016-08-01

    The enantioselective conjugate alkynylation of β-aryl-β-trifluoromethyl enones has been carried out using terminal alkynes and diethylzinc in the presence of 3,3'-bis(perfluorophenyl)BINOL as the chiral ligand to give the corresponding ketones bearing a trifluoromethylated propargylic quaternary stereocenter with fair to good enantioselectivities. Enones bearing a bulky 2-naphthyl attached to the carbonyl group provided the best enantioselectivities. The synthetic applicability of the resulting products has been demonstrated with their iodocyclization to form 4H-pyrans. PMID:27417872

  14. Chemoselectivity in the Cu-catalyzed O-arylation of phenols and aliphatic alcohols.

    PubMed

    Maiti, Debabrata

    2011-08-01

    An orthogonal set of Cu-catalysts for the selective mono-arylation of alkyl aryl diols using aryl iodides is presented. Picolinic acid ligated copper catalyst provided phenol O-arylation only, while alkyl aryl ethers are generated by ligand-free copper catalyst in the presence of 2 equivalents NaOt-Bu. PMID:21698330

  15. Measurements of atmospheric methyl bromide and bromoform

    SciTech Connect

    Cicerone, R.J.; Heidt, L.E.; Pollock, W.H.

    1988-04-20

    We have measured gaseous methyl bromide (CH/sub 3/Br) and bromoform (CHBr/sub 3/) in air samples that were gathered approximately weekly from five ground-level sites: Point Barrow, Alaska; Mauna Loa Observatory and Cape Kumukahi, Hawaii; Matatula, Samoa; and Kaitorete Spit, New Zealand. Approximately 750 samples have been analyzed for CH/sub 3/Br between January 1985 and October 1987 and 990 samples have been analyzed for CHBr/sub 3/ between early 1984 and September 1987, all by gas chromatography/mass spectroscopy. Methyl bromide concentrations are typically 10--11 parts per trillion (ppt) by volume; there are no clear indications of temporal increases. Bromoform concentrations are typically 2--3 ppt, but large seasonal variations are seen at Point Barrow. copyright American Geophysical Union 1988

  16. Removal of bromide and natural organic matter by anion exchange.

    PubMed

    Hsu, Susan; Singer, Philip C

    2010-04-01

    Bromide removal by anion exchange was explored for various water qualities, process configurations, and resin characteristics. Simulated natural waters containing different amounts of natural organic matter (NOM), bicarbonate, chloride, and bromide were treated with a polyacrylate-based magnetic ion exchange (MIEX) resin on a batch basis to evaluate the effectiveness of the resin for removal of bromide. While bromide removal was achieved to some degree, alkalinity (bicarbonate), dissolved organic carbon (DOC), and chloride were shown to inhibit bromide removal in waters with bromide concentrations of 100 and 300 microg/L. Water was also treated using a two-stage batch MIEX process. Two-stage treatment resulted in only a slight improvement in bromide removal compared to single-stage treatment, presumably due to competition with the high concentration of chloride which is present along with bromide in natural waters. In view of the relatively poor bromide removal results for the MIEX resin, a limited set of experiments was performed using polystyrene resins. DOC and bromide removal were compared by treating model waters with MIEX and two polystyrene resins, Ionac A-641 and Amberlite IRA910. The two polystyrene resins were seen to be more effective for bromide removal, while the MIEX resin was more effective at removing DOC. PMID:20045170

  17. [Research advances in methyl bromide in the ocean].

    PubMed

    Du, Hui-na; Xie, Wen-xia; Cui, Yu-qian; Chen, Jian-lei; Ye, Si-yuan

    2014-12-01

    Methyl bromide is an important atmospheric trace gas, which plays significant roles in the global warming and atmospheric chemistry. The ocean plays important and complex roles in the global biogeochemical cycles of methyl bromide, not only the source of atmospheric methyl bromide, but also the sink. Therefore, developing the chemical research of the soluble methyl bromide in the ocean, will not only have a certain guiding significance to the atmospheric ozone layer protection, but also provide a theoretical basis for estimating methyl bromide's contribution to the global environmental change on global scale. This paper reviewed the research advances on methyl bromide in the ocean, from the aspects of the biogeochemical cycle of methyl bromide in the ocean, the analysis and determination method, the concentration distribution, the sea-to-air flux and its sources and sinks in the atmosphere. Some deficiencies in the current studies were put forward, and the directions of the future studies were prospected. PMID:25876424

  18. Methyl bromide: Ocean sources, ocean sinks, and climate sensitivity

    SciTech Connect

    Anbar, A.D.; Yung, Y.L.; Chavez, F.P.

    1996-03-01

    This study was performed to examine conflicting conclusions of two previously published studies which estimated the size of oceanic sources of methyl bromide. In addition, the sensitivity of atmospheric methyl bromide to climatic variations was examined. A steady state mass balance model was used to reexamine data from the previous studies. Linear scaling of methyl bromide production rates to chlorophyll content provided agreement between the two models. The results suggest that the open ocean is a small net sink for atmospheric methyl bromide, rather than a large net source. A high rate of biological production of methyl bromide in seawater is also strongly indicated. A coupled ocean-atmosphere model indicated that methyl bromide variations induced by climatic change can be larger than those resulting from 25% variations in anthropogenic sources. Quantifying marine production rates of methyl bromide is suggested as a necessary step in assessing stratospheric ozone loss. 63 refs., 10 figs., 2 tabs.

  19. Lattice vibrations in lead bromide and chloride

    NASA Astrophysics Data System (ADS)

    Carabatos-Nédelec, C.; Bréhat, F.; Wyncke, B.

    Lead bromide and lead chloride lattice dynamics studies by polarized IR reflectivity and Raman scattering are reported at room temperature and at 10 K. Reflectivity spectra from 20 to 300 cm -1 have been fitted with a model of the factorized form of the dielectric function. The lattice modes frequencies, damping factors and oscillators strengths are given, as well as the effective charges of the polar modes. The study concludes the ionic character of the compounds.

  20. Methyl bromide users search for science

    SciTech Connect

    Winegar, E.D.

    1995-01-01

    Workers, neighbors and the ozone are protected by regulation from this chemical, but those needing it complain that a solid foundation is lacking for the rules. Although not yet featured on {open_quotes}60 Minutes,{close_quotes} the pesticide methyl bromide is gaining widespread attention because of its central position in debates about worker health and safety, environmental toxics exposure and global ozone depletion.

  1. Methyl bromide volatility measurements from treated fields

    SciTech Connect

    Majewski, M.S.; Woodrow, J.E.; Seiber, J.N. |

    1995-12-31

    Methyl bromide is used as an agricultural soil fumigant and concern is growing over the role it may play in the depletion of stratospheric ozone. Methyl bromide is applied using various techniques and little is known about how much of the applied fumigant volatilizes into the atmosphere after application. The post-application volatilization losses of methyl bromide from two fields using different application practices were measured using an aerodynamic-gradient technique. One field was covered with a high-barrier plastic film tarp during application and the other was left uncovered, but the furrows made by the injection shanks were bedded over. The cumulative volatilization losses from the tarped field were 22% of the nominal application within the first 5 days of the experiment and about 32% of the nominal application within 9 days including the one day after the tarp was removed on day 8. The nontarped field lost 89%of the nominal application by volatilization in 5 days. The error associated, with each flux measurement, as well as variations in daily flux losses with differing sampling period lengths show the degree of variability inherent in this type of study.

  2. Methyl bromide fate in fumigated soils

    SciTech Connect

    Anderson, T.A.; Rice, P.J.; Cink, J.H.

    1995-12-31

    Although widespread use of methyl bromide (MeBr) as a sail and structure fumigant has previously been recognized as a potential significant source of atmospheric MeBr, losses have not been well quantified. Our research indicates that, in laboratory studies, MeBr is volatilized rapidly from fumigated soils and that volatility increases with temperature (35{degrees}C > 25{degrees}C and 15{degrees}C) and moisture (0.03 bar and 0.3 bar > 1 bar > 3 bar). Degradation of MeBr in soil, as indicated by production of bromide ion, was also directly related to temperature and moisture. Most of the soil degradation of MeBr in these studies appears to be abiotic based on the observation of toxicity (reduced microbial respiration) in fumigated soils. We also determined the transformation and movement of MeBr in undisturbed soil columns. These studies also indicated that MeBT volatilizes rapidly (> 50% in 48 h) from soil. In addition, MeBr was not detected in the leachate from the soil columns, however, bromide ion was detected at levels above background 48 h after fumigation and peaked at 5 weeks.

  3. Bromate oxidized from bromide during sonolytic ozonation.

    PubMed

    Lu, Ning; Wu, Xue-Fei; Zhou, Ji-Zhi; Huang, Xin; Ding, Guo-Ji

    2015-01-01

    Sonolytic ozonation (US/O3) is an effective way to degrade many pollutants in drinking water as the elevated mass transfer rate of ozone gas and the enhanced forming of hydroxyl radicals (OH). This work investigated the formation of bromate (BrO3(-)) from bromide (Br(-)) in sonolytic ozonation. At neutral pH, the bromate conversion rate ([BrO3(-)]/[Br(-)]0) was increased to 60% by ultrasound at continuous ozone flow (0-0.2Lmin(-1)), much higher than that without ultrasound or without bubbling. This indicates that the promoting effect of sonolysis on BrO3(-) formation is mainly due to the sonolytic decomposition of ozone and the enhancement of gas-liquid transfer. The [BrO3(-)]/[Br(-)]0 was increased with increasing pH. In addition, the reduction of HOBr/OBr(-) with ultrasound demonstrates that bromate may be inhibited as the bromide was formed with the H2O2 generation under ultrasound. This suggests the competition between bromate and bromide during the US/O3 led to the inhibition of bromate formation at high ozone flow. Therefore, our result reveals that the bromate formation under ultrasound is improved remarkably in US/O3 in quick treatment with proper ozone flow (<0.2Lmin(-1)). PMID:24931426

  4. Synthesis of β-arylated alkylamides via Pd-catalyzed one-pot installation of a directing group and C(sp3)–H arylation

    PubMed Central

    Zhang, Yi; Cao, Xiaoji; Wan, Jie-Ping

    2016-01-01

    Summary The synthesis of β-arylated alkylamides via alkyl C–H bond arylation has been realized by means of direct one-pot reactions of acyl chlorides, aryl iodides and 8-aminoquinoline. Depending on the structure of the starting materials, both single and double β-arylated alkylamides could be accessed. PMID:27340500

  5. Palladium-Catalyzed Synthesis of N-Aryl Carbamates

    PubMed Central

    Vinogradova, Ekaterina V.; Park, Nathaniel H.; Fors, Brett P.; Buchwald, Stephen L.

    2013-01-01

    An efficient synthesis of aryl carbamates was achieved by introducing alcohols into the reaction of palladium-catalyzed cross-coupling of ArX (X = Cl, OTf) with sodium cyanate. The use of aryl triflates as electrophilic components in this transformation allowed for an expanded substrate scope for direct synthesis of aryl isocyanates. This methodology provides direct access to major carbamate protecting groups, S-thiocarbamates, and diisocyanate precursors to polyurethane materials. PMID:23441814

  6. Double C-H functionalization in sequential order: direct synthesis of polycyclic compounds by a palladium-catalyzed C-H alkenylation-arylation cascade.

    PubMed

    Ohno, Hiroaki; Iuchi, Mutsumi; Kojima, Naoto; Yoshimitsu, Takehiko; Fujii, Nobutaka; Tanaka, Tetsuaki

    2012-04-23

    Palladium-catalyzed cascade C-H alkenylation and arylation provides convenient access to polycyclic aromatic compounds. Treatment of 3-bromoaniline derivatives bearing a bromocinnamyl group on the nitrogen atom with a catalytic amount of [Pd(OAc)(2)] and PCy(3)·HBF(4) in the presence of Cs(2)CO(3) in dioxane affords naphthalene-fused indole derivatives in good yields. This double cyclization reaction is also applicable to heterocyclic substrates, giving fused indoles containing a heteroaromatic ring such as dibenzofuran, dibenzothiophene, carbazole, indole, or benzofuran through heterocyclic C-H arylation. When using a 2,6-unsubstituted aniline derivative, the first C-H arylation preferentially proceeds at the more hindered position of the aniline ring. PMID:22422703

  7. Environmental exposure to N-aryl compounds

    SciTech Connect

    Guerin, M.R.; Buchanan, M.V.

    1987-01-01

    N-aryl compounds are well-known occupational exposure hazards but are relatively unstudied as an environmental exposure problem. Coal-derived liquid fuels and environmental tobacco smoke are examples of materials potentially leading to significant environmental exposures to aryl amines. Integrated chemical class separation and bacterial mutagenicity testing identified primary aromatic amines as the major contributors to the mutagenicities of crude coal liquids. Studies of sidestream cigarette smoke chemistry show that alkaline constituents of cigarette smoke are preferentially released into the environment as compared to that drawn into the mouth by the smoker. Two to ten times the quantity of aromatic amines are released in the sidestream smoke on a per cigarette basis. Quantities of the more mutagenic and carcinogenic multi-ring aryl amines in both coal liquids and in cigarette smoke are very small and they are accompanied by a wide variety of related compounds. Chemical ionization mass spectrometric methods have been developed to distinguish between closely related amines to facilitate their identification and quantitation at trace levels.

  8. Formation of 2,4,5-triaryl-4,5-dihydro-1 H-imidazoles, ( 1), from aryl aldehydes. Crystal structures of cis-( 1: aryl = pyridin-2-yl), { trans-[( 1: aryl = pyridin-2-yl)H] +[OAc] -·3H 2O}, { cis-[ 1: aryl = thien-2-yl]·0.5H 2O} and trans-( 1: aryl = thien-2-yl)

    NASA Astrophysics Data System (ADS)

    Fernandes, Christiane; Horn, Adolfo; Howie, R. Alan; Schripsema, Jan; Skakle, Janet M. S.; Wardell, James L.

    2007-06-01

    The preparations of cis-2,4,5-triaryl-4,5-dihydro-1 H-imidazoles, (aryl = thien-2-yl or pyridin-2-yl) from aryl aldehydes, ammonium chloride and triethylamine in methanol, and their conversions to the trans-isomers are reported. Crystal structures of cis-( 1: aryl = pyridin-2-yl), cis-[ 1: aryl = thien-2-yl·0.5H 2O], trans-( 1: aryl = thien-2-yl), and trans-{[( 1: aryl = pyridin-2-yl)H] +[OAc] -·3H 2O}, have been determined and compared with related structures.

  9. Fluorodecarboxylation for the Synthesis of Trifluoromethyl Aryl Ethers.

    PubMed

    Zhang, Qing-Wei; Brusoe, Andrew T; Mascitti, Vincent; Hesp, Kevin D; Blakemore, David C; Kohrt, Jeffrey T; Hartwig, John F

    2016-08-01

    The synthesis of mono-, di-, and trifluoromethyl aryl ethers by fluorodecarboxylation of the corresponding carboxylic acids is reported. AgF2 induces decarboxylation of aryloxydifluoroacetic acids, and AgF, either generated in situ or added separately, serves as a source of fluorine to generate the fluorodecarboxylation products. The addition of 2,6-difluoropyridine increased the reactivity of AgF2 , thereby increasing the range of functional groups and electronic properties of the aryl groups that are tolerated. The reaction conditions used for the formation of trifluoromethyl aryl ethers also served to form difluoromethyl and monofluoromethyl aryl ethers. PMID:27384710

  10. Palladium-Catalyzed Zinc-Amide-Mediated C-H Arylation of Fluoroarenes and Heteroarenes with Aryl Sulfides.

    PubMed

    Otsuka, Shinya; Yorimitsu, Hideki; Osuka, Atsuhiro

    2015-10-12

    C-H arylation of polyfluoroarenes and heteroarenes with aryl sulfides proceeds smoothly with the aid of a palladium-N-heterocyclic carbene catalyst. A bulky zinc amide, TMPZnCl⋅LiCl, plays a key role as an effective base to generate the corresponding arylzinc species in situ. This arylation protocol is practically much easier to perform than our previous method, which necessitates preparation of the arylzinc reagents in advance from the corresponding aryl halides. Aryl sulfides that are prepared through sulfur-specific reactions, such as SN Ar sulfanylation and extended Pummerer reactions, undergo this direct arylation, offering interesting transformations that are otherwise difficult to achieve with conventional halogen-based organic synthesis. PMID:26235212

  11. System for testing bearings

    NASA Astrophysics Data System (ADS)

    Gibson, John C.

    1993-07-01

    Disclosed here is a system for testing bearings wherein a pair of spaced bearings provides support for a shaft on which is mounted a bearing to be tested, this bearing being mounted in a bearing holder spaced from and in alignment with the pair of bearings. The bearing holder is provided with an annular collar positioned in an opening in the bearing holder for holding the bearing to be tested. A screw threaded through the bearing holder into engagement with the annular collar can be turned to force the collar radially out of alignment with the pair of bearings to apply a radial load to the bearing.

  12. 2-Aryl-2-nitroacetates as Central Precursors to Aryl Nitromethanes, α-Ketoesters, and α-Amino Acids

    PubMed Central

    Metz, Alison E.

    2013-01-01

    Nitroarylacetates are useful small molecular building blocks that act as precursors to α-ketoesters and aryl nitromethanes as well as α-amino acids. Methods were developed that produce each of these compound types in good yields. Two different conditions for decarboxylation are discussed for substrates with neutral and electron-poor aryl groups versus electron-rich aryl groups. For formation of the α-ketoesters, new mild conditions for the Nef disproportionation were identified. PMID:23245626

  13. Metal-Free Mediated Meerwein-Type Reaction: A Radical Cascade Arylation/Aryl Migration/Desulfonylation of Conjugated Alkenes.

    PubMed

    Ni, Zhangqin; Huang, Xin; Pan, Yuanjiang

    2016-06-01

    A metal-free cascade arylation/aryl migration/desulfonylation of N-phenyl-N-(phenylsulfonyl)methacrylamide is described. The in situ generated diazonium salts from anilines and t-BuONO are used as aryl precursors. This process provides an efficient strategy for the synthesis of α-all-carbon quaternary stereocenters amides. A radical mechanism was proposed for this transformation. PMID:27219900

  14. CUSHIONED BEARING

    DOEpatents

    Rushing, F.C.

    1960-09-01

    A vibration damping device effective to dampen vibrations occurring at the several critical speeds encountered in the operation of a high-speed centrifuge is described. A self-centering bearing mechanism is used to protect both the centrifuge shaft and the damping mechanism. The damping mechanism comprises spaced-apant, movable, and stationary sleeve members arranged concentrically of a rotating shaft with a fluid maintained between the members. The movable sleeve member is connected to the shaft for radial movement therewith.

  15. Tooling Converts Stock Bearings To Custom Bearings

    NASA Technical Reports Server (NTRS)

    Fleenor, E. N., Jr.

    1983-01-01

    Technique for reworking stock bearings saves time and produces helicopter-rotor bearings ground more precisely. Split tapered ring at one end of threaded bolt expands to hold inside of inner race bearing assembly; nut, at other end of bolt, adjusts amount of spring tension. Piece of hardware grasps bearing firmly without interfering with grinding operation. Operation produces bearing of higher quality than commercially available bearings.

  16. Evidence for In Situ Catalyst Modification During the Pd-Catalyzed Conversion of Aryl Triflates to Aryl Fluorides

    PubMed Central

    Maimone, Thomas J.; Milner, Phillip J.; Kinzel, Tom; Zhang, Yong; Takase, Michael K.; Buchwald, Stephen L.

    2012-01-01

    A mechanistic investigation of the Pd-catalyzed conversion of aryl triflates to fluorides is presented. Studies reveal that C—F reductive elimination from an LPd(II)(aryl) fluoride complex (L = t-BuBrettPhos (2), RockPhos (3)) does not occur when the aryl group is electron rich. Evidence is presented that a modified phosphine, generated in-situ, serves as the actual supporting ligand during catalysis with such substrates. A preliminary study of the reactivity of an LPd(II)(aryl) fluoride complex based on this modified ligand is reported. PMID:21999801

  17. Evidence for in situ catalyst modification during the Pd-catalyzed conversion of aryl triflates to aryl fluorides.

    PubMed

    Maimone, Thomas J; Milner, Phillip J; Kinzel, Tom; Zhang, Yong; Takase, Michael K; Buchwald, Stephen L

    2011-11-16

    A mechanistic investigation of the Pd-catalyzed conversion of aryl triflates to fluorides is presented. Studies reveal that C-F reductive elimination from a LPd(II)(aryl)F complex (L = t-BuBrettPhos or RockPhos) does not occur when the aryl group is electron rich. Evidence is presented that a modified phosphine, generated in situ, serves as the actual supporting ligand during catalysis with such substrates. A preliminary study of the reactivity of a LPd(II)(aryl)F complex based on this modified ligand is reported. PMID:21999801

  18. Europium-doped barium bromide iodide

    SciTech Connect

    Gundiah, Gautam; Hanrahan, Stephen M.; Hollander, Fredrick J.; Bourret-Courchesne, Edith D.

    2009-10-21

    Single crystals of Ba0.96Eu0.04BrI (barium europium bromide iodide) were grown by the Bridgman technique. The title compound adopts the ordered PbCl2 structure [Braekken (1932). Z. Kristallogr. 83, 222-282]. All atoms occupy the fourfold special positions (4c, site symmetry m) of the space group Pnma with a statistical distribution of Ba and Eu. They lie on the mirror planes, perpendicular to the b axis at y = +-0.25. Each cation is coordinated by nine anions in a tricapped trigonal prismatic arrangement.

  19. Advanced hydrogen electrode for hydrogen-bromide battery

    NASA Technical Reports Server (NTRS)

    Kosek, Jack A.; Laconti, Anthony B.

    1987-01-01

    Binary platinum alloys are being developed as hydrogen electrocatalysts for use in a hydrogen bromide battery system. These alloys were varied in terms of alloy component mole ratio and heat treatment temperature. Electrocatalyst evaluation, performed in the absence and presence of bromide ion, includes floating half cell polarization studies, electrochemical surface area measurements, X ray diffraction analysis, scanning electron microscopy analysis and corrosion measurements. Results obtained to date indicate a platinum rich alloy has the best tolerance to bromide ion poisoning.

  20. Mechanism-based inactivation of benzo(a)pyrene hydroxylase by aryl acetylenes and aryl olefins

    SciTech Connect

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

    1986-05-01

    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, /sup 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.

  1. Nickel catalyzed α-arylation of ketones with aryltrimethylammonium triflates.

    PubMed

    Li, Jing; Wang, Zhong-Xia

    2016-08-21

    Nickel-catalyzed α-arylation of ketones involving aromatic C-N cleavage has been accomplished. Intermolecular coupling of aromatic ketones with a variety of aryltrimethylammonium triflates was achieved in the presence of Ni(COD)2, IPr·HCl, and LiOBu(t), giving α-arylated ketones in reasonable to excellent yields. PMID:27443786

  2. Aryl Hydrocarbon Receptor and Lung Cancer

    PubMed Central

    Tsay, Junchieh J.; Tchou-Wong, Kam-Meng; Greenberg, Alissa K.; Pass, Harvey; Rom, William N.

    2013-01-01

    The leading cause of lung cancer is exposure to cigarette smoke and other environmental pollutants, which include formaldehyde, acrolein, benzene, dioxin, and polycyclic aromatic hydrocarbons (PAHs). PAHs and dioxins are exogenous ligands that directly bind to the aryl hydrocarbon receptor (AhR), a transcription factor that activates xenobiotic metabolism, histone modification (an important step in DNA methylation), and, ultimately, tumorigenesis. Here we summarize the current understanding of AhR and its role in the development of lung cancer, including its influence on cell proliferation, angiogenesis, inflammation, and apoptosis. PMID:23564762

  3. Fluid lubricated bearing construction

    DOEpatents

    Dunning, John R.; Boorse, Henry A.; Boeker, Gilbert F.

    1976-01-01

    1. A fluid lubricated thrust bearing assembly comprising, in combination, a first bearing member having a plain bearing surface, a second bearing member having a bearing surface confronting the bearing surface of said first bearing member and provided with at least one spiral groove extending inwardly from the periphery of said second bearing member, one of said bearing members having an axial fluid-tight well, a source of fluid lubricant adjacent to the periphery of said second bearing member, and means for relatively rotating said bearing members to cause said lubricant to be drawn through said groove and to flow between said bearing surfaces, whereby a sufficient pressure is built up between said bearing surfaces and in said well to tend to separate said bearing surfaces.

  4. Palladium-Catalyzed Ortho-Arylation of Carbamate-Protected Estrogens.

    PubMed

    Bedford, Robin B; Brenner, Peter B; Durrant, Steven J; Gallagher, Timothy; Méndez-Gálvez, Carolina; Montgomery, Michelle

    2016-05-01

    The palladium-catalyzed ortho-arylation of diethyl carbamate-protected estrone and estriol with aryl iodides gives the 2-arylated analogues. Subsequent removal of the carbamate directing group furnishes 2-arylated estrone, estradiol, or estriol depending on the method used. PMID:27057762

  5. Protecting group-free, selective cross-coupling of alkyltrifluoroborates with borylated aryl bromides via photoredox/nickel dual catalysis

    PubMed Central

    Yamashita, Yohei; Tellis, John C.; Molander, Gary A.

    2015-01-01

    Orthogonal reactivity modes offer substantial opportunities for rapid construction of complex small molecules. However, most strategies for imparting orthogonality to cross-coupling reactions rely on differential protection of reactive sites, greatly reducing both atom and step economies. Reported here is a strategy for orthogonal cross-coupling wherein a mechanistically distinct activation mode for transmetalation of sp3-hybridized organoboron reagents enables C-C bond formation in the presence of various protected and unprotected sp2-hybridized organoborons. This manifold has the potential for broad application, because orthogonality is inherent to the activation mode itself. The diversification potential of this platform is shown in the rapid elaboration of a trifunctional lynchpin through various transition metal-catalyzed processes without nonproductive deprotection or functional group manipulation steps. PMID:26371299

  6. Protecting group-free, selective cross-coupling of alkyltrifluoroborates with borylated aryl bromides via photoredox/nickel dual catalysis.

    PubMed

    Yamashita, Yohei; Tellis, John C; Molander, Gary A

    2015-09-29

    Orthogonal reactivity modes offer substantial opportunities for rapid construction of complex small molecules. However, most strategies for imparting orthogonality to cross-coupling reactions rely on differential protection of reactive sites, greatly reducing both atom and step economies. Reported here is a strategy for orthogonal cross-coupling wherein a mechanistically distinct activation mode for transmetalation of sp(3)-hybridized organoboron reagents enables C-C bond formation in the presence of various protected and unprotected sp(2)-hybridized organoborons. This manifold has the potential for broad application, because orthogonality is inherent to the activation mode itself. The diversification potential of this platform is shown in the rapid elaboration of a trifunctional lynchpin through various transition metal-catalyzed processes without nonproductive deprotection or functional group manipulation steps. PMID:26371299

  7. Cryogenic turbopump bearing materials

    NASA Technical Reports Server (NTRS)

    Bhat, Biliyar N.

    1989-01-01

    Materials used for modern cryogenic turbopump bearings must withstand extreme conditions of loads and speeds under marginal lubrication. Naturally, these extreme conditions tend to limit the bearing life. It is possible to significantly improve the life of these bearings, however, by improving the fatigue and wear resistance of bearing alloys, and improving the strength, liquid oxygen compatibility and lubricating ability of the bearing cage materials. Improved cooling will also help to keep the bearing temperatures low and hence prolong the bearing life.

  8. 40 CFR 180.124 - Methyl bromide; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Methyl bromide; tolerances for residues. 180.124 Section 180.124 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances § 180.124 Methyl bromide; tolerances...

  9. An Ill Wind: Methyl Bromide Use Near California Schools, 1998.

    ERIC Educational Resources Information Center

    Ross, Zev; Walker, Bill

    A California study investigates the use of the toxic pesticide methyl bromide near the state's public schools, explains why proposed safety rules have failed to protect children and others from exposure, and examines regions at particular exposure risk. Study results show an increasing exposure to methyl bromide near schools already at risk while…

  10. 40 CFR 180.124 - Methyl bromide; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Methyl bromide; tolerances for residues. 180.124 Section 180.124 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances § 180.124 Methyl bromide; tolerances...

  11. Interaction of methyl bromide with soil.

    PubMed

    Tao, Ting; Maciel, Gary E

    2002-02-15

    Because methyl bromide (CH3Br) is a widely used agricultural fumigant for soil disinfection, it is important to know the chemical behavior and fate of CH3Br as a result of its use for soil treatment. A solid-state 13C NMR study of 13CH3Br-treated soil and soil-component samples shows that methylation of soil organic matter may be the major pathway for degradation of CH3Br in soils. Adsorption of CH3Br on a dried clay like Ca-montmorillonite or kaolinite does not contribute directly to the degradation of CH3Br. The results are interpreted in terms of the chemical structures of separated soil fractions and the nature of the separation procedure. PMID:11878373

  12. Degradation of methyl bromide in anaerobic sediments

    USGS Publications Warehouse

    Oremland, R.S.; Miller, L.G.; Strohmaler, F.E.

    1994-01-01

    Methyl bromide (MeBr) was anaerobically degraded in saltmarsh sediments after reaction with sulfide. The product of this nucleophilic substitution reaction was methanethiol, which underwent further chemical and bacterial reactions to form dimethyl sulfide. These two gases appeared transiently during sediment incubations because they were metabolized by methanogenic and sulfate-reducing bacteria. A second, less significant reaction of MeBr was the exchange with chloride, forming methyl chloride, which was also susceptible to attack by sulfide. Incubation of 14C-labeled methyl iodide as an analogue of MeBr resulted in the formation of 14CH4 and 14CO2 and also indicated that sulfate-reducing bacteria as well as methanogens metabolized the methylated sulfur intermediates. These results suggest that exposed sediments with abundant free sulfide, such as coastal salt-marshes, may constitute a sink for atmospheric MeBr.

  13. Single ion dynamics in molten sodium bromide

    SciTech Connect

    Alcaraz, O.; Trullas, J.; Demmel, F.

    2014-12-28

    We present a study on the single ion dynamics in the molten alkali halide NaBr. Quasielastic neutron scattering was employed to extract the self-diffusion coefficient of the sodium ions at three temperatures. Molecular dynamics simulations using rigid and polarizable ion models have been performed in parallel to extract the sodium and bromide single dynamics and ionic conductivities. Two methods have been employed to derive the ion diffusion, calculating the mean squared displacements and the velocity autocorrelation functions, as well as analysing the increase of the line widths of the self-dynamic structure factors. The sodium diffusion coefficients show a remarkable good agreement between experiment and simulation utilising the polarisable potential.

  14. Glycopyrronium bromide for the treatment of chronic obstructive pulmonary disease.

    PubMed

    Riario-Sforza, Gian Galeazzo; Ridolo, Erminia; Riario-Sforza, Edoardo; Incorvaia, Cristoforo

    2015-02-01

    Glycopyrronium bromide is a new long-acting muscarinic antagonist to be used once-daily, which is approved as a bronchodilator for the symptomatic maintenance treatment of adult patients with chronic obstructive pulmonary disease (COPD). In the Glycopyrronium bromide in chronic Obstructive pulmonary disease airWays trials, treatment with inhaled glycopyrronium bromide at 50 μg once daily achieved a significantly better lung function than placebo, as measured by the trough forced expiratory volume in 1 s in patients with moderate-to-severe COPD. The lung function improvement was maintained for up to 52 weeks. Other improved indexes were dyspnea scores, health status, exacerbation rates and time of exercise endurance. Studies comparing the efficacy of glycopyrronium versus tiotropium bromide found substantial equivalence of the two drugs. Glycopyrronium was generally well tolerated. These data add inhaled glycopyrronium bromide to the treatment of patients with moderate to severe COPD as an effective once-daily LAMA. PMID:25547422

  15. Atmosphere-plant canopy interactions of methyl bromide

    SciTech Connect

    Taylor, G.E. Jr.; Leonard, T.D.; Gustin, M.S.

    1995-12-31

    In the planetary boundary layer, parcels of air containing background and elevated concentrations of methyl bromide commonly pass through plant canopies in managed (agriculture) and natural (forests, grasslands) ecosystems. It is hypothesized that leaf surfaces are a significant sink or methyl bromide on a local and regional scale and that failure to account for this sink results in a significant overestimation of methyl bromide transport to the stratosphere. Using highly controlled environments, studies are investigating the reactivity of leaf surfaces for methyl bromide at elevated and global background concentrations. Estimates of pathway resistances are being calculated and sites of deposition determined. The results indicate that plant canopies are a significant unrecognized sink for methyl bromide in the atmosphere.

  16. Design, Synthesis, and Structure--Activity Relationship of New 2-Aryl-3,4-dihydro-β-carbolin-2-ium Salts as Antifungal Agents.

    PubMed

    Hou, Zhe; Zhu, Li-Fei; Yu, Xin-chi; Sun, Ma-Qiang; Miao, Fang; Zhou, Le

    2016-04-13

    Twenty-two 2-aryl-9-methyl-3,4-dihydro-β-carbolin-2-ium bromides along with four 9-demethylated derivatives were synthesized and characterized by spectroscopic analysis. By using the mycelium growth rate method, the compounds were evaluated for antifungal activities in vitro against six plant pathogenic fungi, and structure-activity relationships (SAR) were derived. Almost all of the compounds showed obvious inhibition activity on each of the fungi at 150 μM. For all of the fungi, 10 of the compounds showed average inhibition rates of >80% at 150 μM, and most of their EC50 values were in the range of 2.0-30.0 μM. SAR analysis showed that the substitution pattern of the N-aryl ring significantly influences the activity; N9-alkylation improves the activity, whereas aromatization of ring-C reduces the activity. It was concluded that the present research provided a series of new 2-aryl-9-alkyl-3,4-dihydro-β-carbolin-2-iums with excellent antifungal potency and structure optimization design for the development of new carboline antifungal agents. PMID:27004437

  17. Crystal structures of five 1-alkyl-4-aryl-1,2,4-triazol-1-ium halide salts

    PubMed Central

    Guino-o, Marites A.; Talbot, Meghan O.; Slitts, Michael M.; Pham, Theresa N.; Audi, Maya C.; Janzen, Daron E.

    2015-01-01

    The asymmetric units for the salts 4-(4-fluoro­phen­yl)-1-isopropyl-1,2,4-triazol-1-ium iodide, C11H13FN3 +·I−, (1), 1-isopropyl-4-(4-methyl­phen­yl)-1,2,4-triazol-1-ium iodide, C12H16N3 +·I−, (2), 1-isopropyl-4-phenyl-1,2,4-triazol-1-ium iodide, C11H14N3 +·I−, (3), and 1-methyl-4-phenyl-1,2,4-triazol-1-ium iodide, C9H10N3 +·I−, (4), contain one cation and one iodide ion, whereas in 1-benzyl-4-phenyl-1,2,4-triazol-1-ium bromide monohydrate, C15H14N3 +·Br−·H2O, (5), there is an additional single water mol­ecule. There is a predominant C—H⋯X(halide) inter­action for all salts, resulting in a two-dimensional extended sheet network between the triazolium cation and the halide ions. For salts with para-substitution on the aryl ring, there is an additional π–anion inter­action between a triazolium carbon and iodide displayed by the layers. For salts without the para-substitution on the aryl ring, the π–π inter­actions are between the triazolium and aryl rings. The melting points of these salts agree with the predicted substituent inductive effects. PMID:26090137

  18. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY ADMINISTRATION, DEPARTMENT OF TRANSPORTATION HAZARDOUS MATERIALS...

  19. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY ADMINISTRATION, DEPARTMENT OF TRANSPORTATION HAZARDOUS MATERIALS...

  20. Development of a Method for the N-Arylation of Amino Acid Esters with Aryl Triflates.

    PubMed

    King, Sandra M; Buchwald, Stephen L

    2016-08-19

    A general method for the N-arylation of amino acid esters with aryl triflates is described. Both α- and β-amino acid esters, including methyl, tert-butyl, and benzyl esters, are viable substrates. Reaction optimization was carried out by design of experiment (DOE) analysis using JMP software. The mild reaction conditions, which use t-BuBrettPhos Pd G3 or G4 precatalyst, result in minimal racemization of the amino acid ester. This method is the first synthetic application of the t-BuBrettPhos Pd G4 precatalyst. Mechanistic studies show that the observed erosion in enantiomeric excess is due to racemization of the amino acid ester starting material and not of the product. PMID:27498618

  1. No-carrier-added (NCA) aryl ([sup 18]F) fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

    DOEpatents

    Yushin Ding; Fowler, J.S.; Wolf, A.P.

    1993-10-19

    A method for synthesizing no-carrier-added (NCA) aryl [.sup.18 F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method of the present invention includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substitutent on an electron rich ring. The reaction is The U.S. Government has rights in this invention pursuant to Contract Number DE-AC02-76CH00016, between the U.S. Department of Energy and Associated Universities Inc.

  2. No-carrier-added (NCA) aryl (18E) fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

    DOEpatents

    Ding, Yu-Shin; Fowler, Joanna S.; Wolf, Alfred P.

    1993-01-01

    A method for synthesizing no-carrier-added (NCA) aryl [.sup.18 F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method of the present invention includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substitutent on an electron rich ring. The reaction is The U.S. Government has rights in this invention pursuant to Contract Number DE-AC02-76CH00016, between the U.S. Department of Energy and Associated Universities Inc.

  3. Catalytic hydrogenolysis of an aryl-aryl carbon-carbon bond with a rhodium complex

    SciTech Connect

    Perthuisot, C.; Jones, W.D. )

    1994-04-20

    Recent publications have brought renewed interest to the quest for homogeneous catalytic activation of carbon-carbon bonds. However, except for a few reports of biphenylene cleavage, the mechanism and scope of aryl-aryl C-C bond activation remains relatively uninvestigated. In the hope of overcoming the obstacle of weak M-C bonds, we used a rhodium system that should provide a thermodynamically favored C-C cleaved complex by making strong metal-aryl bonds. Reaction of (C[sub 5]Me[sub 5])Rh(PMe[sub 3])(Ph)(H) (1) with 1.5 equiv of biphenylene in cyclohexane-d[sub 12] at 65[degree]C resulted in the quantitative formation of (CC[sub 5]Me[sub 5])Rh(PMe[sub 3]) (biphenylenyl(H)) (2), along with a small amount of a red complex. The cleavage of the well-hidden carbon-carbon bond of biphenylene described relies both on a strained four-membered ring and on the formation of a stable pentametallacycle. The results show that C-H activation and [eta][sup 2] coordination are probably involved in the process leading to C-C bond cleavage, and valuable information can be obtained from studies of this system. 21 refs., 1 fig.

  4. 2-aminopyrimidine-4,6-diol as an efficient ligand for solvent-free copper-catalyzed N-arylations of imidazoles with aryl and heteroaryl halides.

    PubMed

    Xie, Ye-Xiang; Pi, Shao-Feng; Wang, Jian; Yin, Du-Lin; Li, Jin-Heng

    2006-10-13

    Efficient and solvent-free copper-catalyzed N-arylations of imidazoles with aryl and heteroaryl halides have been demonstrated. In the presence of CuBr, 2-aminopyrimidine-4,6-diol, and TBAF (n-Bu4NF), a variety of imidazoles underwent the N-arylation reaction with aryl and heteroaryl halides smoothly in moderate to excellent yields. Noteworthy is that the reaction is conducted under solvent-free conditions. PMID:17025338

  5. Copper-catalyzed aerobic oxidation and cleavage/formation of C-S bond: a novel synthesis of aryl methyl sulfones from aryl halides and DMSO.

    PubMed

    Yuan, Gaoqing; Zheng, Junhua; Gao, Xiaofang; Li, Xianwei; Huang, Liangbin; Chen, Huoji; Jiang, Huanfeng

    2012-08-01

    With atmospheric oxygen as the oxidant, a novel copper(I)-catalyzed synthesis of aryl methyl sulfones from aryl halides and widely available DMSO is described. The procedure tolerates aryl halides with various functional groups (such as methoxy, acetyl, chloro, fluoro and nitro groups), which could afford aryl methyl sulfones in moderate to high yields. The copper-catalyzed aerobic oxidation and the cleavage/formation of C-S bond are the key steps for this transformation. PMID:22728918

  6. Accessing 2,1-Borazaronaphthols: Self-Arylation of 1-Alkyl-2-aryl-3-bromo-2,1-borazaronaphthalenes

    PubMed Central

    2015-01-01

    Unlike their B-alkyl counterparts, brominated N-alkyl B-aryl 2,1-borazaronaphthalenes undergo a self-arylation reaction in the presence of a catalytic amount of palladium and base, in which the azaborine serves as both the electrophile and the nucleophile. The products of the self-arylation are air- and moisture-stable 2,1-borazaronaphthols, previously only observed in basic alcoholic solvents. The steric encumbrance of the azaborine appears to prevent formation of the corresponding boron acid anhydride, allowing access to a family of 2,1-borazaronaphthol derivatives. PMID:25133658

  7. Aryl Hydrocarbon Receptor: linking environment to immunity

    PubMed Central

    Cella, Marina; Colonna, Marco

    2015-01-01

    Mucosal and barrier tissues are unique in that they mediate crosstalk between the host and the surrounding environment, which contains many potentially harmful factors. Therefore, it is critical that cell types present at barrier and mucosal surfaces are equipped with mechanisms to sense changes in the environment and to calibrate their responses accordingly. Aryl Hydrocarbon Receptor (AHR) is a ligand dependent transcription factor well known to generate biological responses to environmental pollutants, such as benzo{a}pyrene and halogenated dioxins. Surprisingly, in the last few years a large body of evidence has shown that AHR is also involved in maintaining homeostasis or in triggering pathology by modulating the biological responses of critical cell types at the barrier and mucosal interfaces. Here, we will review progresses in this field and discuss how targeting AHR activation may impact disease. PMID:26561251

  8. Aryl Hydrocarbon Receptor Control of Adaptive Immunity

    PubMed Central

    2013-01-01

    The aryl hydrocarbon receptor (AhR) is a ligand-activated transcription factor that belongs to the family of basic helix-loop-helix transcription factors. Although the AhR was initially recognized as the receptor mediating the pathologic effects of dioxins and other pollutants, the activation of AhR by endogenous and environmental factors has important physiologic effects, including the regulation of the immune response. Thus, the AhR provides a molecular pathway through which environmental factors modulate the immune response in health and disease. In this review, we discuss the role of AhR in the regulation of the immune response, the source and chemical nature of AhR ligands, factors controlling production and degradation of AhR ligands, and the potential to target the AhR for therapeutic immunomodulation. PMID:23908379

  9. Selective oxidation of bromide in wastewater brines from hydraulic fracturing.

    PubMed

    Sun, Mei; Lowry, Gregory V; Gregory, Kelvin B

    2013-07-01

    Brines generated from oil and natural gas production, including flowback water and produced water from hydraulic fracturing of shale gas, may contain elevated concentrations of bromide (~1 g/L). Bromide is a broad concern due to the potential for forming brominated disinfection byproducts (DBPs) during drinking water treatment. Conventional treatment processes for bromide removal is costly and not specific. Selective bromide removal is technically challenging due to the presence of other ions in the brine, especially chloride as high as 30-200 g/L. This study evaluates the ability of solid graphite electrodes to selectively oxidize bromide to bromine in flowback water and produced water from a shale gas operation in Southwestern PA. The bromine can then be outgassed from the solution and recovered, as a process well understood in the bromine industry. This study revealed that bromide may be selectively and rapidly removed from oil and gas brines (~10 h(-1) m(-2) for produced water and ~60 h(-1) m(-2) for flowback water). The electrolysis occurs with a current efficiency between 60 and 90%, and the estimated energy cost is ~6 kJ/g Br. These data are similar to those for the chlor-alkali process that is commonly used for chlorine gas and sodium hydroxide production. The results demonstrate that bromide may be selectively removed from oil and gas brines to create an opportunity for environmental protection and resource recovery. PMID:23726709

  10. Synthesis of α-Arylphosphonates Using Copper-Catalyzed α-Arylation and Deacylative α-Arylation of β-Ketophosphonates

    PubMed Central

    Rout, Laxmidhar; Regati, Sridhar; Zhao, Cong-Gui

    2011-01-01

    Efficient methods for the direct arylation and deacylative arylation of β-ketophosphonates with iodoarenes in presence of a copper(I) or a copper(II) salt as the catalysts were developed. The corresponding α-arylphosphonates were obtained in high yields. A tentative mechanism for the deacylative arylation reaction was proposed on the basis of the experimental data. PMID:22505878

  11. Stereoconvergent Arylations and Alkenylations of Unactivated Alkyl Electrophiles: Catalytic Enantioselective Synthesis of Secondary Sulfonamides and Sulfones

    PubMed Central

    2015-01-01

    The development of efficient methods for the generation of enantioenriched sulfonamides and sulfones is an important objective for fields such as organic synthesis and medicinal chemistry; however, there have been relatively few reports of direct catalytic asymmetric approaches to controlling the stereochemistry of the sulfur-bearing carbon of such targets. In this report, we describe nickel-catalyzed stereoconvergent Negishi arylations and alkenylations of racemic α-bromosulfonamides and -sulfones that furnish the desired cross-coupling product in very good ee and yield for an array of reaction partners. Mechanistic studies are consistent with the generation of a radical intermediate that has a sufficient lifetime to diffuse out of the solvent cage and to cyclize onto a pendant olefin. PMID:25127186

  12. Pd-catalyzed divergent trifluoroethylation and arylation of arylboronic acids by aryl(2,2,2-trifluoroethyl)iodonium triflates.

    PubMed

    Yang, Jing; Han, Qiu-Yan; Zhao, Cheng-Long; Dong, Tao; Hou, Zhi-Yuan; Qin, Hua-Li; Zhang, Cheng-Pan

    2016-08-10

    Highly electrophilic aryl(2,2,2-trifluoroethyl)iodonium triflates have been used for the first time as trifluoroethyl and aryl transfer reagents in Pd-catalyzed functionalization of arylboronic acids. Electron-rich arylboronic acids reacted with aryl(2,2,2-trifluoroethyl)iodonium triflates (2a-b) in CH3CN in the presence of Pd2(dba)3 and K3PO4 at room temperature to provide trifluoroethyl arenes in up to 82% yield, while the reactions of both electron-rich and -poor arylboronic acids with 2a-b in DMF in the presence of Pd[P(t-Bu)3]2 and Cs2CO3 at 40 °C afforded arylation products in up to 99% yield. This tunable protocol allows access to trifluoroethyl arenes or biaryls in good to excellent yields under mild conditions and without the addition of extra ligands. PMID:27384263

  13. Lithium bromide chiller technology in gas processing

    SciTech Connect

    Huey, M.A.; Leppin, D.

    1995-12-31

    Lithium Bromide (LiBr) Absorption Chillers have been in use for more than half a century, mainly in the commercial air conditioning industry. The Gas Research Institute and EnMark Natural Gas Company co-funded a field test to determine the viability of this commercial air conditioning technology in the gas industry. In 1991, a 10 MMCFC natural gas conditioning plant was constructed in Sherman, Texas. The plant was designed to use a standard, off-the-shelf chiller from Trane with a modified control scheme to maintain tight operating temperature parameters. The main objective was to obtain a 40 F dewpoint natural gas stream to meet pipeline sales specifications. Various testing performed over the past three years has proven that the chiller can be operated economically and on a continuous basis in an oilfield environment with minimal operation and maintenance costs. This paper will discuss how a LiBr absorption chiller operates, how the conditioning plant performed during testing, and what potential applications are available for LiBr chiller technology.

  14. Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

    NASA Astrophysics Data System (ADS)

    Sidera, Mireia; Fletcher, Stephen P.

    2015-11-01

    Csp2-Csp2 cross-coupling reactions between arylboronic acid and aryl halides are widely used in both academia and industry and are strategically important in the development of new agrochemicals and pharmaceuticals. Csp2-Csp3 cross-coupling reactions have been developed, but enantioselective variations are rare and simply retaining the stereochemistry is a problem. Here we report a highly enantioselective Csp2-Csp3 bond-forming method that couples arylboronic acids to racemic allyl chlorides. Both enantiomers of a cyclic chloride are converted into a single enantiomer of product via a dynamic kinetic asymmetric transformation. This Rh-catalysed method uses readily available and inexpensive building blocks and is mild and broadly applicable. For electron-deficient, electron-rich or ortho-substituted boronic acids better results are obtained with racemic allyl bromides. Oxygen substitution in the allyl halide is tolerated and the products can be functionalized to provide diverse building blocks. The approach fills a significant gap in the methods for catalytic asymmetric synthesis.

  15. Health and Environmental Effects Profile for methyl bromide

    SciTech Connect

    Not Available

    1986-06-01

    The Health and Environmental Effects Profile for methyl bromide was prepared to support listings of hazardous constituents of a wide range of waste streams under Section 3001 of the Resource Conservation and Recovery Act (RCRA) and to provide health-related limits for emergency actions under Section 101 of the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Both published literature and information obtained from Agency program office files were evaluated as they pertained to potential human health, aquatic life, and environmental effects. Quantitative estimates are presented provided sufficient data are available. Methyl bromide has been determined to be a systemic toxicant. An Acceptable Daily Intake (ADI), for methyl bromide is 0.0014 mg/kg/day for oral exposure. The Reportable Quantity (RQ) value for methyl bromide is 100.

  16. Kinetics and Mechanism of the Chlorate-Bromide Reaction.

    PubMed

    Sant'Anna, Rafaela T P; Faria, Roberto B

    2015-11-01

    The chlorate-bromide reaction, ClO3(-) + 6Br(-) + 6H(+) → 3Br2 + Cl(-) + 3H2O, was followed at the Br3(-)/Br2 isosbestic point (446 nm). A fifth-order rate law was found: (1)/3 d[Br2]/dt = k[ClO3(-)][Br(-)][H(+)](3) (k = 5.10 × 10(-6) s(-1) L(4) mol(-4)) at 25 °C and I = 2.4 mol L(-1). At high bromide concentrations, the bromide order becomes close to zero, indicating a saturation profile on bromide concentration, similar to the chloride saturation profile observed in the chlorate-chloride reaction. A mechanism is proposed that considers the formation of the intermediate BrOClO2(2-), similar to the intermediate ClOClO2(2-) proposed in the mechanism of the chlorate-chloride reaction. PMID:26467822

  17. Restoration of bearings

    NASA Technical Reports Server (NTRS)

    Parker, R. J.; Zaretsky, E. V.; Hanau, H.

    1977-01-01

    Process consisting of grinding raceways to oversize but original quality condition and installing new oversize balls or bearings restores wornout ball and roller bearings to original quality, thereby doubling their operating life. Evaluations reveal process results in restoration of 90% of replaced bearings at less than 50% of new-bearing costs.

  18. Passive magnetic bearing configurations

    DOEpatents

    Post, Richard F.

    2011-01-25

    A journal bearing provides vertical and radial stability to a rotor of a passive magnetic bearing system when the rotor is not rotating and when it is rotating. In the passive magnetic bearing system, the rotor has a vertical axis of rotation. Without the journal bearing, the rotor is vertically and radially unstable when stationary, and is vertically stable and radially unstable when rotating.

  19. Rolling-Element Bearings

    NASA Technical Reports Server (NTRS)

    Hamrock, B. J.; Anderson, W. J.

    1983-01-01

    Rolling element bearings are a precision, yet simple, machine element of great utility. A brief history of rolling element bearings is reviewed and the type of rolling element bearings, their geometry and kinematics, as well as the materials they are made from and the manufacturing processes they involve are described. Unloaded and unlubricated rolling element bearings, loaded but unlubricated rolling element bearings and loaded and lubricated rolling element bearings are considered. The recognition and understanding of elastohydrodynamic lubrication covered, represents one of the major development in rolling element bearings.

  20. Introduction to ball bearings

    NASA Technical Reports Server (NTRS)

    Hamrock, B. J.; Dowson, D.

    1981-01-01

    The purpose of a ball bearing is to provide a relative positioning and rotational freedom while transmitting a load between two structures, usually a shaft and a housing. For high rotational speeds (e.g., in gyroscope ball bearings) the purpose can be expanded to include rotational freedom with practically no wear in the bearing. This condition can be achieved by separating the bearing parts with a coherent film of fluid known as an elastohydrodynamic film. This film can be maintained not only when the bearing carries the load on a shaft, but also when the bearing is preloaded to position the shaft to within micro- or nano-inch accuracy and stability. Background information on ball bearings is provided, different types of ball bearings and their geometry and kinematics are defined, bearing materials, manufacturing processes, and separators are discussed. It is assumed, for the purposes of analysis, that the bearing carries no load.

  1. Comparison of Diffusion Coefficients of Aryl Carbonyls and Aryl Alcohols in Hydroxylic Solvents. Evidence that the Diffusion of Ketyl Radicals in Hydrogen-Bonding Solvents is Not Anomalous?

    SciTech Connect

    Autrey, S Thomas ); Camaioni, Donald M. ); Kandanarachchi, Pramod H.; Franz, James A. )

    2000-12-01

    The diffusion coefficients of a benzyl-, sec-phenethyl-, and diphenylmethyl alcohol and the corresponding aryl carbonyls (benzaldehyde, acetophenone and benzophenone) were measured by Taylor's dispersion method in both ethyl and isopropyl alcohol. The experimental values are compared to published transient grating measurements of the corresponding aryl ketyl radicals (benzyl-, sec-phenethyl-, and diphenylmethyl-ketyl radical). In general, the diffusion coefficient of the aryl alcohols and the corresponding aryl ketyl radicals are equivalent within experimental error. This work shows that the diffusion of ketyl radicals is not anomalously slow and that aryl alcohols are significantly better models than the corresponding aryl ketones for analyzing the diffusion of aryl ketyl radicals in both ethyl and isopropyl alcohol. Empirical estimates of the diffusion coefficients of aryl alcohols using the Spernol-Wirtz and Wilke-Chang modifications to the Stokes-Einstein diffusion equation do not adequately account for the interactions between the aryl ketyl radicals or aryl alcohols with the hydroxylic solvents ethyl and isopropyl alcohol. The excellent agreement between the experimental diffusion coefficients of the aryl alcohols and the corresponding ketyl radicals show that the transient grating method can provide accurate estimates for the diffusion coefficients of transient species. This is especially important when a stable model is not available, for example the pyranyl radical.

  2. The oceans: A source or a sink of methyl bromide?

    SciTech Connect

    Pilinis, C.; King, D.B.; Saltzman, E.S.

    1996-04-15

    The global ocean/atmosphere flux of methyl bromide has been estimated from shipboard measurements of the saturation anomaly. When such data are extrapolated globally on the basis of constant saturation anomaly, the ocean is a net sink for methyl bromide [Lobert et al.]. The same data can also be extrapolated on the basis of steady-state production rate of methyl bromide in the water column, allowing regional and seasonal variations in temperature to affect the saturation anomaly. The authors have carried out this type of extrapolation, and they found that the oceans are a strong net source of methyl bromide to the atmosphere. The difference arises mainly due to slow degradation rates in water of higher latitudes. A reduction of the applied production rate by more than 35% is needed in order to switch the ocean from a source to a sink of methyl bromide. These results demonstrate the sensitivity of current estimates of oceanic flux to assumptions about methyl bromide production and destruction in the water column. 19 refs., 2 fig.

  3. High efficiency magnetic bearings

    NASA Technical Reports Server (NTRS)

    Studer, Philip A.; Jayaraman, Chaitanya P.; Anand, Davinder K.; Kirk, James A.

    1993-01-01

    Research activities concerning high efficiency permanent magnet plus electromagnet (PM/EM) pancake magnetic bearings at the University of Maryland are reported. A description of the construction and working of the magnetic bearing is provided. Next, parameters needed to describe the bearing are explained. Then, methods developed for the design and testing of magnetic bearings are summarized. Finally, a new magnetic bearing which allows active torque control in the off axes directions is discussed.

  4. Synthesis and evaluation of antitubercular activity of fluorinated 5-aryl-4-(hetero)aryl substituted pyrimidines.

    PubMed

    Verbitskiy, Egor V; Baskakova, Svetlana A; Kravchenko, Marionella A; Skornyakov, Sergey N; Rusinov, Gennady L; Chupakhin, Oleg N; Charushin, Valery N

    2016-08-15

    Various 5-(fluoroaryl)-4-(hetero)aryl substituted pyrimidines have been synthesized based on the Suzuki cross-coupling and nucleophilic aromatic substitution of hydrogen (SN(H)) reactions starting from commercially available 5-bromopyrimidine and their antitubercular activity against Mycobacterium tuberculosis H37Rv has been explored. The outcome of the study disclose that, some of the compounds have showed promising activity in micromolar concentration against Mycobacterium tuberculosis H37Rv, Mycobacterium avium, Mycobacterium terrae, and multidrug-resistant strains isolated from tuberculosis patients in Ural region (Russia). The data concerning the 'structure-activity' relationship for fluorinated compounds have been discussed. PMID:27338658

  5. The toxic chemistry of methyl bromide.

    PubMed

    Bulathsinghala, A T; Shaw, I C

    2014-01-01

    Methyl bromide (MeBr) is a chemically reactive compound that has found use as a fire retardant and fumigant used for wood, soil, fruits and grains. Its use is banned in many countries because of its ozone-depleting properties. Despite this ban, the use of MeBr persists in some parts of the world (e.g. New Zealand) due to its important role in maintaining strict biosecurity of exported and imported products. Its high chemical reactivity leads to a broad toxicological profile ranging from acute respiratory toxicity following inhalation exposure, through carcinogenicity to neurotoxicty. In this article, we discuss the chemistry of MeBr in the context of its mechanisms of toxicity. The chemical reactivity of MeBr clearly underlies its toxicity. Bromine (Br) is electronegative and a good leaving group; the δ+ carbon thus facilitates electrophilic methylation of biological molecules including glutathione (GSH) via its δ- sulphur atom, leading to downstream effects due to GSH depletion. DNA alkylation, either directly by MeBr or indirectly due to reduction in GSH-mediated detoxification of reactive alkylating chemical species, might explain the carcinogenicity of MeBr. The neurotoxicity of MeBr is much more difficult to understand, but we speculate that methyl phosphates formed in cells might contribute to its neurone-specific toxicity via cholinesterase inhibition. Finally, evidence reviewed shows that it is unlikely for Br⁻ liberated by the metabolism of MeBr to have any toxicological effect because the Br⁻ dose is very low. PMID:23800997

  6. Assessment of Ethidium bromide and Ethidium monoazide bromide removal from aqueous matrices by adsorption on cupric oxide nanoparticles.

    PubMed

    Fakhri, Ali

    2014-06-01

    The present study was undertaken to develop an effective adsorbent and to study the adsorption of Ethidium bromide and Ethidium monoazide bromide from aqueous solution using the CuO nanoparticles. The characteristics of CuO nanoparticles were determined and found to have a surface area 89.59m(2)/g. Operational parameters such as pH, contact time and adsorbent concentration, initial concentration and temperature were also studied. The amount of removal increases with the increase in pH from one to seven and reaches the maximum when the pH is nine. Adsorption data fitted well with the Langmuir, Freundlich and Florry-Huggins models. The results show that the best fit was achieved with the Langmuir isotherm equation with maximum adsorption capacities of 0.868 and 0.662mg/g for Ethidium bromide and Ethidium monoazide bromide, respectively. The adsorption process was found to follow pseudo-second-order kinetics. The calculated thermodynamic parameters, namely ΔG, ΔH and ΔS showed that adsorption of Ethidium bromide and Ethidium monoazide bromide was spontaneous and endothermic under examined conditions. PMID:24630576

  7. Control of Reactivity and Regioselectivity for On-Surface Dehydrogenative Aryl-Aryl Bond Formation.

    PubMed

    Kocić, Nemanja; Liu, Xunshan; Chen, Songjie; Decurtins, Silvio; Krejčí, Ondřej; Jelínek, Pavel; Repp, Jascha; Liu, Shi-Xia

    2016-05-01

    Regioselectivity is of fundamental importance in chemical synthesis. Although many concepts for site-selective reactions are well established for solution chemistry, it is not a priori clear whether they can easily be transferred to reactions taking place on a metal surface. A metal will fix the chemical potential of the electrons and perturb the electronic states of the reactants because of hybridization. Additionally, techniques to characterize chemical reactions in solution are generally not applicable to on-surface reactions. Only recent developments in resolving chemical structures by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) paved the way for identifying individual reaction products on surfaces. Here we exploit a combined STM/AFM technique to demonstrate the on-surface formation of complex molecular architectures built up from a heteroaromatic precursor, the tetracyclic pyrazino[2,3-f][4,7]phenanthroline (pap) molecule. Selective intermolecular aryl-aryl coupling via dehydrogenative C-H activation occurs on Au(111) upon thermal annealing under ultrahigh vacuum (UHV) conditions. A full atomistic description of the different reaction products based on an unambiguous discrimination between pyrazine and pyridine moieties is presented. Our work not only elucidates that ortho-hydrogen atoms of the pyrazine rings are preferentially activated over their pyridine equivalents, but also sheds new light onto the participation of substrate atoms in metal-organic coordination bonding during covalent C-C bond formation. PMID:27059121

  8. Nucleophilic Addition of Nitrogen to Aryl Cations: Mimicking Titan Chemistry

    NASA Astrophysics Data System (ADS)

    Li, Anyin; Jjunju, Fred P. M.; Cooks, R. Graham

    2013-11-01

    The reactivity of aryl cations toward molecular nitrogen is studied systematically in an ion trap mass spectrometer at 102 Pascal of nitrogen, the pressure of the Titan main haze layer. Nucleophilic addition of dinitrogen occurs and the nature of aryl group has a significant influence on the reactivity, through inductive effects and by changing the ground state spin multiplicity. The products of nitrogen activation, aryldiazonium ions, react with typical nitriles, aromatic amines, and alkynes (compounds that are relevant as possible Titan atmosphere constituents) to form covalently bonded heterocyclic products. Theoretical calculations at the level [DFT(B3LYP)/6-311++G(d,p)] indicate that the N2 addition reaction is exothermic for the singlet aryl cations but endothermic for their triplet spin isomers. The -OH and -NH2 substituted aryl ions are calculated to have triplet ground states, which is consistent with their decreased nitrogen addition reactivity. The energy needed for the generation of the aryl cations from their protonated precursors (ca. 340 kJ/mol starting with protonated aniline) is far less than that required to directly activate the nitrogen triple bond (the lowest energy excited state of N2 lies ca. 600 kJ/mol above the ground state). The formation of aza-aromatics via arene ionization and subsequent reactions provide a conceivable route to the genesis of nitrogen-containing organic molecules in the interstellar medium and Titan haze layers.

  9. Nucleophilic addition of nitrogen to aryl cations: mimicking Titan chemistry.

    PubMed

    Li, Anyin; Jjunju, Fred P M; Cooks, R Graham

    2013-11-01

    The reactivity of aryl cations toward molecular nitrogen is studied systematically in an ion trap mass spectrometer at 10(2) Pascal of nitrogen, the pressure of the Titan main haze layer. Nucleophilic addition of dinitrogen occurs and the nature of aryl group has a significant influence on the reactivity, through inductive effects and by changing the ground state spin multiplicity. The products of nitrogen activation, aryldiazonium ions, react with typical nitriles, aromatic amines, and alkynes (compounds that are relevant as possible Titan atmosphere constituents) to form covalently bonded heterocyclic products. Theoretical calculations at the level [DFT(B3LYP)/6-311++G(d,p)] indicate that the N2 addition reaction is exothermic for the singlet aryl cations but endothermic for their triplet spin isomers. The -OH and -NH2 substituted aryl ions are calculated to have triplet ground states, which is consistent with their decreased nitrogen addition reactivity. The energy needed for the generation of the aryl cations from their protonated precursors (ca. 340 kJ/mol starting with protonated aniline) is far less than that required to directly activate the nitrogen triple bond (the lowest energy excited state of N2 lies ca. 600 kJ/mol above the ground state). The formation of aza-aromatics via arene ionization and subsequent reactions provide a conceivable route to the genesis of nitrogen-containing organic molecules in the interstellar medium and Titan haze layers. PMID:23982933

  10. Disposition of ( UC)methyl bromide in rats after inhalation

    SciTech Connect

    Bond, J.A.; Dutcher, J.S.; Medinsky, M.A.; Henderson, R.F.; Birnbaum, L.S.

    1985-01-01

    The purpose of this investigation was to determine the disposition and metabolism of ( UC)methyl bromide in rats after inhalation. Male Fischer-344 rats were exposed nose only to a vapor concentration of 337 nmol ( UC)methyl bromide/liter air (9.0 ppm, 25C, 620 torr) for 6 hr. Urine, feces, expired air, and tissues were collected for up to 65 hr after exposure. Elimination of UC as UCO2 was the major route of excretion with about 47% (3900 nmol/rat) of the total ( UC)methyl bromide absorbed excreted by this route. CO2 excretion exhibited a biphasic elimination pattern with 85% of the UCO2 being excreted with a half-time of 3.9 +/- 0.1 hr (anti x +/- SE) and 15% excreted with a half-time of 11.4 +/- 0.2 hr. Half-times for elimination of UC in urine and feces were 9.6 +/- 0.1 and 16.1 +/- 0.1 hr, respectively. By 65 hr after exposure, about 75% of the initial radioactivity had been excreted with 25% remaining in the body. Radioactivity was widely distributed in tissues immediately following exposure with lung (250 nmol equivalents/g), adrenal (240 nmol equivalents/g), and nasal turbinates (110 nmol equivalents/g) containing the highest concentrations of UC. Radioactivity in livers immediately after exposure accounted for about 17% of the absorbed methyl bromide. Radioactivity in all other tissues examined accounted for about 10% of the absorbed methyl bromide. Elimination half-times of UC from tissues were on the order of 1.5 to 8 hr. In all tissues examined, over 90% of the UC in the tissues was methyl bromide metabolities. The data from this study indicate that after inhalation methyl bromide is rapidly metabolized in tissues and readily excreted. 22 references, 4 figures, 4 tables.

  11. [Reaction of 3-aryl-2-nitroacrylates with titanium tetrachloride. Formation of 4H-1,2-oxazines and hydroxy-arylaldehydes].

    PubMed

    Hirotani, S; Zen, S

    1994-04-01

    The reaction of ethyl 3-aryl-2-nitroacrylate (1a: aryl = 3-methoxyphenyl) with toluene in the presence of titanium tetrachloride gave 4-(4'-methyl-phenyl)-4H-1,2-benzoxazine (3) in a 44.2% yield. The acrylate 1a reacted with dichloromethane in the presence of titanium tetrachloride to give 5-methoxy-salicylaldehyde (2a) in a 61.8% yield. Therefore, 2a was presumed to be formed via an intermediate 4H-1,2-benzoxazine (3'), followed by ring opening to quinone methide and cyano formate. In a similar reaction using both toluene and dichloromethane, 1 bearing a 2-naphthyl group gave a dimer of quinone methide and 1-hydroxy-2-naphthaldehyde via 4H-naphth[2,1-e]-1,2-oxazine, respectively. PMID:8201549

  12. Highly regioselective meta arylation of oxalyl amide-protected β-arylethylamine via the Catellani reaction.

    PubMed

    Han, Jian; Zhang, Li; Zhu, Yan; Zheng, Yongxiang; Chen, Xiaolan; Huang, Zhi-Bin; Shi, Da-Qing; Zhao, Yingsheng

    2016-05-25

    The first bidentate directing group assisted highly selective meta arylation of β-arylethylamine derivatives via palladium/norbornene catalysis is reported, and the range of aryl iodides for the oxalyl amide assisted meta-selective arylation reactions is broadest yet reported. This meta arylation also proceeds well with thiophene derivatives, giving the corresponding products in satisfactory yields. And three-step functionalization of arylethyloxalamide with three different functional groups is successfully performed. PMID:27142086

  13. Modular synthesis of triarylmethanes through palladium-catalyzed sequential arylation of methyl phenyl sulfone.

    PubMed

    Nambo, Masakazu; Crudden, Cathleen M

    2014-01-13

    Triarylmethanes, which are valuable structures in materials, sensing and pharmaceuticals, have been synthesized starting from methyl phenyl sulfone as an inexpensive and readily available template. The three aryl groups were installed through two sequential palladium-catalyzed C-H arylation reactions, followed by an arylative desulfonation. This method provides a new synthetic approach to multisubstituted triarylmethanes using readily available haloarenes and aryl boronic acids, and is also valuable for the preparation of unexplored triarylmethane-based materials and pharmaceuticals. PMID:24307286

  14. UV photodissociation of methyl bromide and methyl bromide cation studied by velocity map imaging

    SciTech Connect

    Blanchet, Valerie; Samartzis, Peter C.; Wodtke, Alec M.

    2009-01-21

    We employ the velocity map imaging technique to measure kinetic energy and angular distributions of state selected CH{sub 3} (v{sub 2}=0,1,2,3) and Br ({sup 2}P{sub 3/2}, {sup 2}P{sub 1/2}) photofragments produced by methyl bromide photolysis at 215.9 nm. These results show unambiguously that the Br and Br* forming channels result in different vibrational excitations of the umbrella mode of the methyl fragment. Low energy structured features appear on the images, which arise from CH{sub 3}Br{sup +} photodissociation near 330 nm. The excess energy of the probe laser photon is channeled into CH{sub 3}{sup +} vibrational excitation, most probably in the {nu}{sub 4} degenerate bend.

  15. 40 CFR 721.6220 - Aryl sulfonate of a fatty acid mixture, polyamine condensate.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aryl sulfonate of a fatty acid mixture... Specific Chemical Substances § 721.6220 Aryl sulfonate of a fatty acid mixture, polyamine condensate. (a... generically as an aryl sulfonate of a fatty acid mixture, polyamine condensate (PMN P-91-584) is subject...

  16. 40 CFR 721.6220 - Aryl sulfonate of a fatty acid mixture, polyamine condensate.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aryl sulfonate of a fatty acid mixture... Specific Chemical Substances § 721.6220 Aryl sulfonate of a fatty acid mixture, polyamine condensate. (a... generically as an aryl sulfonate of a fatty acid mixture, polyamine condensate (PMN P-91-584) is subject...

  17. Zinc Bromide Combustion: Implications for the Consolidated Incinerator Facility

    SciTech Connect

    Oji, L.N.

    1998-12-16

    In the nuclear industry, zinc bromide (ZnBr2) is used for radiation shielding. At Savannah River Site (SRS) zinc bromide solution, in appropriate configurations and housings, was used mainly for shielding in viewing windows in nuclear reactor and separation areas. Waste stream feeds that will be incinerated at the CIF will occasionally include zinc bromide solution/gel matrices.The CIF air pollution systems control uses a water-quench and steam atomizer scrubber that collects salts, ash and trace metals in the liquid phase. Water is re-circulated in the quench unit until a predetermined amount of suspended solids or dissolved salts are present. After reaching the threshold limit, "dirty liquid", also called "blowdown", is pumped to a storage tank in preparation for treatment and disposal. The air pollution control system is coupled to a HEPA pre-filter/filter unit, which removes particulate matter from the flue gas stream (1).The objective of this report is to review existing literature data on the stability of zinc bromide (ZnBr2) at CIF operating temperatures (>870 degrees C (1600 degrees F) and determine what the combustion products are in the presence of excess air. The partitioning of the combustion products among the quencher/scrubber solution, bottom ash and stack will also be evaluated. In this report, side reactions between zinc bromide and its combustion products with fuel oil were not taken into consideration.

  18. Effect of Bromide-Hypochlorite Bactericides on Microorganisms1

    PubMed Central

    Shere, Lewis; Kelley, Maurice J.; Richardson, J. Harold

    1962-01-01

    A new principle in compounding stable, granular bactericidal products led to unique combinations of a water-soluble inorganic bromide salt with a hypochlorite-type disinfectant of either inorganic or organic type. Microbiological results are shown for an inorganic bactericide composed of chlorinated trisodium phosphate containing 3.1% “available chlorine” and 2% potassium bromide, and for an organic bactericide formulated from sodium dichloroisocyanurate so as to contain 13.4% “available chlorine” and 8% potassium bromide. Comparison of these products with their nonbromide counterparts are reported for Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Streptococcus lactis, Aerobacter aerogenes, and Proteus vulgaris. Test methods employed were the Chambers test, the A.O.A.C. Germicidal and Detergent Sanitizer-Official test, and the Available Chlorine Germicidal Equivalent Concentration test. The minimal killing concentrations for the bromide-hypochlorite bactericides against this variety of organisms were reduced by a factor 2 to 24 times those required for similar hypochlorite-type disinfectants not containing the bromide. PMID:13977149

  19. Electrophysiological study of intravenous pinaverium bromide in cardiology.

    PubMed

    Guerot, C; Khemache, A; Sebbah, J; Noel, B

    1988-01-01

    Pinaverium bromide is a musculotropic spasmolytic agent which acts by inhibiting transmembrane calcium movements, an effect similar to that of verapamil. Because of this, an investigation was carried out to see if it had any electrophysiological effects in patients with various cardiac disorders. In an open study, 10 patients received 2 mg pinaverium bromide intravenously. In a double-blind study, 10 patients received 4 mg pinaverium bromide intravenously and 10 patients placebo. Patients included those with either normal or pathological basal conduction, such as bundle-branch block and 1st degree atrioventricular block. Measurements were made of electrophysiological parameters before and 10 minutes after injection. The results showed that neither of the two doses of pinaverium bromide had any effect on atrial excitability, sino-atrial conduction, node and trunk atrioventricular conduction or on intraventricular conduction. No significant difference was seen in comparison with placebo. Pinaverium bromide had no anti-arrhythmic properties in these studies. Local, cardiac and general clinical tolerability was good in all patients. PMID:3219882

  20. Aryl Rhodanines Specifically Inhibit Staphylococcal and Enterococcal Biofilm Formation▿ †

    PubMed Central

    Opperman, Timothy J.; Kwasny, Steven M.; Williams, John D.; Khan, Atiyya R.; Peet, Norton P.; Moir, Donald T.; Bowlin, Terry L.

    2009-01-01

    Staphylococcus epidermidis and Staphylococcus aureus are the leading causative agents of indwelling medical device infections because of their ability to form biofilms on artificial surfaces. Here we describe the antibiofilm activity of a class of small molecules, the aryl rhodanines, which specifically inhibit biofilm formation of S. aureus, S. epidermidis, Enterococcus faecalis, E. faecium, and E. gallinarum but not the gram-negative species Pseudomonas aeruginosa or Escherichia coli. The aryl rhodanines do not exhibit antibacterial activity against any of the bacterial strains tested and are not cytotoxic against HeLa cells. Preliminary mechanism-of-action studies revealed that the aryl rhodanines specifically inhibit the early stages of biofilm development by preventing attachment of the bacteria to surfaces. PMID:19651903

  1. Mechanical spin bearings

    NASA Technical Reports Server (NTRS)

    Vranish, John M. (Inventor)

    1998-01-01

    A spin bearing assembly including, a pair of mutually opposing complementary bearing support members having mutually spaced apart bearing support surfaces which may be, for example, bearing races and a set of spin bearings located therebetween. Each spin bearing includes a pair of end faces, a central rotational axis passing through the end faces, a waist region substantially mid-way between the end faces and having a first thickness dimension, and discrete side surface regions located between the waist region and the end faces and having a second thickness dimension different from the first thickness dimension of the waist region and wherein the side surface regions further have respective curvilinear contact surfaces adapted to provide a plurality of bearing contact points on the bearing support members.

  2. Axial Halbach Magnetic Bearings

    NASA Technical Reports Server (NTRS)

    Eichenberg, Dennis J.; Gallo, Christopher A.; Thompson, William K.

    2008-01-01

    Axial Halbach magnetic bearings have been investigated as part of an effort to develop increasingly reliable noncontact bearings for future high-speed rotary machines that may be used in such applications as aircraft, industrial, and land-vehicle power systems and in some medical and scientific instrumentation systems. Axial Halbach magnetic bearings are passive in the sense that unlike most other magnetic bearings that have been developed in recent years, they effect stable magnetic levitation without need for complex active control.

  3. Supertough Stainless Bearing Steel

    NASA Technical Reports Server (NTRS)

    Olson, Gregory B.

    1995-01-01

    Composition and processing of supertough stainless bearing steel designed with help of computer-aided thermodynamic modeling. Fracture toughness and hardness of steel exceeds those of other bearing steels like 440C stainless bearing steel. Developed for service in fuel and oxidizer turbopumps on Space Shuttle main engine. Because of strength and toughness, also proves useful in other applications like gears and surgical knives.

  4. 1-Way Bearing

    NASA Technical Reports Server (NTRS)

    Vranish, John M. (Inventor)

    2003-01-01

    A one-way bearing is provided having sprags and rolling bearings both disposed between an inner and an outer race. The sprags may comprise three-dimensional sprags for preventing rotation in a non-preferential direction. The roll- ing bearings may comprise thrust rollers for transmitting axial, tilt, and radial loads between the inner and outer races.

  5. Selective Metal-Site-Guided Arylation of Proteins.

    PubMed

    Willwacher, Jens; Raj, Ritu; Mohammed, Shabaz; Davis, Benjamin G

    2016-07-20

    We describe palladium-mediated S-arylation that exploits natural metal-binding motifs to ensure high site selectivity for a proximal reactive residue. This allows the chemical identification not only of proteins that bind metals but also the environment of the metal-binding site itself through proteomic analysis of arylation sites. The transformation is easy to perform under standard conditions, does not require the isolation of a reactive Ar-Pd complex, is broad in scope, and is applicable in cell lysates as well as to covalent inhibition/modulation of metal-dependent enzymatic activity. PMID:27336299

  6. NITROSATION OF ARYL AND HETEROARYLTRIFLUOROBORATES WITH NITROSONIUM TETRAFLUOROBORATE

    PubMed Central

    Cavalcanti, Livia N.

    2012-01-01

    Organotrifluoroborates have emerged as an alternative to toxic and air- and moisture sensitive organometallic species for the synthesis of functionalized aryl and heteroaryl compounds. It has been shown that the trifluoroborate moiety can be easily converted into a variety of different substituents in a late synthetic stage. In this paper we disclose a mild, selective, and convenient method for the ipso-nitrosation of organotrifluoroborates using nitrosonium tetrafluoroborate (NOBF4). Aryl- and heteroaryltrifluoroborates were converted into the corresponding nitroso products in good to excellent yields. This method proved to be tolerant of a broad range of functional groups. PMID:22524190

  7. Cetyltrimethyl ammonium bromide assisted hydrothermal growth of hematite hollow cubes

    SciTech Connect

    Wang, Wei-Wei; Yao, Jia-Liang

    2010-11-15

    Hematite hollow cubes have been prepared by forced hydrolysis of ferric chloride solutions under hydrothermal conditions. The effects of reaction time, reaction temperature and cetyltrimethyl ammonium bromide on the transformation process from akageneite to hematite were investigated in detail. The products were characterized by X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy. It is found that cetyltrimethyl ammonium bromide was a critical factor influencing the phase transformation process of akageneite and the final morphology of the as-prepared products. With cetyltrimethyl ammonium bromide, hematite hollow cubes and porous spheres were obtained. Otherwise only dense cubes were observed even prolonging reaction time or increasing reaction temperature. The mechanism was proposed.

  8. Investigation of pyridine/propargyl bromide reaction and strong fluorescence enhancements of the resultant poly(propargyl pyridinium bromide).

    PubMed

    Zhou, Changming; Gao, Yong; Chen, Daoyong

    2012-09-20

    Poly(propargyl pyridinium bromide), a kind of conjugated polyelectrolyte with polyacetylene as the backbone and pyridinium as side groups, was synthesized simply via reaction between pyridine and propargyl bromide under mild conditions. The resultant polymer was characterized by (1)H NMR, elemental analysis, FT-IR, and GPC-MALLS. An alkyne group was confirmed as the end group of the polymer chains by the alkyne/azide click chemistry, which reveals that the polymerization is terminated by the reaction between propargyl bromide and carbon anions. It is known that monosubstituted polyacetylenes reported have very weak fluorescence intensities, which limit their applications. As a monosubstituted polyacetylene, the freshly prepared poly(propargyl pyridinium bromide) also has a very weak fluorescence. However, we confirmed that addition of some anions to the polymer solution in DMF or DMSO leads to the fluorescence enhancements up to 25 times. Besides, heating the polymer solution at a temperature between 70 and 130 °C for longer than 0.5 h greatly enhanced the fluorescence intensity. The interaction with the anions or the heating enhances the effective exciton confinement within the conjugated backbone and thus results in the fluorescence enhancements. After the fluorescence enhancements, poly(propargyl pyridinium bromide) has relatively strong fluorescence emissions, which will make it promising in fluorescence-based applications. PMID:22928912

  9. Transition-metal-free, ambient-pressure carbonylative cross-coupling reactions of aryl halides with potassium aryltrifluoroborates.

    PubMed

    Jin, Fengli; Han, Wei

    2015-06-01

    We disclose an unprecedented transition-metal-free carbonylative cross coupling of aryl halides with potassium aryl trifluoroborates even at atmospheric pressure of carbon monoxide. This protocol is efficient, operationally simple, and shows wide scope with regard to both aryl halides and potassium aryl trifluoroborates containing a series of active functional groups. PMID:25939449

  10. Synthesis, bioactivity and structure-activity relationships of new 2-aryl-8-OR-3,4-dihydroisoquinolin-2-iums salts as potential antifungal agents.

    PubMed

    Zhu, Li-Fei; Hou, Zhe; Zhou, Kun; Tong, Zong-Bo; Kuang, Qian; Geng, Hui-Ling; Zhou, Le

    2016-05-15

    As our continuing research on antifungal dihydroisoquinolin-2-ium salts, forty 2-aryl-8-OR-3,4-dihydroisoquinolin-2-ium bromides were synthesized and characterized by spectroscopic analysis. By using the mycelium growth rate method, the compounds were evaluated for antifungal activity against three plant pathogenic fungi and structure-activity relationships (SAR) were derived. The vast majority of the compounds displayed the medium to high activity with inhibition rates of 50-100% at 150μM. About half of the compounds were more active than their natural model compounds sanguinarine and chelerythrine for all the fungi, and part or most of them were more active than positive drugs thiabendazole and azoxystrobin. SAR analysis showed that both substitution patterns of the C-ring and the type of 8-OR group significantly influenced the activity. Thus, a series of new title compounds with excellent antifungal potency emerged. PMID:27072907

  11. Oxidation of manganese(II) during chlorination: role of bromide.

    PubMed

    Allard, S; Fouche, L; Dick, J; Heitz, A; von Gunten, U

    2013-08-01

    The oxidation of dissolved manganese(II) (Mn(II)) during chlorination is a relatively slow process which may lead to residual Mn(II) in treated drinking waters. Chemical Mn(II) oxidation is autocatalytic and consists of a homogeneous and a heterogeneous process; the oxidation of Mn(II) is mainly driven by the latter process. This study demonstrates that Mn(II) oxidation during chlorination is enhanced in bromide-containing waters by the formation of reactive bromine species (e.g., HOBr, BrCl, Br2O) from the oxidation of bromide by chlorine. During oxidation of Mn(II) by chlorine in bromide-containing waters, bromide is recycled and acts as a catalyst. For a chlorine dose of 1 mg/L and a bromide level as low as 10 μg/L, the oxidation of Mn(II) by reactive bromine species becomes the main pathway. It was demonstrated that the kinetics of the reaction are dominated by the adsorbed Mn(OH)2 species for both chlorine and bromine at circumneutral pH. Reactive bromine species such as Br2O and BrCl significantly influence the rate of manganese oxidation and may even outweigh the reactivity of HOBr. Reaction orders in [HOBr]tot were found to be 1.33 (±0.15) at pH 7.8 and increased to 1.97 (±0.17) at pH 8.2 consistent with an important contribution of Br2O which is second order in [HOBr]tot. These findings highlight the need to take bromide, and the subsequent reactive bromine species formed upon chlorination, into account to assess Mn(II) removal during water treatment with chlorine. PMID:23859083

  12. Intensification of sonochemical degradation of malachite green by bromide ions.

    PubMed

    Moumeni, Ouarda; Hamdaoui, Oualid

    2012-05-01

    Sonochemical oxidation has been investigated as a viable advanced oxidation process (AOP) for the destruction of various pollutants in water. Ultrasonic irradiation generates ()OH radicals that can recombine, react with other gaseous species present in the cavity, or diffuse out of the bubble into the bulk liquid medium where they are able to react with solute molecules. The extent of degradation of an organic dye such as malachite green (MG) is limited by the quantity of hydroxyl radicals diffused from cavitation bubbles. In this work, the effect of bromide ions on sonolytic degradation of MG was investigated. The obtained results clearly demonstrated the considerable enhancement of sonochemical destruction of MG in the presence of bromide. No significant differences were observed in the presence of chloride and sulfate, excluding the salting-out effect. Positive effect of bromide ions, which increases with increasing bromide level and decreasing MG concentration, is due to the generation of dibromine radical anion (Br(2)(-)) formed by reaction of Br(-) with ()OH radicals followed by rapid complexation with another anion. The generated Br(2)(-) radicals, reactive but less than ()OH, are likely able to migrate far from the cavitation bubbles towards the solution bulk and are suitable for degradation of an organic dye such as MG. Additionally, Br(2)(-) radicals undergo radical-radical recombination at a lesser extent than hydroxyl radicals and would be more available than ()OH for substrate degradation, both at the bubble surface and in the solution bulk. This effect compensates for the lower reactivity of Br(2)(-) compared to ()OH toward organic substrate. Addition of bromide to natural and sea waters induces a slight positive effect on MG degradation. In the absence of bromide, ultrasonic treatment for the removal of MG was promoted in complex matrices such as natural and sea waters. PMID:21911308

  13. Methyl bromide emissions from a covered field: II. Volatilization

    SciTech Connect

    Yates, S.R.; Gan, J.; Ernst, F.F.

    1996-01-01

    An experiment to investigate the environmental fate and transport of methyl bromide in agricultural fields is described. The methyl bromide volatilization rate was determined as a function of time for conditions where methyl bromide was applied at a rate of 843 kg in a 3.5-ha (i.e., 240 kg/ha) field covered with plastic at a depth of 25 cm. Three methods were used to estimate the methyl bromide volatilization rate, including: the aerodynamic, theoretical profile shape and integrated horizontal flux methods. The highest methyl bromide volatilization rates were at the beginning of the experiment. Within the first 24 h, approximately 36% of the applied methyl bromide mass was lost. Diurnally, the largest volatilization rates occurred during the day when temperatures were high and the atmosphere was unstable. Cooler temperatures, light winds, and neutral to stable atmospheric conditions were present at night, reducing the flux. The total emission calculated using these methods was found to be approximately 64% ({+-} 10%) of the applied mass. A mass balance was calculated using each flux estimation technique and several methods for analyzing the data. The average mass recovery using all the flux methods was 867 kg ({+-}83 kg), which was 102.8% ({+-}9.8%) of the applied (i.e., 843 kg). The range in the mass balance percent (i.e., percent of applied mass that is measured) is from 88 to 112%. The averaged mass balance percent for the aerodynamic method, which involved using the measured data directly, was approximately 100.8%. The total emission calculated using the aerodynamic method was found to be approximately 62% ({+-}11%) of the applied mass. 29 refs., 7 figs., 1 tab.

  14. Photochemistry of alkyl bromides trapped in water ice films

    NASA Astrophysics Data System (ADS)

    Schrems, O.; Okaikwei, B.; Bluszcz, Th.

    2012-04-01

    Photochemical reactions of atmospheric trace gases taking place at the surface of atmospheric ice particles and in bulk ice are important in stratospheric and tropospheric chemistry but also in polar and alpine snowpack chemistry. Consequently, the understanding of the uptake und incorporation of atmospheric trace gases in water ice as well as their interactions with water molecules is very important for the understanding of processes which occur in ice particles and at the air/ice interface. Reactive atmospheric trace gases trapped in ice are subject of photochemical reactions when irradiated with solar UV radiation. Among such compounds bromine species are highly interesting due to their potential of depleting ozone both in the stratosphere and troposphere. Organic bromine gases can carry bromine to the stratosphere. Methyl bromide (CH3Br) is the largest bromine carrier to the stratosphere. It has both natural and anthropogenic sources. In this contribution we will present the results of our laboratory studies of alkyl bromides (methyl, bromide (CH3Br), dimethyl bromide (CH2Br2), n-propyl bromide (C3H7Br), 1,2-dibromoethane C2H4Br2)), trapped in water ice. We have simulated the UV photochemistry of these brominated alkanes isolated in ice films kept at 16 K and for comparison in solid argon matrices. The photoproducts formed in the ice have been identified by means of FTIR spectroscopy. Reflection absorption infrared spectroscopy (RAIRS) is especially useful to study nascent ice surfaces, kinetics of adsorption/decomposition, and heterogeneous catalysis. Among the observed photoproducts we could identify carbon monoxide and carbon dioxide for each alkyl bromide studied. The photoproduct HBr is dissociated in the bulk ice. Based on the experimental observations possible reaction mechanisms will be discussed.

  15. CuI/Oxalic Diamide Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amines.

    PubMed

    Zhou, Wei; Fan, Mengyang; Yin, Junli; Jiang, Yongwen; Ma, Dawei

    2015-09-23

    A class of oxalic diamides are found to be effective ligands for promoting CuI-catalyzed aryl amination with less reactive (hetero)aryl chlorides. The reaction proceeds at 120 °C with K3PO4 as the base in DMSO to afford a wide range of (hetero)aryl amines in good to excellent yields. The bis(N-aryl) substituted oxalamides are superior ligands to N-aryl-N'-alkyl substituted or bis(N-alkyl) substituted oxalamides. Both the electronic nature and the steric property of the aromatic rings in ligands are important for their efficiency. PMID:26352639

  16. Chan-Evans-Lam Amination of Boronic Acid Pinacol (BPin) Esters: Overcoming the Aryl Amine Problem.

    PubMed

    Vantourout, Julien C; Law, Robert P; Isidro-Llobet, Albert; Atkinson, Stephen J; Watson, Allan J B

    2016-05-01

    The Chan-Evans-Lam reaction is a valuable C-N bond forming process. However, aryl boronic acid pinacol (BPin) ester reagents can be difficult coupling partners that often deliver low yields, in particular in reactions with aryl amines. Herein, we report effective reaction conditions for the Chan-Evans-Lam amination of aryl BPin with alkyl and aryl amines. A mixed MeCN/EtOH solvent system was found to enable effective C-N bond formation using aryl amines while EtOH is not required for the coupling of alkyl amines. PMID:27045570

  17. NH-Heterocyclic Aryliodonium Salts and their Selective Conversion into N1-Aryl-5-iodoimidazoles.

    PubMed

    Wu, Yichen; Izquierdo, Susana; Vidossich, Pietro; Lledós, Agustí; Shafir, Alexandr

    2016-06-13

    The synthesis of N-arylimidazoles substituted at the sterically encumbered 5-position is a challenge for modern synthetic approaches. A new family of imidazolyl aryliodonium salts is reported, which serve as a stepping stone on the way to selective formation of N1-aryl-5-iodoimidazoles. Iodine acts as a "universal" placeholder poised for replacement by aryl substituents. These new λ(3) -iodanes are produced by treating the NH-imidazole with ArI(OAc)2 , and are converted to N1-aryl-5-iodoimidazoles by a selective copper-catalyzed aryl migration. The method tolerates a variety of aryl fragments and is also applicable to substituted imidazoles. PMID:27142566

  18. Bearings working group

    NASA Technical Reports Server (NTRS)

    1985-01-01

    The service life of the Space Shuttle Main Engine (SSME) turbomachinery bearings was a predominant factor in engine durability and maintenance problems. Recent data has indicated that bearing life is about one order of magnitude lower than the goal of seven and one-half hours particularly those in the High Pressure Oxidizer Turbopump (HPOTP). Bearing technology, primarily cryogenic turbomachinery bearing technology, is expanded by exploring the life and performance effects of design changes; design concept changes; materials changes; manufacturing technique changes; and lubrication system changes. Each variation is assessed against the current bearing design in full scale cryogenic tests.

  19. Cryogenic Hybrid Magnetic Bearing

    NASA Technical Reports Server (NTRS)

    Meeks, Crawford R.; Dirusso, Eliseo; Brown, Gerald V.

    1994-01-01

    Cryogenic hybrid magnetic bearing is example of class of magnetic bearings in which permanent magnets and electromagnets used to suspend shafts. Electromagnets provide active control of position of shaft. Bearing operates at temperatures from -320 degrees F (-196 degrees C) to 650 degrees F (343 degrees C); designed for possible use in rocket-engine turbopumps, where effects of cryogenic environment and fluid severely limit lubrication of conventional ball bearings. This and similar bearings also suitable for terrestrial rotating machinery; for example, gas-turbine engines, high-vacuum pumps, canned pumps, precise gimbals that suspend sensors, and pumps that handle corrosive or gritty fluids.

  20. Investigation of possible interaction between pinaverium bromide and digoxin.

    PubMed

    Weitzel, O; Seidel, G; Engelbert, S; Berksoy, M; Eberhardt, G; Bode, R

    1983-01-01

    A single-blind study was carried out in 25 patients, who were receiving maintenance therapy for congestive heart failure with digoxin, to investigate the effect on steady-state plasma digoxin levels of concomitant administration of the spasmolytic, pinaverium bromide (50 mg 3-times daily). Patients received pinaverium bromide for 12 days followed by placebo for a further 7 days. Assessment of the results in 21 patients showed no evidence of any statistically significant variations in plasma digoxin levels during either treatment period or in the clinical observations which might indicate drug interaction. PMID:6653138

  1. Action of pinaverium bromide on calmodulin-regulated functions.

    PubMed

    Wuytack, F; De Schutter, G; Casteels, R

    1985-08-01

    Pinaverium bromide at concentrations below 10(-5) M did not inhibit calmodulin-dependent enzymes such as phosphodiesterase and the Ca transport ATPase of the plasma membrane. At higher concentrations the compound interacted with the stimulation of those enzymes by calmodulin and also inhibited the calmodulin-independent activity. A similar inhibitory action was observed for the NaK ATPase. It is concluded that the inhibitory action of pinaverium bromide on smooth muscle concentration at concentrations below 10(-5) M was due to its interaction with the voltage-dependent Ca channels and not to its interference with the calmodulin-dependent activation of the contractile proteins. PMID:2995077

  2. CuO-promoted construction of N-2-aryl-substituted-1,2,3-triazoles via azide-chalcone oxidative cycloaddition and post-triazole arylation.

    PubMed

    Zhang, Yuanqing; Li, Xiaolong; Li, Jihui; Chen, Jinying; Meng, Xu; Zhao, Mingming; Chen, Baohua

    2012-01-01

    An efficient one-pot three-component stepwise approach for the synthesis of N-2-aryl-substituted-1,2,3-triazoles has been developed. By using this azide-chalcone oxidative cycloaddition and post-triazole arylation, a series of N-2-aryl-substituted-1,2,3-triazoles are readily prepared under mild conditions in excellent yields and high regioselectivity. Both the catalyst and substrates are readily available. PMID:22133007

  3. Synthesis of Dibenzosultams by "Transition-Metal-Free" Photoinduced Intramolecular Arylation of N-Aryl-2-halobenzenesulfonamides.

    PubMed

    Guerra, Walter D; Rossi, Roberto A; Pierini, Adriana B; Barolo, Silvia M

    2016-06-17

    A new and general synthetic route to prepare dibenzosultams is here reported. This approach involves the synthesis of N-aryl-2-halobenzenesulfonamides (3), followed by intramolecular C-C photoinduced arylation under soft conditions without the use of "Transition Metal". The photostimulated reactions exhibit very good tolerance to different substituent groups with good to excellent isolated yields (42-98%) of products. Moreover, it is shown that LED (λ = 395 nm) is an efficient light energy source to initiate efficiently the reactions. Theoretical inspection of the mechanism was made to probe the involvement of the radical-anion SRN1 process. PMID:27166973

  4. Magnesium Lewis Acid Assisted Oxidative Bromoetherification Involving Bromine Transfer from Alkyl Bromides with Aldehydes by Umpolung of Bromide.

    PubMed

    Moriyama, Katsuhiko; Nishinohara, Chihiro; Togo, Hideo

    2016-08-16

    An oxidative bromoetherification involving a bromine transfer from alkyl bromides upon reacting them with aldehydes in a Grignard reaction with a concurrent oxidation of bromide was developed to provide substituted tetrahydrofurans in high yields. This reaction, which proceeds through two types of bromine transfer, was promoted by the addition of a Brønsted acid. Mechanistic studies suggested that a magnesium Lewis acid activates hypobromate, which is generated in situ from the reaction of bromide and Oxone to improve the electrophilicity of the bromonium ion (Br(+) ) for the oxidative bromoetherification of alkenyl alcohols. Furthermore, the magnesium Lewis acid catalyzed oxidative bromoetherification of an alkenyl alcohol proceeded to provide a cyclization product in 92 % yield. PMID:27304660

  5. New Trends in Aryl Hydrocarbon Receptor Biology

    PubMed Central

    Mulero-Navarro, Sonia; Fernandez-Salguero, Pedro M.

    2016-01-01

    Traditionally considered as a critical intermediate in the toxic and carcinogenic response to dioxin (2,3,7,8-tetrachlorodibenzo-p-dioxin, TCDD), the Aryl hydrocarbon/Dioxin receptor (AhR) has proven to be also an important regulator of cell physiology and organ homeostasis. AhR has become an interesting and actual area of research mainly boosted by a significant number of recent studies analyzing its contribution to the proper functioning of the immune, hepatic, cardiovascular, vascular and reproductive systems. At the cellular level, AhR establishes functional interactions with signaling pathways governing cell proliferation and cell cycle, cell morphology, cell adhesion and cell migration. Two exciting new aspects in AhR biology deal with its implication in the control of cell differentiation and its more than likely involvement in cell pluripotency and stemness. In fact, it is possible that AhR could help modulate the balance between differentiation and pluripotency in normal and transformed tumor cells. At the molecular level, AhR regulates an increasingly large array of physiologically relevant genes either by traditional transcription-dependent mechanisms or by unforeseen processes involving genomic insulators, chromatin dynamics and the transcription of mobile genetic elements. AhR is also closely related to epigenetics, not only from the point of view of target gene expression but also with respect to its own regulation by promoter methylation. It is reasonable to consider that deregulation of these many functions could have a causative role, or at least contribute to, human disease. Consequently, several laboratories have proposed that AhR could be a valuable tool as diagnostic marker and/or therapeutic target in human pathologies. An additional point of interest is the possibility of regulating AhR activity by endogenous non-toxic low weight molecules agonist or antagonist molecules that could be present or included in the diet. In this review, we will

  6. Palladium-catalyzed arylation of simple arenes with iodonium salts.

    PubMed

    Storr, Thomas E; Greaney, Michael F

    2013-03-15

    The development of an arylation protocol for simple arenes with diaryliodonium salts using the Herrmann-Beller palladacycle catalyst is reported. The reaction takes simple aromatic feedstocks and creates valuable biaryls for use in all sectors of the chemical industry. PMID:23461706

  7. Selective, nickel-catalyzed hydrogenolysis of aryl ethers.

    PubMed

    Sergeev, Alexey G; Hartwig, John F

    2011-04-22

    Selective hydrogenolysis of the aromatic carbon-oxygen (C-O) bonds in aryl ethers is an unsolved synthetic problem important for the generation of fuels and chemical feedstocks from biomass and for the liquefaction of coal. Currently, the hydrogenolysis of aromatic C-O bonds requires heterogeneous catalysts that operate at high temperature and pressure and lead to a mixture of products from competing hydrogenolysis of aliphatic C-O bonds and hydrogenation of the arene. Here, we report hydrogenolyses of aromatic C-O bonds in alkyl aryl and diaryl ethers that form exclusively arenes and alcohols. This process is catalyzed by a soluble nickel carbene complex under just 1 bar of hydrogen at temperatures of 80 to 120°C; the relative reactivity of ether substrates scale as Ar-OAr>Ar-OMe>ArCH(2)-OMe (Ar, Aryl; Me, Methyl). Hydrogenolysis of lignin model compounds highlights the potential of this approach for the conversion of refractory aryl ether biopolymers to hydrocarbons. PMID:21512027

  8. Alkyl Aryl Ether Bond Formation with PhenoFluor**

    PubMed Central

    Shen, Xiao; Neumann, Constanze N.; Kleinlein, Claudia; Claudia, Nathaniel W.; Ritter, Tobias

    2015-01-01

    An alkyl aryl ether bond formation reaction between phenols and primary and secondary alcohols with PhenoFluor has been developed. The reaction features a broad substrate scope and tolerates many functional groups, and substrates that are challenging for more conventional ether bond forming processes may be coupled. A preliminary mechanistic study indicates reactivity distinct from conventional ether bond formation. PMID:25800679

  9. Methyl Bromide Alternatives for Floriculture Production in a Problem Site

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Successful methyl bromide alternatives must manage a variety of pest problems in floriculture and vegetable production systems including weeds, plant-parasitic nematodes, and soil-borne diseases. Methods that may be successful in some situations may be challenged in sites with unusually heavy pest p...

  10. EFFECT OF BROMIDE ION ON FORMATION OF HAAS DURING CHLORINATION

    EPA Science Inventory

    loacetic acids (HAAs) during chlorination and he effects of independent variables, including pH, reaction time, and chlorine dosage. Almost all of the indpendent loaetic acids (HAAs) during chlorin...designed to statistically evaluate the influence of bromide ion on the formatio...

  11. Methyl bromide alternatives for postharvest insect disinfestation of California walnuts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Before shipment, California inshell walnuts destined for the valuable export market must be disinfested of both field pests (codling moth and navel orangeworm) and common storage pests (Indianmeal moth and red flour beetle). Until recently fumigation with methyl bromide has been the most common dis...

  12. A COMPARISON OF BROMIDE AND NITRATE TRANSPORT IN SOILS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sandy soils (with sand content 95-98%) are used for agricultural production, which require careful management of water, chemicals, and nutrients to minimize leaching below the rooting zone. Bromide is used as an indicator of downward transport of soluble nutrients in soils. A leching column study ...

  13. HEALTH AND ENVIRONMENTAL EFFECTS PROFILE FOR METHYL BROMIDE

    EPA Science Inventory

    The Health and Environmental Effects Profile for Methyl Bromide was prepared to support listings of hazardous constituents of a wide range of waste streams under Section 3001 of the Resource Conservation and Recovery Act (RCRA) and to provide health-related limits for emergency a...

  14. Nickel-Catalyzed Reductive Amidation of Unactivated Alkyl Bromides.

    PubMed

    Serrano, Eloisa; Martin, Ruben

    2016-09-01

    A user-friendly, nickel-catalyzed reductive amidation of unactivated primary, secondary, and tertiary alkyl bromides with isocyanates is described. This catalytic strategy offers an efficient synthesis of a wide range of aliphatic amides under mild conditions and with an excellent chemoselectivity profile while avoiding the use of stoichiometric and sensitive organometallic reagents. PMID:27357076

  15. Reactive films for mitigating methyl bromide emissions from fumigated soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Emissions of methyl bromide (MeBr) from agricultural fumigation can lead to depletion of the stratospheric ozone layer, and so its use is being phased out. However, as MeBr is still widely used under Critical Use Exemptions, strategies are still required to control such emissions. In this work, nove...

  16. Calla lily production with methyl bromide alternatives – Year 2

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cut flower and ornamental bulb industries rely heavily on a methyl bromide/chloropicrin (MB/Pic) mixture as a key pest management tool. The loss of MB will seriously affect the cut flower and bulb industry, and, in the future, will require growers to use alternative fumigants. Past experiments have...

  17. Depleting methyl bromide residues in soil by reaction with bases

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Despite generally being considered the most effective soil fumigant, methyl bromide (MeBr) use is being phased out because its emissions from soil can lead to stratospheric ozone depletion. However, a large amount is still currently used due to Critical Use Exemptions. As strategies for reducing the...

  18. Methyl bromide alternatives for postharvest insect disinfestation of California walnuts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Before shipment, California inshell walnuts destined for the valuable export market must be disinfested of both field pests (codling moth and navel orangeworm) and common storage pests (Indianmeal moth and red flour beetle). Until recently fumigation with methyl bromide has been the most common disi...

  19. The Fate of Alternative Soil Funigants to Methyl Bromide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soil fumigation is an important agricultural practice for the control of soil-borne pests. Since the phase–out of methyl bromide, due to its role in the depletion of stratospheric ozone, several alternatives such as 1,3-dichloropropene (1,3-D), chloropicrin (CP), and dimethyl disulfide (DMDS) are b...

  20. Status of Alternatives for Methyl Bromide in the United States

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide is a fumigant used for disinfestation of soils, commodities and structures. Listed as an ozone-depleting chemical international environmental protocols and the U.S. Clean Air Act require that its use be severely restricted. Although use of this fumigant has fallen considerably, the U....

  1. Weed Control with Methyl Bromide Alternatives: A Review.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide (MeBr) has been used for several decades for pre-plant soil fumigation in high value agricultural and horticultural crops because it can provide broad-spectrum control of insects, nematodes, pathogens, and weeds. However, MeBr has been identified as a powerful ozone-depleting chemica...

  2. Methyl bromide phase out could affect future reforestation efforts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide has long been an integral component in producing healthy tree seedlings in forest nurseries of California, Idaho, Montana, Oregon and Washington. The fumigant was supposed to be completely phased out of use in the United States of America by 2005, but many forest nurseries continue to...

  3. REVIEW OF CONTROL OPTIONS FOR METHYL BROMIDE IN COMMODITY TREATMENT

    EPA Science Inventory

    The report describes recent developments in the control of methyl bromide (MeBr) and discusses technical considerations and requirements for and economic feasibility of recovery. (NOTE: MeBr, fumigant for agricultural commodities, is an ozone depleting chemical. The U.S. EPA has ...

  4. Investigation of bromide's spectra by high resolution UV-laser

    NASA Astrophysics Data System (ADS)

    Zhang, Jin; Ma, Jian-guo

    2011-12-01

    Experimental investigation has been carried out for dissociation/ionisation of methyl bromide using time of flight mass spectrometer, then, the mass signals were assigned to H+, CHm+ (m= 0-3), iBr+ (i = 79, 81), and the main processes of multi-photon ionization and dissociation of CH3Br were given.

  5. PHYTOREMEDIATON POTENTIALS OF SELECTED TROPICAL PLANTS FOR ETHIDIUM BROMIDE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Research and development has its own benefits and inconveniences. One of the inconveniences is the generation of enormous quantity of diverse toxic and hazardous wastes and its eventual contamination to soil and groundwater resources. Ethidium bromide (EtBr) is one of the commonly used substances i...

  6. BROMIDE-OXIDANT INTERACTIONS AND THM (TRIHALOMETHANE) FORMATION: A LITERATURE REVIEW

    EPA Science Inventory

    The review focuses on the interactions, not only of bromide and chlorine, but also of bromide and two common oxidation alternatives to chlorine--chlorine dioxide and monochloramine. The data evaluations include discussions of reaction products, potentials for trihalomethane (THM)...

  7. Biaryl and aryl ketone synthesis via Pd-catalyzed decarboxylative coupling of carboxylate salts with aryl triflates.

    PubMed

    Goossen, Lukas J; Linder, Christophe; Rodríguez, Nuria; Lange, Paul P

    2009-09-21

    A bimetallic catalyst system has been developed that for the first time allows the decarboxylative cross-coupling of aryl and acyl carboxylates with aryl triflates. In contrast to aryl halides, these electrophiles give rise to non-coordinating anions as byproducts, which do not interfere with the decarboxylation step that leads to the generation of the carbon nucleophilic cross-coupling partner. As a result, the scope of carboxylate substrates usable in this transformation was extended from ortho-substituted or otherwise activated derivatives to a broad range of ortho-, meta-, and para-substituted aromatic carboxylates. Two alternative protocols have been optimized, one involving heating the substrates in the presence of Cu(I)/1,10-phenanthroline (10-15 mol %) and PdI(2)/phosphine (2-3 mol %) in NMP for 1-24 h, the other involving Cu(I)/1,10-phenanthroline (6-15 mol %) and PdBr(2)/Tol-BINAP (2 mol %) in NMP using microwave heating for 5-10 min. While most products are accessible using standard heating, the use of microwave irradiation was found to be beneficial especially for the conversion of non-activated carboxylates with functionalized aryl triflates. The synthetic utility of the transformation is demonstrated with 48 examples showing the scope and limitations of both protocols. In mechanistic studies, the special role of microwave irradiation is elucidated, and further perspectives of decarboxylative cross-couplings are discussed. PMID:19718720

  8. T-type Ca2+ channel modulation by otilonium bromide

    PubMed Central

    Strege, Peter R.; Sha, Lei; Beyder, Arthur; Bernard, Cheryl E.; Perez-Reyes, Edward; Evangelista, Stefano; Gibbons, Simon J.; Szurszewski, Joseph H.

    2010-01-01

    Antispasmodics are used clinically to treat a variety of gastrointestinal disorders by inhibition of smooth muscle contraction. The main pathway for smooth muscle Ca2+ entry is through L-type channels; however, there is increasing evidence that T-type Ca2+ channels also play a role in regulating contractility. Otilonium bromide, an antispasmodic, has previously been shown to inhibit L-type Ca2+ channels and colonic contractile activity. The objective of this study was to determine whether otilonium bromide also inhibits T-type Ca2+ channels. Whole cell currents were recorded by patch-clamp technique from HEK293 cells transfected with cDNAs encoding the T-type Ca2+ channels, CaV3.1 (α1G), CaV3.2 (α1H), or CaV3.3 (α1I) alpha subunits. Extracellular solution was exchanged with otilonium bromide (10−8 to 10−5 M). Otilonium bromide reversibly blocked all T-type Ca2+ channels with a significantly greater affinity for CaV3.3 than CaV3.1 or CaV3.2. Additionally, the drug slowed inactivation in CaV3.1 and CaV3.3. Inhibition of T-type Ca2+ channels may contribute to inhibition of contractility by otilonium bromide. This may represent a new mechanism of action for antispasmodics and may contribute to the observed increased clinical effectiveness of antispasmodics compared with selective L-type Ca2+ channel blockers. PMID:20203058

  9. Bearings: Technology and needs

    NASA Technical Reports Server (NTRS)

    Anderson, W. J.

    1982-01-01

    A brief status report on bearing technology and present and near-term future problems that warrant research support is presented. For rolling element bearings a material with improved fracture toughness, life data in the low Lambda region, a comprehensive failure theory verified by life data and incorporated into dynamic analyses, and an improved corrosion resistant alloy are perceived as important needs. For hydrodynamic bearings better definition of cavitation boundaries and pressure distributions for squeeze film dampers, and geometry optimization for minimum power loss in turbulent film bearings are needed. For gas film bearings, foil bearing geometries that form more nearly optimum film shapes for maximum load capacity, and more effective surface protective coatings for high temperature operation are needed.

  10. Scaffold-hopping of bioactive flavonoids: Discovery of aryl-pyridopyrimidinones as potent anticancer agents that inhibit catalytic role of topoisomerase IIα.

    PubMed

    Priyadarshani, Garima; Amrutkar, Suyog; Nayak, Anmada; Banerjee, Uttam C; Kundu, Chanakya N; Guchhait, Sankar K

    2016-10-21

    A strategy of scaffold-hopping of bioactive natural products, flavones and isoflavones, leading to target-based discovery of potent anticancer agents has been reported for the first time. Scaffold-hopped flavones, 2-aryl-4H-pyrido[1,2-a]pyrimidin-4-ones and the scaffold-hopped isoflavones, 3-aryl-pyrido[1,2-a]pyrimidin-4-ones were synthesized via Pd-catalyzed activation-arylation methods. Most of the compounds were found to exhibit pronounced human topoisomerase IIα (hTopoIIα) inhibitory activities and several compounds were found to be more potent than etoposide (a hTopoIIα-inhibiting anticancer drug). These classes of compounds were found to be hTopoIIα-selective catalytic inhibitors while not interfering with topoisomerase I and interacted with DNA plausibly in groove domain. Cytotoxicities against various cancer cells, low toxicity in normal cells, and apoptotic effects were observed. Interestingly, compared to parent flavones/isoflavones, their scaffold-hopped analogs bearing alike functionalities showed significant/enhanced hTopoIIα-inhibitory and cytotoxic properties, indicating the importance of a natural product-based scaffold-hopping strategy in the drug discovery. PMID:27343852

  11. Bear Spray Safety Program

    USGS Publications Warehouse

    Blome, C.D.; Kuzniar, R.L.

    2009-01-01

    A bear spray safety program for the U.S. Geological Survey (USGS) was officially initiated by the Firearms Safety Committee to address accident prevention and to promote personnel training in bear spray and its transportation, storage, and use for defense against wild animals. Used as part of a system including firearms, or used alone for those who choose not to carry a firearm, bear spray is recognized as an effective tool that can prevent injury in a wild animal attack.

  12. Bearing restoration by grinding

    NASA Technical Reports Server (NTRS)

    Hanau, H.; Parker, R. J.; Zaretsky, E. V.; Chen, S. M.; Bull, H. L.

    1976-01-01

    A joint program was undertaken by the NASA Lewis Research Center and the Army Aviation Systems Command to restore by grinding those rolling-element bearings which are currently being discarded at aircraft engine and transmission overhaul. Three bearing types were selected from the UH-1 helicopter engine (T-53) and transmission for the pilot program. No bearing failures occurred related to the restoration by grinding process. The risk and cost of a bearing restoration by grinding programs was analyzed. A microeconomic impact analysis was performed.

  13. Extending bearing life

    SciTech Connect

    Boyer, D.

    1997-08-01

    Long-term bearing operation cannot be achieved unless proper handling, storage, installation, and maintenance procedures are followed. These factors can shorten--sometimes drastically--expected bearing service life. Failures are generally related to improper lubrication or installation and induced conditions. Most major bearing manufacturers offer technical assistance in inspection, evaluation, and reporting on bearings which have failed in service. Actual percentages associated with each failure category vary, depending on the source, but generally they are 70% from lubrication and installation, 20% from induced factors, and 10% from reaching their fatigue limit or design life. The paper describes lubricant-related failures and procedures for the correct handling, storage, installation, and maintenance.

  14. Linear magnetic bearing

    NASA Technical Reports Server (NTRS)

    Studer, P. A. (Inventor)

    1983-01-01

    A linear magnetic bearing system having electromagnetic vernier flux paths in shunt relation with permanent magnets, so that the vernier flux does not traverse the permanent magnet, is described. Novelty is believed to reside in providing a linear magnetic bearing having electromagnetic flux paths that bypass high reluctance permanent magnets. Particular novelty is believed to reside in providing a linear magnetic bearing with a pair of axially spaced elements having electromagnets for establishing vernier x and y axis control. The magnetic bearing system has possible use in connection with a long life reciprocating cryogenic refrigerator that may be used on the space shuttle.

  15. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  16. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  17. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  18. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  19. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  20. 40 CFR 721.4090 - Ethanaminium, N-[bis(diethylamino)-methylene]-N-ethyl-, bromide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Ethanaminium, N- -N-ethyl-, bromide... Substances § 721.4090 Ethanaminium, N- -N-ethyl-, bromide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanaminium, N- -N-ethyl-, bromide (PMN...

  1. 40 CFR 721.4090 - Ethanaminium, N-[bis(diethylamino)-methylene]-N-ethyl-, bromide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethanaminium, N- -N-ethyl-, bromide... Substances § 721.4090 Ethanaminium, N- -N-ethyl-, bromide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanaminium, N- -N-ethyl-, bromide (PMN...

  2. 40 CFR 721.4090 - Ethanaminium, N-[bis(diethylamino)-methylene]-N-ethyl-, bromide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Ethanaminium, N- -N-ethyl-, bromide... Substances § 721.4090 Ethanaminium, N- -N-ethyl-, bromide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanaminium, N- -N-ethyl-, bromide (PMN...

  3. 40 CFR 721.4090 - Ethanaminium, N-[bis(diethylamino)-methylene]-N-ethyl-, bromide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ethanaminium, N- -N-ethyl-, bromide... Substances § 721.4090 Ethanaminium, N- -N-ethyl-, bromide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanaminium, N- -N-ethyl-, bromide (PMN...

  4. Application of an enyne metathesis/Diels-Alder cycloaddition sequence: a new versatile approach to the syntheses of C-aryl glycosides and spiro-C-aryl glycosides.

    PubMed

    Subrahmanyam, Ayyagari V; Palanichamy, Kalanidhi; Kaliappan, Krishna P

    2010-07-26

    An efficient approach for the synthesis of a variety of C-aryl and spiro-C-aryl glycosides is described. This diversity-oriented strategy employed here relies on a sequential enyne metathesis to generate the 1,3-diene moiety and Diels-Alder reaction with different dienophiles followed by aromatisation. Whereas cross-enyne metathesis with ethylene gas is used to install the 1,3-diene moiety at the anomeric centre for the synthesis of C-aryl glycosides, an intramolecular enyne metathesis on the sugar enyne is performed to generate the 1,3-diene moiety for the synthesis of spiro-C-aryl glycosides. Efforts to extend this strategy to the synthesis of the core structure of natural C-aryl glycoside gilvocarcin are also described. A combination of both C-aryl and spiro-C-aryl glycosides in the same moiety to combine the features thereof has also been accomplished. A tandem enyne metathesis/Diels-Alder reaction/aromatisation has also been attempted to directly access the C-aryl glycosides in one pot albeit in low yield. PMID:20549721

  5. Ligand-free Pd-catalyzed and copper-assisted C-H arylation of quinazolin-4-ones with aryl iodides under microwave heating.

    PubMed

    Laclef, Sylvain; Harari, Marine; Godeau, Julien; Schmitz-Afonso, Isabelle; Bischoff, Laurent; Hoarau, Christophe; Levacher, Vincent; Fruit, Corinne; Besson, Thierry

    2015-04-01

    A microwave-assisted method for the palladium-catalyzed direct arylation of quinazolin-4-one has been developed under copper-assistance. This method is applicable to a wide range of aryl iodides and substituted (2H)-quinazolin-4-ones. This protocol provides a simple and efficient way to synthesize biologically relevant 2-arylquinazolin-4-one backbones. PMID:25781369

  6. Reactions of nitroxides 15. Cinnamates bearing a nitroxyl moiety synthesized using a Mizoroki–Heck cross-coupling reaction

    PubMed Central

    Huras, Bogumiła

    2015-01-01

    Summary Cinnamic acid derivatives bearing a nitroxyl moiety (2,2,6,6-tetramethyl-1-oxyl-4-piperidyl 3-E-aryl acrylates) were synthesized in 30–100% yield using a Mizoroki–Heck cross-coupling reaction between 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl and iodobenzene derivatives in the presence of palladium(II) acetate coordinated with a tri(o-tolyl)phosphine ligand immobilized in a polyurea matrix. PMID:26199672

  7. Reactions of nitroxides 15. Cinnamates bearing a nitroxyl moiety synthesized using a Mizoroki-Heck cross-coupling reaction.

    PubMed

    Zakrzewski, Jerzy; Huras, Bogumiła

    2015-01-01

    Cinnamic acid derivatives bearing a nitroxyl moiety (2,2,6,6-tetramethyl-1-oxyl-4-piperidyl 3-E-aryl acrylates) were synthesized in 30-100% yield using a Mizoroki-Heck cross-coupling reaction between 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl and iodobenzene derivatives in the presence of palladium(II) acetate coordinated with a tri(o-tolyl)phosphine ligand immobilized in a polyurea matrix. PMID:26199672

  8. Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.

    PubMed

    Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier

    2016-08-19

    Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity. PMID:27276418

  9. A universal procedure for the [¹⁸F]trifluoromethylation of aryl iodides and aryl boronic acids with highly improved specific activity.

    PubMed

    van der Born, Dion; Sewing, Claudia; Herscheid, J Koos D M; Windhorst, Albert D; Orru, Romano V A; Vugts, Danielle J

    2014-10-01

    Herein, we describe a valuable method for the introduction of the [(18)F]CF3 group into arenes with highly improved specific activity by the reaction of [(18)F]trifluoromethane with aryl iodides or aryl boronic acids. This [(18)F]trifluoromethylation reaction is the first to be described in which the [(18)F]CF3 products are generated in actual trace amounts and can therefore effectively be used as PET tracers. The method shows broad scope with respect to possible aryl iodide and aryl boronic acid substrates, as well as good to excellent conversion. In particular, the [(18)F]trifluoromethylation of boronic acids was found to outperform [(18)F]trifluoromethylation reactions of halogenated aryl precursors with regard to conversion, reaction conditions, and kinetics. PMID:25155042

  10. Passive Magnetic Bearing

    NASA Technical Reports Server (NTRS)

    Studer, P. A.

    1983-01-01

    Magnetic bearing for limited rotation devices requires no feedback control system to sense and correct shaft position. Passive Magnetic Torsion Bearing requires no power supply and has no rubbing parts. Torsion wire restrains against axial instability. Magnetic flux geometry chosen to assure lateral stability with radial restoring force that maintains alignment.

  11. Bearing servicing tool

    NASA Technical Reports Server (NTRS)

    Boyce, Rex A. (Inventor)

    1992-01-01

    A tool for removing and/or replacing bearings in situ is presented. The tool is comprised of a brace having a first end adapted to engage a first end of the bearing housing, and a second end adapted to engage a second end of the bearing housing. If the two ends of the bearing housing are different in configuration, then the respective ends of the brace are configured accordingly. An elongate guide member integral with the brace has two parts, each projecting endwise from a respective end of the brace. A removable pressure plate can be mounted on either part of the guide member for longitudinal movement therealong and has first and second ends of different configurations adapted to engage the first and second ends of the bearing. A threaded-type drive is cooperative between the guide and the pressure plate to move the pressure plate longitudinally along the guide and apply a force to the bearing, either to remove the bearing from its housing, or to emplace a new bearing in the housing.

  12. Bearing fatigue investigation 3

    NASA Technical Reports Server (NTRS)

    Nahm, A. H.; Bamberger, E. N.; Signer, H. R.

    1982-01-01

    The operating characteristics of large diameter rolling-element bearings in the ultra high speed regimes expected in advanced turbine engines for high performance aircraft were investigated. A high temperature lubricant, DuPont Krytox 143 AC, was evaluated at bearing speeds to 3 million DN. Compared to the results of earlier, similar tests using a MIL-L-23699 (Type II) lubricant, bearings lubricated with the high density Krytox fluid showed significantly higher power requirements. Additionally, short bearing lives were observed when this fluid was used with AISI M50 bearings in an air atmosphere. The primary mode of failure was corrosion initiated surface distress (fatigue) on the raceways. The potential of a case-carburized bearing to sustain a combination of high-tangential and hertzian stresses without experiencing race fracture was also investigated. Limited full scale bearing tests of a 120 mm bore ball bearing at a speed of 25,000 rpm (3 million DN) indicated that a carburized material could sustain spalling fatigue without subsequent propagation to fracture. Planned life tests of the carburized material had to be aborted, however, because of apparent processing-induced material defects.

  13. Cylindrical bearing analysis

    NASA Technical Reports Server (NTRS)

    Kleckner, R. J.; Pirvics, J.

    1981-01-01

    Program CYBEAN computes behavior of rolling-element bearings including effects of bearing geometry, shaft misalinement, and temperature. Accurate assessment is possible for various outer-ring and housing configurations. CYBEAN is structured for coordinated execution of modules that perform specific analytical tasks. It is written in FORTRAN IV for use on the UNIVAC 1100/40 computer.

  14. A convenient synthesis and screening of benzosuberone bearing 1,2,3-triazoles against Mycobacterium tuberculosis.

    PubMed

    Sajja, Yasodakrishna; Vanguru, Sowmya; Jilla, Lavanya; Vulupala, Hanmanth Reddy; Bantu, Rajashaker; Yogeswari, Perumal; Sriram, Dharmarajan; Nagarapu, Lingaiah

    2016-09-01

    A series of benzosuberone bearing 1,2,3-triazoles were rationally designed and alkyl/aryl groups appended on 1,2,3-triazole derivatives 5a-o were synthesized using click chemistry and evaluated for their in vitro antimycobacterial activity against Mycobacterium tuberculosis H37Rv (ATCC27294). Compounds 5h (MIC: 3.125μg/mL) and 5l, 5m, 5o (MIC: 6.25μg/mL) exhibited promising hits. This is the first Letter on the synthesis and in vitro antimycobacterial activity against Mycobacterium tuberculosis H37Rv of benzosuberone alkyl/aryl groups appended on 1,2,3-triazole derivatives. PMID:27476139

  15. Arcturus and the Bears

    NASA Astrophysics Data System (ADS)

    Antonello, E.

    2009-08-01

    Arcturus is the brightest star in Bootes. The ancient Greek name Arktouros means Bear Guard. The star, however, is not close to Ursa Maior (Big She-Bear) and Ursa Minor (Little She-Bear), as the name would suggest. This curious discrepancy could be explained by the star proper motion, assuming the name Bear Guard is a remote cultural heritage. The proper motion analysis could allow us to get an insight also into an ancient myth regarding Ursa Maior. Though we cannot explain scientifically such a myth, some interesting suggestions can be obtained about its possible origin, in the context of the present knowledge of the importance of the cult of the bear both during the Palaeolithic times and for several primitive populations of modern times, as shown by the ethnological studies.

  16. OTV bearing deflection investigation

    NASA Astrophysics Data System (ADS)

    Reimer, B. L.; Diepenbrock, R. T.; Millis, M. G.

    1993-04-01

    The primary goal of the Bearing Deflectometer Investigation was to gain experience in the use of fiber optic displacement probe technology for bearing health monitoring in a liquid hydrogen turbo pump. The work specified in this Task Order was conducted in conjunction with Air Force Rocket Propulsion Laboratory Contract F04611-86-C-0010. APD conducted the analysis and design coordination to provide a displacement probe design compatible with the XLR-134 liquid hydrogen turbo pump assembly (TPA). Specifications and requirements of the bearing deflectometer were established working with Mechanical Technology Instruments, Inc. (MTI). The TPA design accommodated positioning of the probe to measure outer race cyclic deflections of the pump inlet bearing. The fiber optic sensor was installed as required in the TPA and sensor output was recorded during the TPA testing. Data review indicated that no bearing deflection signature could be differentiated from the inherent system noise. Alternate sensor installations were not investigated, but might yield different results.

  17. Synthesis and photophysical properties of 2-aryl-6,8-bis(arylethenyl)-4-methoxyquinolines.

    PubMed

    Khoza, Tebogo Ankie; Maluleka, Marole Maria; Mama, Neliswa; Mphahlele, Malose Jack

    2012-01-01

    Iodine-methanol mediated oxidative-aromatization of 2-aryl-6,8-dibromo-2,3-dihydroquinolin-4(1H)-ones afforded the corresponding 2-aryl-6,8-dibromo-4-methoxy-quinolines in high yield and purity. The isomeric 1-(2-amino-3,5-dibromophenyl)-3-aryl-2-propen-1-ones reacted with iodine in methanol afford in a single pot operation the corresponding 2-aryl-6,8-dibromo-4-methoxyquinoline (major) and 2-aryl-6,8-dibromoquinolin-4(1H)-one (minor) products that were separated in sequence by column chromatography on silica gel. Suzuki-Miyaura cross-coupling of the 6,8-dibromo-4-methoxyquinoline derivatives with excess arylvinylboronic acids afforded the corresponding 2-aryl-6,8-bis(2-arylethenyl)-4-methoxyquinolines. The absorption and fluorescence properties of these compounds were also determined. PMID:23201639

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

    PubMed Central

    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

  19. Hybrid biobattery based on arylated carbon nanotubes and laccase.

    PubMed

    Stolarczyk, Krzysztof; Sepelowska, Małgorzata; Lyp, Dominika; Zelechowska, Kamila; Biernat, Jan F; Rogalski, Jerzy; Farmer, Kevin D; Roberts, Ken N; Bilewicz, Renata

    2012-10-01

    Single-walled carbon nanotubes (SWCNT) were covalently modified with anthracene and anthraquinone and used for the construction of cathodes for biocatalytic reduction of dioxygen. The nanotubes with aromatic groups casted onto the electrode increased the working surface of the electrode and enabled efficient direct electron transfer (DET) between the enzyme and the electrode. The aryl groups enter the hydrophobic pocket of the T1 center of laccase responsible for exchanging electrons with the substrate. Glassy carbon electrode covered with arylated SWCNT and coated with a layer of neutralized Nafion containing laccase was found to be a very efficient cathode in the hybrid battery. Zn wire covered with a Nafion film served as the anode. The cell parameters were determined: power density was 2 mW/cm(2) and the open circuit potential was 1.5 V. PMID:22078125

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

    PubMed

    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. PMID:21235520

  1. Functionalization of poly(aryl ether ether ketone)

    SciTech Connect

    Wang, Fei; Roovers, J.

    1993-12-31

    Bromomethyl and dibromomethyl substituted poly(aryl ether ether ketone) have been prepared from methyl poly(aryl ether ether ketone) by bromination with bromine. These brominated polymers are intermediates that can be further functionalized by: hydrolysis, oxidation, substitution etc. A series of new functionalized PEEK polymers has been prepared. The functional group includes -CH{sub 2}OH, -CH{sub 2}OCH{sub 3}, -CHO, -COOH, -COOCH{sub 3}, -CH{sub 2}CN, -CH{sub 2}COOH, -CH{sub 2}OCOCH{sub 3}, -CH{sub 2}N{sup +}H(CH{sub 2}CH{sub 3}){sub 2}Br{sup {minus}}, -CH{sub 2}N(CH{sub 2}CH{sub 3}){sub 2}, -CH{sub 2}N{sup +}H(CH{sub 2}CH{sub 3}){sub 3}Br{sup {minus}}.

  2. Ion and molecular recognition using aryl-ethynyl scaffolding.

    PubMed

    Vonnegut, Chris L; Tresca, Blakely W; Johnson, Darren W; Haley, Michael M

    2015-03-01

    The aryl-ethynyl linkage has been extensively employed in the construction of hosts for a variety of guests. Uses range from ion detection (e.g., of metal cations in the environment or industrial waste and of anions prevalent in nature), to molecular mimics for biological systems, and to applications targeting future safety issues (such as CO2 capture and indicators for the manufacture of chemical weapons). This Focus Review examines the utilization of the aryl-ethynyl linkage in engineering host molecules for a variety of different guests, and how the alkyne unit plays an integral part as both a rigid scaffolding section in host geometry design as well as a linker to allow conjugative communication between discrete π-electron systems. PMID:25586943

  3. A Structure-Activity Study with Aryl Acylamidases

    PubMed Central

    Villarreal, David T.; Turco, Ronald F.; Konopka, Allan

    1994-01-01

    We examined the relationship between chemical structure and biodegradability of acylanilide herbicides by using a set of model compounds. Four bacterial isolates (one gram-negative and three gram-positive) that grew on acetanilide were used. These soil isolates cleaved the amide bond of acetanilide via an aryl acylamidase reaction, producing aniline and the organic acid acetate. A series of acetanilide analogs with alkyl substitutions on the nitrogen atom or the aromatic ring were tested for their ability to induce aryl acylamidase activity and act as substrates for the enzyme. The substrate range, in general, was limited to those analogs not disubstituted in the ortho position of the benzene ring or which did not contain an alkyl group on the nitrogen atom. These same N-substituted compounds did not induce enzyme activity either, whereas the ortho-substituted compounds could in some cases. PMID:16349428

  4. A structure-activity study with aryl acylamidases.

    PubMed

    Villarreal, D T; Turco, R F; Konopka, A

    1994-11-01

    We examined the relationship between chemical structure and biodegradability of acylanilide herbicides by using a set of model compounds. Four bacterial isolates (one gram-negative and three gram-positive) that grew on acetanilide were used. These soil isolates cleaved the amide bond of acetanilide via an aryl acylamidase reaction, producing aniline and the organic acid acetate. A series of acetanilide analogs with alkyl substitutions on the nitrogen atom or the aromatic ring were tested for their ability to induce aryl acylamidase activity and act as substrates for the enzyme. The substrate range, in general, was limited to those analogs not disubstituted in the ortho position of the benzene ring or which did not contain an alkyl group on the nitrogen atom. These same N-substituted compounds did not induce enzyme activity either, whereas the ortho-substituted compounds could in some cases. PMID:16349428

  5. Lithium bromide absorption chiller passes gas conditioning field test

    SciTech Connect

    Lane, M.J.; Huey, M.A.

    1995-07-31

    A lithium bromide absorption chiller has been successfully used to provide refrigeration for field conditioning of natural gas. The intent of the study was to identify a process that could provide a moderate level of refrigeration necessary to meet the quality restrictions required by natural-gas transmission companies, minimize the initial investment risk, and reduce operating expenses. The technology in the test proved comparatively less expensive to operate than a propane refrigeration plant. Volatile product prices and changes in natural-gas transmission requirements have created the need for an alternative to conventional methods of natural-gas processing. The paper describes the problems with the accumulation of condensed liquids in pipelines, gas conditioning, the lithium bromide absorption cycle, economics, performance, and operating and maintenance costs.

  6. Aluminium Electroplating on Steel from a Fused Bromide Electrolyte

    SciTech Connect

    Prabhat Tripathy; Laura Wurth; Eric Dufek; Toni Y. Gutknecht; Natalie Gese; Paula Hahn; Steven Frank; Guy Fredrickson; J Stephen Herring

    2014-08-01

    A quaternary bromide bath (LiBr-KBr-CsBr-AlBr3) was used to electro-coat aluminium on steel substrates. The electrolyte was prepared by the addition of AlBr3 into the eutectic LiBr-KBr-CsBr melt. A smooth, thick, adherent and shiny aluminium coating could be obtained with 80 wt.% AlBr3 in the ternary melt. The SEM photographs of the coated surfaces suggest the formation of thick and dense coatings with good aluminium coverage. Both salt immersion and open circuit potential measurement suggest that the coatings did display good corrosion-resistance behavior. Annealing of the coated surfaces, prior to corrosion tests, suggested the robustness of the metallic aluminium coating in preventing the corrosion of the steel surfaces. Studies also indicated that the quaternary bromide plating bath can potentially provide a better aluminium coating on both ferrous and non-ferrous metals, including complex surfaces/geometries.

  7. Aluminum electroplating on steel from a fused bromide electrolyte

    SciTech Connect

    Prabhat K. Tripathy; Laura A. Wurth; Eric J. Dufek; Toni Y. Gutknecht; Natalie J. Gese; Paula Hahn; Steven M. Frank; Guy L. Frederickson; J. Stephen Herring

    2014-08-01

    A quaternary bromide bath (LiBr–KBr–CsBr–AlBr3) was used to electro-coat aluminum on steel substrates. The electrolytewas prepared by the addition of AlBr3 into the eutectic LiBr–KBr–CsBr melt. A smooth, thick, adherent and shiny aluminum coating could be obtained with 80 wt.% AlBr3 in the ternary melt. The SEM photographs of the coated surfaces suggest the formation of thick and dense coatings with good aluminum coverage. Both salt immersion and open circuit potential measurement suggested that the coatings did display a good corrosionresistance behavior. Annealing of the coated surfaces, prior to corrosion tests, suggested the robustness of the metallic aluminum coating in preventing the corrosion of the steel surfaces. Studies also indicated that the quaternary bromide plating bath can potentially provide a better aluminumcoating on both ferrous and non-ferrous metals, including complex surfaces/geometries.

  8. A novel and robust conditioning lesion induced by ethidium bromide

    PubMed Central

    Hollis, Edmund R; Ishiko, Nao; Tolentino, Kristine; Doherty, Ernest; Rodriguez, Maria J.; Calcutt, Nigel A.; Zou, Yimin

    2015-01-01

    Molecular and cellular mechanisms underlying the peripheral conditioning lesion remain unsolved. We show here that injection of a chemical demyelinating agent, ethidium bromide, into the sciatic nerve induces a similar set of regeneration-associated genes and promotes a 2.7-fold greater extent of sensory axon regeneration in the spinal cord than sciatic nerve crush. We found that more severe peripheral demyelination correlates with more severe functional and electrophysiological deficits, but more robust central regeneration. Ethidium bromide injection does not activate macrophages at the demyelinated sciatic nerve site, as observed after nerve crush, but briefly activates macrophages in the dorsal root ganglion. This study provides a new method for investigating the underlying mechanisms of the conditioning response and suggests that loss of the peripheral myelin may be a major signal to change the intrinsic growth state of adult sensory neurons and promote regeneration. PMID:25541322

  9. Viscosity and density of some lower alkyl chlorides and bromides

    SciTech Connect

    Rutherford, W.M.

    1988-07-01

    A high-pressure capillary viscometer, used previously to measure the viscosity of methyl chloride was rebuilt to eliminate the first-order dependence of the measured viscosity on the value assumed for the density of the fluid being investigated. At the same time, the system was arranged so that part of the apparatus could be used to measure density by a volumetric displacement technique. Viscosity and density were measured for ethyl chloride, 1-chloropropane, 1-chlorobutane, methyl bromide, ethyl bromide, and 1-bromopropane. The temperature and pressure ranges of the experiments were 20-150 /sup 0/C and 0.27-6.99 MPa, respectively. The accuracy of the viscosity measurements was estimated to be +-1% and of the density measurements, +-0.2%.

  10. [The use of syntropium bromide as an antispasmodic].

    PubMed

    Galeone, M; Cacioli, D; Moise, G; Bossi, M; Benazzi, E; Monti, G

    1985-09-22

    The following trials were carried out to evaluate the antispasmodic effect of sintropium bromide in a group of 30 patients. The antispasmodic effect on the gastroduodenal system was observed endoscopically. The results were compared by means of double blind tests carried out using placebo and rociverine. The effect in a group of 10 patients was examined by X-ray of the digestive tract. The effect on another group of 20 patients suffering from abdominal colic was clinically evaluated. Sintropium bromide has a prompt anticholinergic action and for this reason may be used in the treatment of painful conditions of the bile, gastro-enteric and renal tracts, and also during the course of endoscopic examinations. PMID:3900811

  11. Synthesis of tricyclic heterocycles via a tandem aryl alkylation/heck coupling sequence.

    PubMed

    Alberico, Dino; Rudolph, Alena; Lautens, Mark

    2007-02-01

    A norbornene-mediated palladium-catalyzed sequence is described in which two alkyl-aryl bonds and one alkenyl-aryl bond are formed in one pot with use of microwave irradiation. A variety of symmetrical and unsymmetrical oxygen-, nitrogen-, silicon-, and sulfur-containing tricyclic heterocycles were synthesized from a Heck acceptor and an aryl iodide containing two tethered alkyl halides. This approach was further applied to the synthesis of a tricyclic mescaline analogue. PMID:17253794

  12. Palladium-Catalyzed Heteroarylation and Concomitant ortho-Alkylation of Aryl Iodides.

    PubMed

    Lei, Chuanhu; Jin, Xiaojia; Zhou, Jianrong Steve

    2015-11-01

    Three-component couplings were achieved from common aryl halides, alkyl halides, and heteroarenes under palladium and norbornene co-catalysis. The reaction forges hindered aryl-heteroaryl bonds and introduces ortho-alkyl groups to aryl rings. Various heterocycles such as oxazoles, thiazoles and thiophenes underwent efficient coupling. The heteroarenes were deprotonated in situ by bases without the assistance of palladium catalysts. PMID:26358935

  13. Methyl aryl ethers from coal liquids as gasoline extenders and octane improvers

    SciTech Connect

    Singerman, G.M.

    1980-11-01

    A mixture of methyl aryl ethers derived from the phenols present in direct liquefaction coal liquids shows considerable promise as a gasoline blending agent and octane improver. The mixture of methyl aryl ethers was blended at five volume percent with a commercial, unleaded gasoline. The properties and performance of the blend in a variety of laboratory and automotive tests is reported. The tests show that the mixture of methyl aryl ethers improves gasoline octane without degrading other gasoline properties.

  14. Factors influencing the formation of polybromide monoanions in solutions of ionic liquid bromide salts.

    PubMed

    Easton, Max E; Ward, Antony J; Chan, Bun; Radom, Leo; Masters, Anthony F; Maschmeyer, Thomas

    2016-03-01

    Six different bromide salts - tetraethylammonium bromide ([N2,2,2,2]Br, Br), 1-ethyl-1-methylpiperidinium bromide ([C2MPip]Br, Br), 1-ethyl-1-methylpyrrolidinium bromide ([C2MPyrr]Br, Br), 1-ethyl-3-methylimidazolium bromide ([C2MIm]Br, Br), 1-ethylpyridinium bromide ([C2Py]Br, Br), and 1-(2-hydroxyethyl)pyridinium bromide ([C2OHPy]Br, Br) - were studied in regards to their capacity to form polybromide monoanion products on addition of molecular bromine in acetonitrile solutions. Using complementary spectroscopic and computational methods for the examination of tribromide and pentabromide anion formation, key factors influencing polybromide sequestration were identified. Here, we present criteria for the targeted synthesis of highly efficient bromine sequestration agents. PMID:26890026

  15. Oceanic Uptake of Methyl Bromide: Implications for Oceanic Production

    NASA Astrophysics Data System (ADS)

    Yvon-Lewis, S. A.; Butler, J. H.; King, D. B.; Saltzman, E. S.; Tokarczyk, R.

    2002-12-01

    Methyl bromide (CH3Br) is a source of inorganic bromine (Br) in the stratosphere, where it contributes to the depletion of stratospheric ozone. Unlike the chlorofluorocarbons, which are entirely anthropogenic, methyl bromide has both natural and anthropogenic sources. At ~10 parts per trillion in the troposphere, methyl bromide is believed to be the single largest contributor of stratospheric Br. Once in the stratosphere, Br is approximately 50 times more effective in depleting stratospheric ozone than Cl. However, the budget for CH3Br remains largely unbalanced with known sinks outweighing sources by ~50%. With production and degradation occurring in the ocean, the ocean is both a source and a sink for CH3Br. The balance between production and degradation results in the net undersaturation of CH3Br that has been observed over much of the world's ocean with an estimated global net ocean sink ranging from -11 to -20 Gg/y [King et al., 2000 and references therein]. However, effects of climate change, such as changes in windspeed distribution or sea-surface temperature could alter this balance. Modeling the potential effect of such forcing on the net flux of this important trace gas requires an understanding of the factors controlling the distributions of production and degradation in the surface ocean. During three recent research cruises (North Atlantic, North Pacific, and Southern Ocean), CH3Br degradation rate constants were measured along with saturation anomalies. Here we incorporate these data into a gridded global box model to examine the distribution of oceanic production rates necessary to support the observations. King, D.B., J.H. Butler, S.A. Montzka, S.A. Yvon-Lewis, and J.W. Elkins, Implications of methyl bromide supersaturations in the temperate North Atlantic Ocean, J. of Geophys. Res., 105 (D15), 19763-19769, 2000.

  16. Problems with NIOSH method 2520 for methyl bromide

    SciTech Connect

    Tharr, D.

    1994-03-01

    The National Institute for Occupational Safety and Health (NIOSH) publishes the NIOSH Manual of Analytical Methods (NMAM), a collection of analytical methods for characterizing exposures to environmental chemicals. When an industrial hygienist selects a method to monitor worker exposure, it is important to remember that not all the methods in the NMAM have undergone the same level of evaluation, as the following case demonstrates. As part of an industrywide study of the health effects resulting from methyl bromide exposure in structural and agricultural applicators, NIOSH researchers conducted industrial hygiene monitoring for methyl bromide in Florida during July 1990. NIOSH method 2520 was used. This method recommends use of two charcoal tubes (400 mg/100 mg) in series, desorption with carbon disulfide, and analysis by gas chromatography with a flame ionization detector. Sampling results from these surveys indicated a capacity problem. A project was then initiated to determine the reason for the methyl bromide breakthrough that occurred during industrial hygiene monitoring. While conducting research to define and solve this problem, several other problems were identified: reduced adsorption capacity caused by high humidity, difficulty in preparing standard solutions, sample instability, change in recovery with loading, and insufficiently low quantitation limit. The addition of a drying tube to the sampling train, as well as changes to the analytical technique, to the desorption solvent, and to the time till analysis, resulted in an improved method for methyl bromide. This case study demonstrates the importance of noting the conditions under which a method was evaluated and the benefit of testing method performance under conditions likely to exist at a field site. 5 refs.

  17. Criticality in aqueous solutions of 3-methylpyridine and sodium bromide.

    PubMed

    Kostko, A F; Anisimov, M A; Sengers, J V

    2004-08-01

    We address a controversial issue regarding the nature of critical behavior in ternary electrolyte solutions of water, 3-methylpyridine, and sodium bromide. Earlier light-scattering studies showed an anomalous critical behavior in this system that was attributed to the formation of a microheterogeneous phase associated with ion-molecule clustering [M.A. Anisimov, J. Jacob, A. Kumar, V.A. Agayan, and J. V. Sengers, Phys. Rev. Lett. 85, 2336 (2000)

  18. Methyl Bromide Poisoning—A Bizarre Neurological Disorder

    PubMed Central

    Collins, Raymond P.

    1965-01-01

    Methyl bromide, a widely used fumigant, may cause burns of the skin, fatalities accompanied by coma and convulsions, or prolonged neurologic and psychiatric symptoms. Burns are more likely to occur where evaporation is prevented under protective clothing. Symptoms of serious illness may not develop for hours after exposure. Since action appears to be one of methylation, especially of SH groups, B.A.L. may be helpful if used promptly. PMID:14347974

  19. Novel progesterone receptor modulators: 4-aryl-phenylsulfonamides.

    PubMed

    McComas, Casey; Cohen, Jeffrey; Huselton, Christine; Marella, Michael; Melenski, Edward; Mugford, Cheryl; Slayden, Ov; Winneker, Richard; Wrobel, Jay; Yudt, Matthew R; Fensome, Andrew

    2012-12-01

    We have developed a new series of progesterone receptor modulators based upon the 4-aryl-phenylsulfonamide. Initial work in the series afforded potent compounds with good properties, however an advanced intermediate proved to be genotoxic in a non-GLP Ames assay following metabolic activation. We subsequently solved this problem and identified advanced leads which demonstrated oral efficacy in rhesus monkey pharmacodynamic and kinetics models. PMID:23079530

  20. Rhodium-Catalyzed Enantioselective Arylation of Aliphatic Imines.

    PubMed

    Kato, Naoya; Shirai, Tomohiko; Yamamoto, Yasunori

    2016-06-01

    Chiral rhodium(I)-catalyzed highly enantioselective arylation of aliphatic N-sulfonyl aldimines with arylboronic acids has been developed. This transformation is achieved by the use of a rhodium/bis(phosphoramidite) catalyst to give enantiomerically enriched α-branched amines (up to 99 % ee). In addition, this system enables efficient synthesis of (+)-NPS R-568 and Cinacalcet which are calcimimetic agents. PMID:27119262

  1. Aryne 1,2,3-Trifunctionalization with Aryl Allyl Sulfoxides.

    PubMed

    Li, Yuanyuan; Qiu, Dachuan; Gu, Rongrong; Wang, Junli; Shi, Jiarong; Li, Yang

    2016-08-31

    An aryne 1,2,3-trisubstitution with aryl allyl sulfoxides is accomplished, featuring an incorporation of C-S, C-O, and C-C bonds on the consecutive positions of a benzene ring. The reaction condition is mild with broad substrate scope. Preliminary mechanistic study suggests a cascade formal [2 + 2] reaction of aryne with S═O bond, an allyl S → O migration, and a Claisen rearrangement. PMID:27527334

  2. Group 9 Metal Complexes of meso-Aryl-Substituted Rubyrin.

    PubMed

    Soya, Takanori; Osuka, Atsuhiro

    2015-07-20

    Invited for the cover of this issue are Takanori Soya and Atsuhiro Osuka at Kyoto University. The image depicts Group 9 metal (Co, Rh, and Ir) complexes of meso-aryl-substituted rubyrin and a meteorite approaching to the atmosphere. A large amount of Iridium is often contained in meteorites. Read the full text of the article at 10.1002/chem.201501080. PMID:26042817

  3. Arylation of rhodium(II) azavinyl carbenes with boronic acids.

    PubMed

    Selander, Nicklas; Worrell, Brady T; Chuprakov, Stepan; Velaparthi, Subash; Fokin, Valery V

    2012-09-12

    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 catalysis. PMID:22913576

  4. A three-component synthesis of aryl(heteroaryl)acylamides.

    PubMed

    Loska, Rafał; Bukowska, Patrycja

    2015-10-14

    A three-component reaction of azole or azine N-oxides, 1,1-difluorostyrenes and amines gives amides of α-aryl-α-heteroarylacetic or propionic acids. The key step is 1,3-dipolar cycloaddition between N-oxide and difluorostyrene leading to the acyl fluoride intermediate, which has been identified and characterized by NMR spectroscopy. The whole process is an example of selective functionalization of C-H bonds in both 5- and 6-membered heterocyclic systems. PMID:26288176

  5. Structural, vibrational and theoretical studies of L-histidine bromide

    NASA Astrophysics Data System (ADS)

    Ahmed, A. Ben; Feki, H.; Abid, Y.; Boughzala, H.; Mlayah, A.

    2008-10-01

    This paper presents the results of our calculations of the geometric parameters, vibrational spectra and hyperpolarizability of a non linear optical material, L-histidine bromide. Due to the lack of sufficiently precise information on the geometric structure available in literature, theoretical calculations were preceded by re-determination of the crystal X-ray structure. Single crystals of L-histidine bromide have been grown by slow evaporation of an aqueous solution at room temperature. The compound crystallizes in the non-Centro symmetric space group P2 12 12 1 of the orthorhombic system. Raman spectra have been recorded in the range [200-3500 cm -1]. All observed vibrational bands have been discussed and assigned to normal mode or to combinations and overtones on the basis of our calculations. The optimized geometric bond lengths and bond angles obtained by using HF and DFT (B3LYP and BLYP) show good agreement with the experimental data. Comparison between the measured and the calculated vibrational frequencies indicate that B3LYP is superior to the scaled HF approach for molecular vibrational problems. To investigate microscopic second order non linear optical properties of L-histidine bromide, the electric dipole μ, the polarizability α and the hyperpolarizability β were computed using DFT//B3LYP/6-31G(d) method. According to our calculations, the title compound exhibits non-zero β value revealing microscopic second order NLO behaviour.

  6. The Thz Absorption of Methyl Bromide (CH_3BR)

    NASA Astrophysics Data System (ADS)

    Ramos, Marlon; Drouin, Brian J.

    2011-06-01

    The possibility of monitoring Methyl Bromide is of interest for both environmental and health concerns. It has an ozone depletion potential of 0.2% and falls under regulations of the Clean Air Act. Neurological effects from long term exposure may result from its major use as a pesticide. Recent improvements in microwave limb sounding at mm & submm wavelengths have resulted in retrievals of Methyl Chloride from atmospheric spectra. It is conceivable that Methyl Bromide would also be measurable by this technique. In an effort to extend and improve the previous work, the THz spectrum of Methyl Bromide has been measured at JPL. We used an isotopically enriched 13CH_3Br (90%) sample and recorded spectra from 750 - 1200 GHz. Our assignment covers the CH_379Br, CH_381Br, 13CH_379Br and 13CH_381Br isotopologues with J< 66 and K< 17 for the ground vibrational state. We plan to assign vibrational satellites and investigate possible perturbations near K =12 in the ground state.

  7. [Manometric effects of pinaverium bromide in irritable bowel syndrome].

    PubMed

    Soifer, L; Varela, E; Olmos, J

    1992-01-01

    The effects of pinaverium bromide on colonic motility were investigated in a controlled, controlled, cross-over study in 32 patients with irritable bowel syndrome. Constipation was clearly predominant in one group of 16 patients, and diarrhea in the other group of 16. Manometric measurements were taken of the colonic motor response generated by distention of a balloon inserted to the rectosigmoid junction. Measurements were taken before and one hour after ingestion of two tablets containing placebo or two tablets each containing 50 mg of pinaverium bromide. Following intake of placebo the motility index increased from the basal value in patients with constipation, and resistance to distention decreased in the diarrhea group. These changes were attributable to repetition of the mechanical stimulus within a relatively brief time lapse, or more probably to the ingestion of liquid which accompanied intake of tablets. Compared with placebo, pinaverium bromide induced inhibition of both effects. From the therapeutic point of view, the decrease in motility index seen in patients with irritable bowel syndrome and constipation is particularly interesting. PMID:1295286

  8. L-Tryptophan L-tryptophanium bromide: Anhydrous and monohydrate

    NASA Astrophysics Data System (ADS)

    Ghazaryan, V. V.; Giester, G.; Fleck, M.; Petrosyan, A. M.

    2015-12-01

    L-Tryptophan L-tryptophanium bromide (I) and L-tryptophan L-tryptophanium bromide monohydrate (II) are new salts with (A⋯A+) type dimeric cation. The salt (I) crystallizes in the monoclinic system (space group P21, Z = 2) and is isostructural with respective chloride (V.V. Ghazaryan et al., Spectrochim. Acta A 136(2015) 743-750), while the salt (II) was obtained previously (T. Takigawa et al., Bull. Chem. Soc. Jap. 39(1966) 2369-2378) and described as hemyhydrate without structure determination. The salt (II) crystallizes in orthorhombic system (space group P212121, Z = 4). The dimeric cations in (I) and (II) are formed by O-H⋯O hydrogen bonds with the O⋯O distances equal to 2.538(3) Å and 2.481(3) Å respectively. The infrared and Raman spectra of the crystals are studied and compared with the spectra of L-tryptophan L-tryptophanium chloride and L-tryptophanium bromide.

  9. Anomalous signal of solvent bromides used for phasing of lysozyme.

    PubMed

    Dauter, Z; Dauter, M

    1999-05-28

    The anomalous signal of bromide ions, present in the crystal structure of tetragonal hen egg-white lysozyme through the substitution of NaCl by NaBr in the crystallization medium, was used for phasing of X-ray data collected to 1.7 A resolution with a wavelength near the absorption edge of bromine. Phasing of a single wavelength data set, based purely on anomalous deltaf " contribution, led to easily interpretable electron density, equivalent to the complete multiwavelength anonalous dispersion phasing based on four-wavelength data. The classic small-structure direct methods program SHELXS run against all anomalous differences gave a successful solution of six highest peaks corresponding to six bromide ions in the structure with data limited up to a resolution of 3.5 A. Interpretable maps were obtained at a resolution up to 3.0 A using programs MLPHARE and DM. Bromide ions occupy well ordered positions at the protein surface. Phasing based on the single wavelength signal of anomalous scatterers introduced into the ordered solvent shell can be proposed as a tool for solving structures of well diffracting crystals. PMID:10339408

  10. Touchdown Ball-Bearing System for Magnetic Bearings

    NASA Technical Reports Server (NTRS)

    Kingsbury, Edward P.; Price, Robert; Gelotte, Erik; Singer, Herbert B.

    2003-01-01

    The torque-limited touchdown bearing system (TLTBS) is a backup mechanical-bearing system for a high-speed rotary machine in which the rotor shaft is supported by magnetic bearings in steady-state normal operation. The TLTBS provides ball-bearing support to augment or supplant the magnetic bearings during startup, shutdown, or failure of the magnetic bearings. The TLTBS also provides support in the presence of conditions (in particular, rotational acceleration) that make it difficult or impossible to control the magnetic bearings or in which the magnetic bearings are not strong enough (e.g., when the side load against the rotor exceeds the available lateral magnetic force).

  11. Magnetically-controlled bearing lubrication

    NASA Technical Reports Server (NTRS)

    Whitaker, A. F.

    1977-01-01

    Proposed magnetic-lubricant ball-bearing assembly has permanently-magnetized bearing retainer fabricated of porous material. Pores of retainer are filled with ferrolubricant. Surface tension causes retainer to deliver sufficient lubricant to nonmagnetic ball bearings.

  12. Ligand-Free, Cu- and Fe-Catalyzed Selective Ring-Opening Arylations of Benzoxazoles with Aryl Iodides.

    PubMed

    He, Yue; Mao, Jincheng; Rong, Guangwei; Yan, Hong; Zhang, Guoqi

    2016-06-01

    Cu- or Fe-based catalyst systems have been reported to selectively catalyze the N,N-diarylation or N-monoarylation of benzoxazoles ring-opening with aryl iodides in the absence of additional added ligand in polyethylene glycol under an inert atmosphere. Two types of coupling products (triphenylamines and diphenylamines) have been examined and the reaction routes can be simply controlled by changing the metal salts (Cu or Fe) as catalyst. A range of substrates have been investigated for the diverse reactions, and the corresponding arylation products were achieved in good to high yields. This selective, low-cost, and environmentally friendly protocol displays great potential for replacing existing methodologies as well as extending the synthetic applications of benzoxazoles. PMID:27037845

  13. Ball Bearing Mechanics

    NASA Technical Reports Server (NTRS)

    Hamrock, B. J.; Dowson, D.

    1981-01-01

    Load-deflection relationships for different types of elliptical contacts such as those found in a ball bearing are developed. Simplified expressions that allow quick calculations of deformation to be made simply from a knowledge of the applied load, the material properties, and the geometry of the contacting elements are presented. Ball bearings subjected to radial, thrust and combined ball loads are analyzed. A design criterion for fatigue life of ball bearings is developed. The section of a satisfactory lubricant, as well as describing systems that provide a constant flow of lubricant to the contact, is considered.

  14. Magnetic bearing update

    SciTech Connect

    Fowler, T.K.

    1995-05-25

    Stabilization of whirl instability by floppy, viscous bearing mounts is discussed and required material properties are estimated for the new tilt-whirl mode in eddy-current stabilized magnetic bearings. A relatively low Young`s modules Y {approximately} 10{sup 5} and high viscosity {zeta} {approximately} 10{sup 7} are required (both in MKS units), suggesting the need for careful mounting design. New information on periodic bearings shows that, thus far, Earshaw`s Theorem cannot be defeated by periodicity, despite the author`s earlier claims.

  15. Ball and Roller Bearings. A Teaching Reference.

    ERIC Educational Resources Information Center

    American Association for Vocational Instructional Materials, Athens, GA.

    The manual provides a subject reference for ball and roller bearings. The following topics are included: (1) bearing nomenclature, (2) bearing uses, (3) bearing capacities, (4) shop area working conditions, (5) bearing removal, (6) bearing cleaning and inspection, (7) bearing replacement, (8) bearing lubrication, (9) bearing installation, (10)…

  16. Effect of remote aryl substituents on the conformational equilibria of 2,2-diaryl-1,3-dioxanes: importance of electrostatic interactions.

    PubMed

    Bailey, William F; Lambert, Kyle M; Wiberg, Kenneth B; Mercado, Brandon Q

    2015-04-17

    The conformational preference of a variety of 2,2-diaryl-1,3-dioxanes bearing remote substituents on the phenyl rings has been studied via equilibration of configurationally isomeric 2,2-diaryl-cis-4,6-dimethyl-1,3-dioxane epimers, X-ray crystallography, (1)H NOESY analysis, and B3LYP/6-311+G* calculations. When the aryl ring bears a remote electron-withdrawing substituent, the isomer having both the higher dipole moment and the electron-withdrawing group in the equatorial phenyl ring and/or an electron-donating group in the axial ring has the lower energy. These results differ from the conclusions reported in a previous study of similar systems. The conformational energy differences of para-substituted 2,2-diaryl-1,3-dioxanes are linearly related to the Hammett σ values with a slope (ρ) of 0.6. In addition, there is a trend toward longer bond lengths between the C(2) ketal center and the aryl ring as the electron-withdrawing nature of the para-substituent is increased. Electrostatic interactions, rather than a hyperconjugative anomeric effect, appear to be responsible for the conformational behavior of such molecules. PMID:25803722

  17. Arkansas black bear hunter survey

    USGS Publications Warehouse

    Pharris, Larry D.; Clark, Joseph D.

    1987-01-01

    Questionnaires were mailed to black bear (Ursus americanus) hunters in Arkansas following the 1980-84 bear seasons to determine participation, hunter success, and number of bears observed by hunters. Man-days of hunting to harvest a bear ranged from 148 to 671 and hunter success ranged from 0.4% to 2.2%. With the exception of 1980, number of permits issued, man-days of bear hunting, and bears harvested appear affected by hunting permit cost. 

  18. 40 CFR 180.123a - Inorganic bromide residues in peanut hay and peanut hulls; statement of policy.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... containing residues of inorganic bromides from the use of methyl bromide are unsuitable as an ingredient in... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Inorganic bromide residues in peanut... RESIDUES IN FOOD Specific Tolerances § 180.123a Inorganic bromide residues in peanut hay and peanut...

  19. 40 CFR 180.123a - Inorganic bromide residues in peanut hay and peanut hulls; statement of policy.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... containing residues of inorganic bromides from the use of methyl bromide are unsuitable as an ingredient in... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Inorganic bromide residues in peanut... RESIDUES IN FOOD Specific Tolerances § 180.123a Inorganic bromide residues in peanut hay and peanut...

  20. 40 CFR 180.123a - Inorganic bromide residues in peanut hay and peanut hulls; statement of policy.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... containing residues of inorganic bromides from the use of methyl bromide are unsuitable as an ingredient in... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Inorganic bromide residues in peanut... RESIDUES IN FOOD Specific Tolerances § 180.123a Inorganic bromide residues in peanut hay and peanut...

  1. EFFECT OF BROMIDE ION IN WATER TREATMENT. 2. A LITERATURE REVIEW OF OZONE AND BROMIDE ION INTERACTIONS AND THE FORMATION OF ORGANIC BROMINE COMPOUNDS

    EPA Science Inventory

    Where bromide ion is found in water used as a source of drinking water, and chlorination is used for disinfection, bromide ion is oxidized to bromine and can result in the formation of organic bromine compounds. There are presently no treatment techniques available for economic r...

  2. Spatial Variation Scales of Rainfall Characteristics and Bromide Leaching

    NASA Astrophysics Data System (ADS)

    Wendroth, O. O.; Vasquez, V.; Matocha, C.

    2010-12-01

    Amount and intensity of rainfall are known as important characteristics that affect the leaching of surface-applied agri-chemicals. Besides these, the effect of the time interval between a fertilizer, pesticide or tracer application and subsequent rainfall on solute leaching is not well understood. Moreover, little is known about the spatial representativity of the solute concentration based on a relatively small soil sample in field-scale transport studies. To know the spatial representativity of a solute concentration sample at a time is crucial for analyzing solute leaching behavior over time as well as over space. The objectives of this study were to identify the impact of rainfall intensity and amount as well as the application time delay on solute transport in a well-drained Maury silt loam soil. Moreover, an experimental design and protocol had to be developed that exhibited spatial variability structure and representativity of bromide concentration. For this purpose, the variation scale of each of the factors investigated was chosen differently to apply frequency domain statistics. The study was conducted in a Maury silt loam soil at the University of Kentucky, College of Agriculture Experimental Farm Spindletop. Along a 64-m transect, 32 plots each 2-m long and 4-m wide were established. The three different treatments were spatially laid out in sinusoidal patterns at three respective wavelengths. Two different rainfall amounts were applied in blocks of eight consecutive plots, hence a wavelength of 32 m. These two different rainfall amounts were applied at four rates, spatially distributed in two waves each of 16 m length. Individual plots received the irrigation at specific times after the tracer had been applied. Four application delay times were chosen, hence the wavelength for this treatment was 8 m. Bromide concentration was measured for soil samples that were taken with a percussion auger at every 50 cm distance along the 64-m-transect. Auger cores

  3. Decarboxylative Palladium(II)-Catalyzed Synthesis of Aryl Amidines from Aryl Carboxylic Acids: Development and Mechanistic Investigation

    PubMed Central

    Rydfjord, Jonas; Svensson, Fredrik; Trejos, Alejandro; Sjöberg, Per J R; Sköld, Christian; Sävmarker, Jonas; Odell, Luke R; Larhed, Mats

    2013-01-01

    A fast and convenient synthesis of aryl amidines starting from carboxylic acids and cyanamides is reported. The reaction was achieved by palladium(II)-catalysis in a one-step microwave protocol using [Pd(O2CCF3)2], 6-methyl-2,2′-bipyridyl and trifluoroacetic acid (TFA) in N-methylpyrrolidinone (NMP), providing the corresponding aryl amidines in moderate to excellent yields. The protocol is very robust with regards to the cyanamide coupling partner but requires electron-rich ortho-substituted aryl carboxylic acids. Mechanistic insight was provided by a DFT investigation and direct ESI-MS studies of the reaction. The results of the DFT study correlated well with the experimental findings and, together with the ESI-MS study, support the suggested mechanism. Furthermore, a scale-out (scale-up) was performed with a non-resonant microwave continuous-flow system, achieving a maximum throughput of 11 mmol h−1 by using a glass reactor with an inner diameter of 3 mm at a flow rate of 1 mL min−1. PMID:23983102

  4. Decarboxylative palladium(II)-catalyzed synthesis of aryl amidines from aryl carboxylic acids: development and mechanistic investigation.

    PubMed

    Rydfjord, Jonas; Svensson, Fredrik; Trejos, Alejandro; Sjöberg, Per J R; Sköld, Christian; Sävmarker, Jonas; Odell, Luke R; Larhed, Mats

    2013-10-01

    A fast and convenient synthesis of aryl amidines starting from carboxylic acids and cyanamides is reported. The reaction was achieved by palladium(II)-catalysis in a one-step microwave protocol using [Pd(O2 CCF3 )2 ], 6-methyl-2,2'-bipyridyl and trifluoroacetic acid (TFA) in N-methylpyrrolidinone (NMP), providing the corresponding aryl amidines in moderate to excellent yields. The protocol is very robust with regards to the cyanamide coupling partner but requires electron-rich ortho-substituted aryl carboxylic acids. Mechanistic insight was provided by a DFT investigation and direct ESI-MS studies of the reaction. The results of the DFT study correlated well with the experimental findings and, together with the ESI-MS study, support the suggested mechanism. Furthermore, a scale-out (scale-up) was performed with a non-resonant microwave continuous-flow system, achieving a maximum throughput of 11 mmol h(-1) by using a glass reactor with an inner diameter of 3 mm at a flow rate of 1 mL min(-1) . PMID:23983102

  5. Roller bearing geometry design

    NASA Technical Reports Server (NTRS)

    Savage, M.; Pinkston, B. H. W.

    1976-01-01

    A theory of kinematic stabilization of rolling cylinders is extended and applied to the design of cylindrical roller bearings. The kinematic stabilization mechanism puts a reverse skew into the rolling elements by changing the roller taper. Twelve basic bearing modification designs are identified amd modeled. Four have single transverse convex curvature in their rollers while eight have rollers which have compound transverse curvature made up of a central cylindrical band surrounded by symmetric bands with slope and transverse curvature. The bearing designs are modeled for restoring torque per unit axial displacement, contact stress capacity, and contact area including dynamic loading, misalignment sensitivity and roller proportion. Design programs are available which size the single transverse curvature roller designs for a series of roller slopes and load separations and which design the compound roller bearings for a series of slopes and transverse radii of curvature. The compound rollers are proportioned to have equal contact stresses and minimum size. Design examples are also given.

  6. Magnetically levitated superconducting bearing

    SciTech Connect

    Weinberger, B.R.; Lynds, L. Jr.

    1993-10-26

    A magnetically levitated superconducting bearing includes a magnet mounted on a shaft that is rotatable around an axis of rotation and a Type II superconductor supported on a stator in proximity to the magnet. The superconductor is positioned so that when it is cooled to its superconducting state in the presence of a magnetic field, it interacts with the magnet to produce an attractive force that levitates the magnet and supports a load on the shaft. The interaction between the superconductor and magnet also produces surface screening currents that generate a repulsive force perpendicular to the load. The bearing also has means for maintaining the superconductor at a temperature below its critical temperature. The bearing could also be constructed so the magnet is supported on the stator and the superconductor is mounted on the shaft. The bearing can be operated by cooling the superconductor to its superconducting state in the presence of a magnetic field. 6 figures.

  7. The performance of PEGylated nanocapsules of perfluorooctyl bromide as an ultrasound contrast agent.

    PubMed

    Díaz-López, Raquel; Tsapis, Nicolas; Santin, Mathieu; Bridal, Sharon Lori; Nicolas, Valérie; Jaillard, Danielle; Libong, Danielle; Chaminade, Pierre; Marsaud, Véronique; Vauthier, Christine; Fattal, Elias

    2010-03-01

    The surface of polymeric nanocapsules used as ultrasound contrast agents (UCAs) was modified with PEGylated phospholipids in order to escape recognition and clearance by the mononuclear phagocyte system and achieve passive tumor targeting. Nanocapsules consisted of a shell of poly(lactide-co-glycolide) (PLGA) encapsulating a liquid core of perfluorooctyl bromide (PFOB). They were decorated with poly(ethylene glycol-2000)-grafted distearoylphosphatidylethanolamine (DSPE-PEG) incorporated in the organic phase before the solvent emulsification-evaporation process. The influence of DSPE-PEG concentration on nanocapsule size, surface charge, morphology, hydrophobicity and complement activation was evaluated. Zeta potential measurements, Hydrophobic interaction chromatography and complement activation provide evidence of DSPE-PEG presence at nanocapsule surface. Electronic microscopy reveals that the core/shell structure is preserved up to 2.64 mg of DSPE-PEG for 100 mg PLGA. In vivo ultrasound imaging was performed in mice bearing xenograft tumor with MIA PaCa-2 cells, either after an intra-tumoral or intravenous injection of nanocapsules. Tumor was observed only after the intra-tumoral injection. Despite the absence of echogenic signal in the tumor after intravenous injection of nanocapsules, histological analysis reveals their accumulation within the tumor tissue demonstrating that tissue distribution is not the unique property required for ultrasound contrast agents to be efficient. PMID:19948357

  8. Hydrostatic bearing support

    NASA Technical Reports Server (NTRS)

    Cunningham, R. E. (Inventor)

    1977-01-01

    A hydrostatic bearing support system is provided which comprises a bearing housing having a polygonally configured outer surface which defines at least three symmetrically disposed working faces and a plurality of pressure plates, each of which is disposed relatively opposite a corresponding working face and spaced therefrom to define a gap therebetween. A hydrostatic support film is created in the gap for supporting the housing in spaced relationship to the pressure plates.

  9. Gear bearing drive

    NASA Technical Reports Server (NTRS)

    Weinberg, Brian (Inventor); Mavroidis, Constantinos (Inventor); Vranish, John M. (Inventor)

    2011-01-01

    A gear bearing drive provides a compact mechanism that operates as an actuator providing torque and as a joint providing support. The drive includes a gear arrangement integrating an external rotor DC motor within a sun gear. Locking surfaces maintain the components of the drive in alignment and provide support for axial loads and moments. The gear bearing drive has a variety of applications, including as a joint in robotic arms and prosthetic limbs.

  10. Deformable bearing seat

    NASA Technical Reports Server (NTRS)

    Moreman, O. S., III (Inventor)

    1977-01-01

    A deformable bearing seat is described for seating a bearing assembly in a housing. The seat includes a seating surface in the housing having a first predetermined spheroidal contour when the housing is in an undeformed mode. The seating surface is deformable to a second predetermined spherically contoured surface when the housing is in a deformed mode. The seat is particularly adaptable for application to a rotating blade and mounting ring assembly in a gas turbine engine.

  11. Comparison of Heat and Bromide as Ground Water Tracers Near Streams

    USGS Publications Warehouse

    Constantz, J.; Cox, M.H.; Su, G.W.

    2003-01-01

    Heat and bromide were compared as tracers for examining stream/ground water exchanges along the middle reaches of the Santa Clara River, California, during a 10-hour surface water sodium bromide injection test. Three cross sections that comprise six shallow (<1 m) piezometers were installed at the upper, middle, and lower sections of a 17 km long study reach, to monitor temperatures and bromide concentrations in the shallow ground water beneath the stream. A heat and ground water transport simulation model and a closely related solute and ground water transport simulation model were matched up for comparison of simulated and observed temperatures and bromide concentrations in the streambed. Vertical, one-dimensional simulations of sediment temperature were fitted to observed temperature results, to yield apparent streambed hydraulic conductivities in each cross section. The temperature-based hydraulic conductivities were assigned to a solute and ground water transport model to predict sediment bromide concentrations, during the sodium bromide injection test. Vertical, one-dimensional simulations of bromide concentrations in the sediments yielded a good match to the observed bromide concentrations, without adjustment of any model parameters except solute dispersivities. This indicates that, for the spatial and temporal scales examined on the Santa Clara River, the use of heat and bromide as tracers provide comparable information with respect to apparent hydraulic conductivities and fluxes for sediments near streams. In other settings, caution should be used due to differences in the nature of conservative (bromide) versus nonconservative (heat) tracers, particularly when preferential flowpaths are present.

  12. C-H arylation of benzoquinone in water through aniline activation: synergistic effect of graphite-supported copper oxide nanoparticles.

    PubMed

    Honraedt, Aurélien; Le Callonnec, François; Le Grognec, Erwan; Fernandez, Vincent; Felpin, François-Xavier

    2013-05-01

    A homemade CuONPs/Gr catalyst was found to be efficient for the C-H arylation of benzoquinone. This methodology represents the first example of a Meerwein arylation catalyzed by a heterogeneous catalyst. PMID:23551327

  13. Copper catalyzed N-arylation of amidines with aryl boronic acids and one-pot synthesis of benzimidazoles by a Chan-Lam-Evans N-arylation and C-H activation/C-N bond forming process.

    PubMed

    Li, Jihui; Bénard, Sébastien; Neuville, Luc; Zhu, Jieping

    2012-12-01

    Mono-N-arylation of benzamidines 1 with aryl boronic acids 2 was effectively achieved in the presence of a catalytic amount of Cu(OAc)(2) and NaOPiv under mild aerobic conditions. Combining this step with an intramolecular direct C-H bond functionalization, catalyzed by the same catalytic system but under oxygen at 120 °C, afforded benzimidazoles 3 in good to excellent yields. PMID:23151245

  14. Load responsive hydrodynamic bearing

    DOEpatents

    Kalsi, Manmohan S.; Somogyi, Dezso; Dietle, Lannie L.

    2002-01-01

    A load responsive hydrodynamic bearing is provided in the form of a thrust bearing or journal bearing for supporting, guiding and lubricating a relatively rotatable member to minimize wear thereof responsive to relative rotation under severe load. In the space between spaced relatively rotatable members and in the presence of a liquid or grease lubricant, one or more continuous ring shaped integral generally circular bearing bodies each define at least one dynamic surface and a plurality of support regions. Each of the support regions defines a static surface which is oriented in generally opposed relation with the dynamic surface for contact with one of the relatively rotatable members. A plurality of flexing regions are defined by the generally circular body of the bearing and are integral with and located between adjacent support regions. Each of the flexing regions has a first beam-like element being connected by an integral flexible hinge with one of the support regions and a second beam-like element having an integral flexible hinge connection with an adjacent support region. A least one local weakening geometry of the flexing region is located intermediate the first and second beam-like elements. In response to application of load from one of the relatively rotatable elements to the bearing, the beam-like elements and the local weakening geometry become flexed, causing the dynamic surface to deform and establish a hydrodynamic geometry for wedging lubricant into the dynamic interface.

  15. Magnetic bearing and motor

    NASA Technical Reports Server (NTRS)

    Studer, P. A. (Inventor)

    1983-01-01

    A magnetic bearing for passively suspending a rotatable element subjected to axial and radial thrust forces is disclosed. The magnetic bearing employs a taut wire stretched along the longitudinal axis of the bearing between opposed end pieces and an intermediate magnetic section. The intermediate section is segmented to provide oppositely directed magnetic flux paths between the end pieces and may include either an axially polarized magnets interposed between the segments. The end pieces, separated from the intermediate section by air gaps, control distribution of magnetic flux between the intermediate section segments. Coaxial alignment of the end pieces with the intermediate section minimizes magnetic reluctance in the flux paths endowing the bearing with self-centering characteristics when subjected to radial loads. In an alternative embodiment, pairs of oppositely wound armature coils are concentrically interposed between segments of the intermediate section in concentric arcs adjacent to radially polarized magnets to equip a magnetic bearing as a torsion drive motor. The magnetic suspension bearing disclosed provides long term reliability without maintenance with application to long term space missions such as the VISSR/VAS scanning mirror instrument in the GOES program.

  16. Investigation of Pressurized Wave Bearings

    NASA Technical Reports Server (NTRS)

    Keith, Theo G., Jr.; Dimofte, Florin

    2003-01-01

    The wave bearing has been pioneered and developed by Dr. Dimofte over the past several years. This bearing will be the main focus of this research. It is believed that the wave bearing offers a number of advantages over the foil bearing, which is the bearing that NASA is currently pursuing for turbomachinery applications. The wave bearing is basically a journal bearing whose film thickness varies around the circumference approximately sinusoidally, with usually 3 or 4 waves. Being a rigid geometry bearing, it provides precise control of shaft centerlines. The wave profile also provides good load capacity and makes the bearing very stable. Manufacturing techniques have been devised that should allow the production of wave bearings almost as cheaply as conventional full-circular bearings.

  17. 40 CFR 721.6220 - Aryl sulfonate of a fatty acid mixture, polyamine condensate.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., polyamine condensate. 721.6220 Section 721.6220 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6220 Aryl sulfonate of a fatty acid mixture, polyamine condensate. (a... generically as an aryl sulfonate of a fatty acid mixture, polyamine condensate (PMN P-91-584) is subject...

  18. 40 CFR 721.6220 - Aryl sulfonate of a fatty acid mixture, polyamine condensate.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., polyamine condensate. 721.6220 Section 721.6220 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6220 Aryl sulfonate of a fatty acid mixture, polyamine condensate. (a... generically as an aryl sulfonate of a fatty acid mixture, polyamine condensate (PMN P-91-584) is subject...

  19. 40 CFR 721.6220 - Aryl sulfonate of a fatty acid mixture, polyamine condensate.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., polyamine condensate. 721.6220 Section 721.6220 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6220 Aryl sulfonate of a fatty acid mixture, polyamine condensate. (a... generically as an aryl sulfonate of a fatty acid mixture, polyamine condensate (PMN P-91-584) is subject...

  20. Repetitive synthetic method for o,o,p-oligophenylenes using C-H arylation.

    PubMed

    Manabe, Kei; Kimura, Takeshi

    2013-01-18

    A synthetic method for the preparation of o,o,p-oligophenylenes has been developed. It involves Miura's C-H arylation of 2-biphenols with aryl nonaflates as the key step. Oligophenylenes with defined lengths are successfully synthesized using this method. PMID:23289430

  1. 40 CFR 721.10367 - Hydroxy-aryl, polymer with substituted benzene, cyanate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... benzene, cyanate (generic). 721.10367 Section 721.10367 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10367 Hydroxy-aryl, polymer with substituted benzene... substance identified generically as hydroxy-aryl, polymer with substituted benzene, cyanate (PMN P-10-83)...

  2. 40 CFR 721.10367 - Hydroxy-aryl, polymer with substituted benzene, cyanate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... benzene, cyanate (generic). 721.10367 Section 721.10367 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10367 Hydroxy-aryl, polymer with substituted benzene... substance identified generically as hydroxy-aryl, polymer with substituted benzene, cyanate (PMN P-10-83)...

  3. 40 CFR 721.10367 - Hydroxy-aryl, polymer with substituted benzene, cyanate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... benzene, cyanate (generic). 721.10367 Section 721.10367 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10367 Hydroxy-aryl, polymer with substituted benzene... substance identified generically as hydroxy-aryl, polymer with substituted benzene, cyanate (PMN P-10-83)...

  4. Intermolecular decarboxylative direct C-3 arylation of indoles with benzoic acids.

    PubMed

    Cornella, Josep; Lu, Pengfei; Larrosa, Igor

    2009-12-01

    A palladium catalyzed C-H activation of indoles and a silver catalyzed decarboxylative C-C activation of ortho substituted benzoic acids are synergistically combined to synthesize indoles arylated exclusively in the C-3 position. This novel decarboxylative C-H arylation methodology is compatible with electron-donating and -withdrawing substituents in both coupling partners. PMID:19877661

  5. Direct ortho-arylation of ortho-substituted benzoic acids: overriding Pd-catalyzed protodecarboxylation.

    PubMed

    Arroniz, Carlos; Ironmonger, Alan; Rassias, Gerry; Larrosa, Igor

    2013-02-15

    ortho-Arylation of ortho-substituted benzoic acids is a challenging process due to the tendency of the reaction products toward Pd-catalyzed protodecarboxylation. A simple method for preventing decarboxylation in sterically hindered benzoic acids is reported. The method described represents a reliable and broadly applicable entry to 2-aryl-6-substituted benzoic acids. PMID:23373630

  6. PALLADIUM CATALYZED COUPLING OF ARYL HALIDES WITH ARYLHALOSILANES IN AIR AND WATER. (R828129)

    EPA Science Inventory

    In the presence of a palladium catalyst, various aryl halides reacted with arylhalosilanes in aqueous media and under an air atmosphere to give the corresponding unsymmetrical aryl–aryl coupling products conveniently.

    Radical C-H arylations of (hetero)arenes catalysed by gallic acid.

    PubMed

    Perretti, Marcelle D; Monzón, Diego M; Crisóstomo, Fernando P; Martín, Víctor S; Carrillo, Romen

    2016-07-12

    Gallic acid efficiently catalyses radical arylations in water-acetone at room temperature. This methodology proved to be versatile and scalable. Therefore, it constitutes a greener alternative to arylation. Moreover, considering that gallic acid is an abundant vegetable tannin, this work also unleashes an alternative method for the reutilisation of bio-wastes. PMID:26804947

  7. One-pot sequential asymmetric hydrogenation of β-aryl-β-aryloxy acroleins.

    PubMed

    Liu, Yufeng; Chen, Jianzhong; Zhang, Zhenfeng; Qin, Jian; Zhao, Min; Zhang, Wanbin

    2016-08-01

    A one-pot sequential asymmetric hydrogenation of β-aryl-β-aryloxy acroleins has been realized for the preparation of chiral 3-aryl-3-aryloxy alcohols with excellent yields and good enantioselectivities. This methodology can be employed in new synthetic routes for the synthesis of fluoxetine, atomoxetine, and related analogues. PMID:27439010

  8. p-Toluenesulphonic acid-promoted, I2-catalysed sulphenylation of pyrazolones with aryl sulphonyl hydrazides.

    PubMed

    Zhao, Xia; Zhang, Lipeng; Li, Tianjiao; Liu, Guiyan; Wang, Haomeng; Lu, Kui

    2014-11-01

    Aryl pyrazolone thioethers were synthesized via the I2-catalysed cross-coupling of pyrazolones with aryl sulphonyl hydrazides in the presence of p-toluenesulphonic acid, which has been proposed to promote the reaction by facilitating the decomposition of sulphonyl hydrazides. PMID:25225659

  9. Palladium-catalyzed intramolecular C-H arylation of arenes using tosylates and mesylates as electrophiles.

    PubMed

    Nervig, Christine S; Waller, Peter J; Kalyani, Dipannita

    2012-09-21

    This paper describes a method for the palladium catalyzed intramolecular C-H arylation using tosylates and mesylates as electrophiles. The transformation is efficient for the synthesis of various heterocyclic motifs including furans, carbazoles, indoles, and lactams. Additionally, a protocol for the one-pot sequential tosylation/arylation of phenol derivatives is presented. PMID:22974229

  10. Simple palladium(II) precatalyst for Suzuki-Miyaura couplings: efficient reactions of benzylic, aryl, heteroaryl, and vinyl coupling partners.

    PubMed

    Burns, Michael J; Fairlamb, Ian J S; Kapdi, Anant R; Sehnal, Petr; Taylor, Richard J K

    2007-12-20

    trans-PdBr(N-Succ)(PPh3)2 (1) is a universally effective precatalyst for Suzuki-Miyaura cross-couplings of benzylic halides with aryl- or heteroarylboronic acids. Substituted aryl halides and halogenated cyclic enones can be cross-coupled with aryl- or vinylboronic acids in excellent yields. Catalyst recycling is also demonstrated. PMID:18047357

  11. Automated determination of bromide in waters by ion chromatography with an amperometric detector

    USGS Publications Warehouse

    Pyen, G.S.; Erdmann, D.E.

    1983-01-01

    An automated ion chromatograph, including a program controller, an automatic sampler, an integrator, and an amperometric detector, was used to develop a procedure for the determination of bromide in rain water and many ground waters. Approximately 10 min is required to obtain a chromatogram. The detection limit for bromide is 0.01 mg l-1 and the relative standard deivation is <5% for bromide concentrations between 0.05 and 0.5 mg l-1. Chloride interferes if the chloride-to-bromide ratio is greater than 1 000:1 for a range of 0.01-0.1 mg l-1 bromide; similarly, chloride interferes in the 0.1-1.0 mg l-1 range if the ratio is greater than 5 000:1. In the latter case, a maximum of 2 000 mg l-1 of chloride can be tolerated. Recoveries of known concentrations of bromide added to several samples, ranged from 97 to 110%. ?? 1983.

  12. Simple modeling of hydrostatic bearings

    NASA Astrophysics Data System (ADS)

    Hull, Charlie

    2014-07-01

    Hydrostatic bearings are a key component for many large telescopes due to their high load bearing capacity, stiffness and low friction. A simple technique is presented to model these bearings to understand the effects of geometry, oil viscosity, flow control, temperature, etc. on the bearings behavior.

  13. Climate Drives Polar Bear Origins

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In their provocative analysis of northern bears (“Nuclear genomic sequences reveal that polar bears are an old and distinct bear lineage,” Reports, 20 April, p. 344), F. Hailer et al. use independent nuclear loci to show that polar bears originated during the middle Pleistocene, rather than during t...

  14. Magnetic Bearing Consumes Low Power

    NASA Technical Reports Server (NTRS)

    Studer, P. A.

    1982-01-01

    Energy-efficient linear magnetic bearing maintains a precise small separation between its moving and stationary parts. Originally designed for cryogenic compressors on spacecraft, proposed magnetic bearing offers an alternative to roller or gas bearing in linear motion system. Linear noncontacting bearing operates in environments where lubricants cannot be used.

  15. Interaction between gaseous ozone and crystalline potassium bromide

    NASA Astrophysics Data System (ADS)

    Levanov, A. V.; Maksimov, I. B.; Isaikina, O. Ya.; Antipenko, E. E.; Lunin, V. V.

    2016-07-01

    The formation of nonvolatile products of the oxidation of a bromide ion during the interaction between gaseous ozone and powdered crystalline KBr is studied. It is found that potassium bromate KBrO3 is the main product of the reaction. The influence of major experimental factors (the duration of ozonation, the concentration of ozone, the humidity of the initial gas, and the temperature) on the rate of formation of bromate is studied. The effective constants of the formation of bromate during the interaction between O3 and Br- in a heterogeneous gas-solid body system and in a homogeneous aqueous solution are compared.

  16. Photodissociation of methyl chloride and methyl bromide in the atmosphere

    NASA Technical Reports Server (NTRS)

    Robbins, D. E.

    1976-01-01

    Methyl chloride (CH3Cl) and methyl bromide (CH3Br) have been suggested to be significant sources of the stratospheric halogens. The breakup of these compounds in the stratosphere by photodissociation or reaction with OH releases halogen atoms which catalytically destroy ozone. Experimental results are presented for ultraviolet photoabsorption cross sections of CH3Cl and CH3Br. Calculations are presented of loss rates for the methyl halides due to photodissociation and reaction with OH and of mixing ratios of these species in the stratosphere.

  17. Pseudoephedrine-Directed Asymmetric α-Arylation of α-Amino Acid Derivatives.

    PubMed

    Atkinson, Rachel C; Fernández-Nieto, Fernando; Mas Roselló, Josep; Clayden, Jonathan

    2015-07-27

    Available α-amino acids undergo arylation at their α position in an enantioselective manner on treatment with base of N'-aryl urea derivatives ligated to pseudoephedrine as a chiral auxiliary. In situ silylation and enolization induces diastereoselective migration of the N'-aryl group to the α position of the amino acid, followed by ring closure to a hydantoin with concomitant explulsion of the recyclable auxiliary. The hydrolysis of the hydantoin products provides derivatives of quaternary amino acids. The arylation avoids the use of heavy-metal additives, and is successful with a range of amino acids and with aryl rings of varying electronic character. PMID:26083236

  18. α-Quaternary Proline Derivatives by Intramolecular Diastereoselective Arylation of N-Carboxamido Proline Ester Enolates.

    PubMed

    Maury, Julien; Clayden, Jonathan

    2015-11-01

    Pyrrolidine-2-carboxylate esters substituted in the 3-, 4- or 5-positions were converted to their N'-aryl urea derivatives. Deprotonation at the 2-position to form a potassium enolate led to migration of the N'-aryl substituent to the 2 position of the pyrrolidine ring, followed by cyclization of the resulting urea to give bicyclic α-aryl hydantoin derivatives of substituted prolines. Depending on the substitution pattern of the starting material, high diastereoselectivity was observed in the aryl migration, allowing formation of the products in enantiomerically enriched form, despite the intermediacy of a planar enolate. The hydrolysis of the bicyclic hydantoins under basic conditions gave a range of enantiopure and enantioenriched quaternary α-aryl proline derivatives. PMID:26421443

  19. Effects of pinaverium bromide and verapamil on the motility of the rat isolated colon.

    PubMed

    Baumgartner, A; Drack, E; Halter, F; Scheurer, U

    1985-09-01

    Pinaverium bromide was 30 times less potent than verapamil in inhibiting intraluminal pressure responses of in vitro rat colonic segments to barium chloride, acetylcholine, FK 33-824 or field stimulation. The inhibitory effects of both verapamil and pinaverium bromide on the pressure responses to field stimulation were antagonized similarly by exogenous calcium administration. These results support the concept that pinaverium bromide acts on calcium channels in the smooth muscle cell membrane. PMID:4052731

  1. Effects of pinaverium bromide and verapamil on the motility of the rat isolated colon.

    PubMed Central

    Baumgartner, A.; Drack, E.; Halter, F.; Scheurer, U.

    1985-01-01

    Pinaverium bromide was 30 times less potent than verapamil in inhibiting intraluminal pressure responses of in vitro rat colonic segments to barium chloride, acetylcholine, FK 33-824 or field stimulation. The inhibitory effects of both verapamil and pinaverium bromide on the pressure responses to field stimulation were antagonized similarly by exogenous calcium administration. These results support the concept that pinaverium bromide acts on calcium channels in the smooth muscle cell membrane. PMID:4052731

  2. Fluid lubricated bearing assembly

    DOEpatents

    Boorse, Henry A.; Boeker, Gilbert F.; Menke, John R.

    1976-01-01

    1. A support for a loaded rotatable shaft comprising in combination on a housing having a fluid-tight cavity encasing an end portion of said shaft, a thrust bearing near the open end of said cavity for supporting the axial thrust of said shaft, said thrust bearing comprising a thrust plate mounted in said housing and a thrust collar mounted on said shaft, said thrust plate having a central opening the peripheral portion of which is hermetically sealed to said housing at the open end of said cavity, and means for supplying a fluid lubricant to said thrust bearing, said thrust bearing having a lubricant-conducting path connecting said lubricant supplying means with the space between said thrust plate and collar intermediate the peripheries thereof, the surfaces of said plate and collar being constructed and arranged to inhibit radial flow of lubricant and, on rotation of said thrust collar, to draw lubricant through said path between the bearing surfaces and to increase the pressure therebetween and in said cavity and thereby exert a supporting force on said end portion of said shaft.

  3. [Synthesis and antidepressant activities of aryl alkanol piperidine derivatives].

    PubMed

    Zheng, Yong-yong; Gao, Kai; Weng, Zhi-jie; Li, Jian-qi

    2010-03-01

    To explore novel monoamine reuptake inhibitor with antidepressant activity, a series of substituted aryl alkanol piperidine derivatives were designed and synthesized. All of them were new compounds, and their structures were confirmed with 1H NMR and HR-MS. The results showed that compounds 4, 5 and 8 displayed strong 5-HT, NA and DA reuptake inhibiting activities in vitro. Among the tested compounds, 4, 5 and 13 exhibited potent antidepressant activities in the mice forced swimming test. Compounds 4 and 5 have potent antidepressant activities and are worth further development. PMID:21351508

  4. Copper Mediated Difluoromethylation of Aryl and Vinyl Iodides

    PubMed Central

    Fier, Patrick S.

    2012-01-01

    Selectively fluorinated molecules are important as materials, pharmaceuticals, and agrochemicals, but their synthesis by simple, mild, laboratory methods is challenging. We report a straightforward method for the cross-coupling of a difluoromethyl group with readily available reagents to form difluoromethylarenes. The reaction of electron-neutral, electron-rich, and sterically hindered aryl and vinyl iodides with the combination of CuI, CsF and TMSCF2H leads to the formation of difluoromethylarenes in high yield with good functional group compatibility. This transformation is surprising, in part, because of the prior observation of the instability of CuCF2H. PMID:22397683

  5. Functionalization of Rhenium Aryl Bonds by O-Atom Transfer

    SciTech Connect

    Bischof, Steven M.; Cheng, Mu-Jeng; Nielsen, Robert J.; Gunnoe, T. Brent; Goddard, William A.; Periana, Roy A.

    2011-03-29

    Aryltrioxorhenium (ArReO3) has been demonstrated to show rapid oxy-functionalization upon reaction with O-atom donors, YO, to selectively generate the corresponding phenols in near quantitative yields. 18O-Labeling experiments show that the oxygen in the products is exclusively from YO. DFT studies reveal a 10.7 kcal/mol barrier (Ar = Ph) for oxy-functionalization with H2O2 via a Baeyer-Villiger type mechanism involving nucleophilic attack of the aryl group on an electrophilic oxygen of YO coordinated to rhenium.

  6. Sulfinyl and sulfonyl derivatives of aryl substituted cis-1-thiadecalins

    SciTech Connect

    Klimenko, S.K.; Sorokin, N.N.; Tyrina, T.I.; Stolbova, T.V.

    1987-10-01

    Individual 2..cap alpha..-aryl- and 2..cap alpha..,4..cap alpha..-diaryl-cis-thiadecalin-1..beta..-oxides and 1,1-dioxides have been synthesized. The effect of sulfinyl and sulfonyl groups has been observed on the chemical shifts of carbon atoms in these conformationally homogeneous, stereochemically similar systems. IR spectra were obtained in mineral oil with a UR-20 spectrometer. /sup 13/C NMR spectra were obtained with a Varian FT-80A instrument (20 MHz) at 30/sup 0/. The spectra were parametrized with respect to the signal of the secondary standard, for which the signal of CDCl/sub 3/ solvent was used.

  7. Copper-catalyzed asymmetric hydrogenation of aryl and heteroaryl ketones.

    PubMed

    Krabbe, Scott W; Hatcher, Mark A; Bowman, Roy K; Mitchell, Mark B; McClure, Michael S; Johnson, Jeffrey S

    2013-09-01

    High throughput screening enabled the development of a Cu-based catalyst system for the asymmetric hydrogenation of prochiral aryl and heteroaryl ketones that operates at H2 pressures as low as 5 bar. A ligand combination of (R,S)-N-Me-3,5-xylyl-BoPhoz and tris(3,5-xylyl)phosphine provided benzylic alcohols in good yields and enantioselectivities. The electronic and steric characteristics of the ancillary triarylphosphine were important in determining both reactivity and selectivity. PMID:23980941

  8. Aryl hydrocarbon receptor–dependent enrichment of a megakaryocytic precursor with a high potential to produce proplatelets

    PubMed Central

    Brouard, Nathalie; Mallo, Lea; Receveur, Nicolas; Mangin, Pierre; Eckly, Anita; Bieche, Ivan; Tarte, Karin; Gachet, Christian; Lanza, François

    2016-01-01

    The mechanisms regulating megakaryopoiesis and platelet production (thrombopoiesis) are still incompletely understood. Identification of a progenitor with enhanced thrombopoietic capacity would be useful to decipher these mechanisms and to improve our capacity to produce platelets in vitro. Differentiation of peripheral blood CD34+ cells in the presence of bone marrow–human mesenchymal stromal cells (MSCs) enhanced the production of proplatelet-bearing megakaryocytes (MKs) and platelet-like elements. This was accompanied by enrichment in a MK precursor population exhibiting an intermediate level of CD41 positivity while maintaining its expression of CD34. Following sorting and subculture with MSCs, this CD34+CD41low population was able to efficiently generate proplatelet-bearing MKs and platelet-like particles. Similarly, StemRegenin 1 (SR1), an antagonist of the aryl hydrocarbon receptor (AhR) transcription factor known to maintain CD34 expression of progenitor cells, led to an enriched CD34+CD41low fraction and to an increased capacity to generate proplatelet-producing MKs and platelet-like elements ultrastructurally and functionally similar to circulating platelets. The effect of MSCs, like that of SR1, appeared to be mediated by an AhR-dependent mechanism because both culture conditions resulted in repression of its downstream effector CYP1B1. This newly described isolation of a precursor exhibiting strong MK potential could be exploited to study normal and abnormal thrombopoiesis and for in vitro platelet production. PMID:26966088

  9. Aryl hydrocarbon receptor-dependent enrichment of a megakaryocytic precursor with a high potential to produce proplatelets.

    PubMed

    Strassel, Catherine; Brouard, Nathalie; Mallo, Lea; Receveur, Nicolas; Mangin, Pierre; Eckly, Anita; Bieche, Ivan; Tarte, Karin; Gachet, Christian; Lanza, François

    2016-05-01

    The mechanisms regulating megakaryopoiesis and platelet production (thrombopoiesis) are still incompletely understood. Identification of a progenitor with enhanced thrombopoietic capacity would be useful to decipher these mechanisms and to improve our capacity to produce platelets in vitro. Differentiation of peripheral blood CD34(+) cells in the presence of bone marrow-human mesenchymal stromal cells (MSCs) enhanced the production of proplatelet-bearing megakaryocytes (MKs) and platelet-like elements. This was accompanied by enrichment in a MK precursor population exhibiting an intermediate level of CD41 positivity while maintaining its expression of CD34. Following sorting and subculture with MSCs, this CD34(+)CD41(low) population was able to efficiently generate proplatelet-bearing MKs and platelet-like particles. Similarly, StemRegenin 1 (SR1), an antagonist of the aryl hydrocarbon receptor (AhR) transcription factor known to maintain CD34 expression of progenitor cells, led to an enriched CD34(+)CD41(low) fraction and to an increased capacity to generate proplatelet-producing MKs and platelet-like elements ultrastructurally and functionally similar to circulating platelets. The effect of MSCs, like that of SR1, appeared to be mediated by an AhR-dependent mechanism because both culture conditions resulted in repression of its downstream effector CYP1B1. This newly described isolation of a precursor exhibiting strong MK potential could be exploited to study normal and abnormal thrombopoiesis and for in vitro platelet production. PMID:26966088

  10. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

    PubMed Central

    Shrestha, Bijay

    2015-01-01

    Summary We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  11. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents.

    PubMed

    Shrestha, Bijay; Giri, Ramesh

    2015-01-01

    We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N',N'-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  12. Synthetic studies towards putative yuremamine using an iterative C(sp(3))-H arylation strategy.

    PubMed

    Calvert, Matthew B; Sperry, Jonathan

    2016-06-28

    An overview of an iterative, 8-aminoquinoline (AQ)-directed C(sp(3))-H arylation strategy towards the pyrroloindole structure initially assigned to the alkaloid yuremamine is described. During initial efforts using a model indane system, it was discovered that the iodoresorcinol unit was not a viable C(sp(3))-H arylation partner when masked as its dimethyl ether but upon switching to a MOM group, the ether oxygen served to stabilise the high valent Pd intermediate during the reaction, thus promoting reductive elimination and leading to acceptable yields of the C(sp(3))-H arylation product. The second C(sp(3))-H arylation with an iodopyrogallol gave a 1,3-diarylated model yuremamine system possessing the desired 1,3-cis relationship. When the successful model studies were applied to a pyrroloindole system in pursuit of yuremamine, it became apparent that C9 underwent competing C(sp(2))-H arylation if left vacant, but installing a tryptamine side chain at this site prevented the desired C(sp(3))-H arylation from occurring altogether. However, a C9-methyl pyrroloindole underwent iterative C(sp(3))-H arylation at C1 with an iodoresorcinol followed by C3 with an iodopyrogallol to give a diarylated product with the aryl groups in the undesired 1,3-trans-relationship, arising from epimerisation at C1 during the second C(sp(3))-H arylation event. Although the synthesis of putative yuremamine was not accomplished, several findings are disclosed that will serve as useful additions to the burgeoning field of directed C(sp(3))-H arylations and related C-H functionalization reactions. PMID:26891188

  13. Transient neuromyopathy after bromide intoxication in a dog with idiopathic epilepsy

    PubMed Central

    2012-01-01

    A seven-year old Australian Shepherd, suffering from idiopathic epilepsy under treatment with phenobarbitone and potassium bromide, was presented with generalised lower motor neuron signs. Electrophysiology and muscle-nerve biopsies revealed a neuromyopathy. The serum bromide concentration was increased more than two-fold above the upper reference value. Clinical signs disappeared after applying diuretics and reducing the potassium bromide dose rate. This is the first case report describing electrophysiological and histopathological findings associated with bromide induced lower motor neuron dysfunction in a dog. PMID:23216950

  14. Solving bearing overheating problems

    SciTech Connect

    Jendzurski, T.

    1995-05-08

    Overheating is a major indicator, along with vibration and noise, of an underlying problem affecting a bearing or related components. Because normal operating temperatures vary widely from one application to another, no single temperature is a reliable sign of overheating in every situation. By observing an application when it is running smoothly, a technician can establish a benchmark temperature for a particular bearing arrangement. Wide deviations from this accepted norm generally indicate troublesome overheating. The list of possible causes of over-heating ranges from out-of-round housings and oversize shaft diameters to excessive lubrication and bearing preloading. These causes fall into two major categories: improper or faulty lubrication and mechanical problems, such as incorrect fits and tolerances. These are discussed along with solutions.

  15. Radial Halbach Magnetic Bearings

    NASA Technical Reports Server (NTRS)

    Eichenberg, Dennis J.; Gallo, Christopher A.; Thompson, William K.

    2009-01-01

    Radial Halbach magnetic bearings have been investigated as part of an effort to develop increasingly reliable noncontact bearings for future high-speed rotary machines that may be used in such applications as aircraft, industrial, and land-vehicle power systems and in some medical and scientific instrumentation systems. Radial Halbach magnetic bearings are based on the same principle as that of axial Halbach magnetic bearings, differing in geometry as the names of these two types of bearings suggest. Both radial and axial Halbach magnetic bearings are passive in the sense that unlike most other magnetic bearings that have been developed in recent years, they effect stable magnetic levitation without need for complex active control. Axial Halbach magnetic bearings were described in Axial Halbach Magnetic Bearings (LEW-18066-1), NASA Tech Briefs, Vol. 32, No. 7 (July 2008), page 85. In the remainder of this article, the description of the principle of operation from the cited prior article is recapitulated and updated to incorporate the present radial geometry. In simplest terms, the basic principle of levitation in an axial or radial Halbach magnetic bearing is that of the repulsive electromagnetic force between (1) a moving permanent magnet and (2) an electric current induced in a stationary electrical conductor by the motion of the magnetic field. An axial or radial Halbach bearing includes multiple permanent magnets arranged in a Halbach array ("Halbach array" is defined below) in a rotor and multiple conductors in the form of wire coils in a stator, all arranged so the rotary motion produces an axial or radial repulsion that is sufficient to levitate the rotor. A basic Halbach array (see Figure 1) consists of a row of permanent magnets, each oriented so that its magnetic field is at a right angle to that of the adjacent magnet, and the right-angle turns are sequenced so as to maximize the magnitude of the magnetic flux density on one side of the row while

  16. Magnetic bearings for spacecraft

    NASA Technical Reports Server (NTRS)

    Studer, P. A.

    1972-01-01

    Magnetic bearings have been successfully applied to motorized rotor systems in the multi-kilogram range, at speeds up to 1200 radians per second. These engineering models also indicated the need for continued development in specific areas to make them feasible for spacecraft applications. Significant power reductions have recently been attained. A unique magnetic circuit, combining permanent magnets with electromagnetic control, has a bidirectional forcing capability with improved current sensitivity. The multi-dimensional nature of contact-free rotor support is discussed. Stable continuous radial suspension is provided by a rotationally symmetric permanent magnet circuit. Two bearings, on a common shaft, counteract the normal instability perpendicular to the rotational axis. The axial direction is servoed to prevent contact. A new bearing technology and a new field of application for magnetics is foreseen.

  17. Partial tooth gear bearings

    NASA Technical Reports Server (NTRS)

    Vranish, John M. (Inventor)

    2010-01-01

    A partial gear bearing including an upper half, comprising peak partial teeth, and a lower, or bottom, half, comprising valley partial teeth. The upper half also has an integrated roller section between each of the peak partial teeth with a radius equal to the gear pitch radius of the radially outwardly extending peak partial teeth. Conversely, the lower half has an integrated roller section between each of the valley half teeth with a radius also equal to the gear pitch radius of the peak partial teeth. The valley partial teeth extend radially inwardly from its roller section. The peak and valley partial teeth are exactly out of phase with each other, as are the roller sections of the upper and lower halves. Essentially, the end roller bearing of the typical gear bearing has been integrated into the normal gear tooth pattern.

  18. IUPAC-NIST Solubility Data Series. 94. Rare Earth Metal Iodides and Bromides in Water and Aqueous Systems. Part 2. Bromides

    NASA Astrophysics Data System (ADS)

    Mioduski, Tomasz; Gumiński, Cezary; Zeng, Dewen; Voigt, Heidelore

    2013-03-01

    This work presents solubility data for rare earth metal bromides in water and in aqueous ternary systems. Compilations of all available experimental data are introduced for each rare earth metal bromide with a corresponding critical evaluation. Every such evaluation contains a collection of all solubility results in water, a selection of suggested solubility data and a brief discussion of the multicomponent systems. Because the ternary systems were almost never studied more than once, no critical evaluations of such data were possible. Only simple bromides (no complexes) are treated as the input substances in this work. The literature has been covered through the end of 2011.

  19. Blood Pump Bearing System

    NASA Technical Reports Server (NTRS)

    Aber, Gregory S. (Inventor)

    2000-01-01

    An apparatus is provided for a blood pump bearing system within a pump housing to support long-term highspeed rotation of a rotor with an impeller blade having a plurality of individual magnets disposed thereon to provide a small radial air gap between the magnets and a stator of less than 0.025 inches. The bearing system may be mounted within a flow straightener, diffuser, or other pump element to support the shaft of a pump rotor. The bearing system includes a zirconia shaft having a radiused end. The radiused end has a first radius selected to be about three times greater than the radius of the zirconia shaft. The radiused end of the zirconia shaft engages a flat sapphire endstone. Due to the relative hardness of these materials a flat is quickly produced during break-in on the zirconia radiused end of precisely the size necessary to support thrust loads whereupon wear substantially ceases. Due to the selection of the first radius, the change in shaft end-play during pump break-in is limited to a total desired end-play of less than about 0.010 inches. Radial loads are supported by an olive hole ring jewel that makes near line contact around the circumference of the Ir shaft to support big speed rotation with little friction. The width of olive hole ring jewel is small to allow heat to conduct through to thereby prevent heat build-up in the bearing. A void defined by the bearing elements may fill with blood that then coagulates within the void. The coagulated blood is then conformed to the shape of the bearing surfaces.

  20. Blood Pump Bearing System

    NASA Technical Reports Server (NTRS)

    Aber, Gregory S. (Inventor)

    1999-01-01

    Methods and apparatus are provided for a blood pump bearing system within a pump housing to support long-term high-speed rotation of a rotor with an impeller blade having a plurality of individual magnets disposed thereon to provide a small radial air gap between the magnets and a stator of less than 0.025 inches. The bearing system may be mounted within a flow straightener, diffuser, or other pump element to support the shaft of a pump rotor. The bearing system includes a zirconia shaft having a radiused end. The radiused end has a first radius selected to be about three times greater than the radius of the zirconia shaft. The radiused end of the zirconia shaft engages a flat sapphire endstone. Due to the relative hardness of these materials a flat is quickly produced during break-in on the zirconia radiused end of precisely the size necessary to support thrust loads whereupon wear substantially ceases. Due to the selection of the first radius, the change in shaft end-play during pump break-in is limited to a total desired end-play of less than about 0.010 inches. Radial loads are supported by an olive hole ring jewel that makes near line contact around the circumference of the shaft to support high speed rotation with little friction. The width of olive hole ring jewel is small to allow heat to conduct through to thereby prevent heat build-up in the bearing. A void defined by the bearing elements may fill with blood that then coagulates within the void. The coagulated blood is then conformed to the shape of the bearing surfaces.

  1. Bromoform formation in ozonated groundwater containing bromide and humic substances

    SciTech Connect

    Cooper, W.J.; Amy, G.L.; Moore, C.A.; Zika, R.G.

    1986-01-01

    The effect of bromide ion, organic carbon concentration (natural aquatic humic substances), pH, and solar irradiation on the formation of bromoform in ozonated groundwater has been studied. The studies were conducted on four unique samples of groundwater taken from different regions of the Biscayne Aquifer in southern Florida. All other conditions being equal, increases in bromide ion concentrations resulted in increases in CHBr/sub 3/ formation. In three of the four samples, CHBr/sub 3/ formation decreased as the pH level increased from 5 to 9. The fourth sample exhibited an opposite trend whereby the CHBr/sub 3/ concentration increased with increasing pH. Bromoform concentration increased with increased O/sub 3/ concentration over an ozone dosage range of 3.4 to 6.7 mg/L. Ozonated samples placed in sunlight immediately after ozone addition showed a decrease in the formation of CHBr/sub 3/ presumably due to the photodecomposition of HOBr/OBr.

  2. Modular gear bearings

    NASA Technical Reports Server (NTRS)

    Vranish, John M. (Inventor)

    2009-01-01

    A gearing system using modular gear bearing components. Each component is composed of a core, one or more modules attached to the core and two or more fastening modules rigidly attaching the modules to the core. The modules, which are attached to the core, may consist of gears, rollers or gear bearing components. The core orientation affects the orientation of the modules attached to the core. This is achieved via the keying arrangement of the core and the component modules that attach to the core. Such an arrangement will also facilitate the phase tuning of gear modules with respect to the core and other gear modules attached to the core.

  3. Efficient Catalyst One-Pot Synthesis of 7-(Aryl)-10,10-dimethyl-10,11-dihydrochromeno[4,3-b]chromene-6,8(7H,9H)-dione Derivatives Complemented by Antibacterial Activity

    PubMed Central

    Al-Majedy, Yasameen K.; Kadhum, Abdul Amir H.; Mohamad, Abu Bakar

    2016-01-01

    The problem of bacteria resistance to many known agents has inspired scientists and researchers to discover novel efficient antibacterial drugs. Three rapid, clean, and highly efficient methods were developed for one-pot synthesis of 7-(aryl)-10,10-dimethyl-10,11-dihydrochromeno[4,3-b]chromene-6,8(7H,9H)-dione derivatives. Three components are condensed in the synthesis, 4-hydroxycoumarin, 5,5-dimethyl-1,3-cyclohexanedione, and aromatic aldehydes, using tetrabutylammonium bromide (TBAB), diammonium hydrogen phosphate (DAHP), or ferric chloride (FeCl3), respectively. Each method has different reaction mechanisms according to the catalyst. The present methods have advantages, including one-pot synthesis, excellent yields, short reaction times, and easy isolation of product. All catalysts utilized in our study could be reused several times without losing their catalytic efficiency. All synthesized compounds were fully characterized and evaluated for their antibacterial activity. PMID:27563671

  4. Efficient Catalyst One-Pot Synthesis of 7-(Aryl)-10,10-dimethyl-10,11-dihydrochromeno[4,3-b]chromene-6,8(7H,9H)-dione Derivatives Complemented by Antibacterial Activity.

    PubMed

    Al-Majedy, Yasameen K; Al-Amiery, Ahmed A; Kadhum, Abdul Amir H; Mohamad, Abu Bakar

    2016-01-01

    The problem of bacteria resistance to many known agents has inspired scientists and researchers to discover novel efficient antibacterial drugs. Three rapid, clean, and highly efficient methods were developed for one-pot synthesis of 7-(aryl)-10,10-dimethyl-10,11-dihydrochromeno[4,3-b]chromene-6,8(7H,9H)-dione derivatives. Three components are condensed in the synthesis, 4-hydroxycoumarin, 5,5-dimethyl-1,3-cyclohexanedione, and aromatic aldehydes, using tetrabutylammonium bromide (TBAB), diammonium hydrogen phosphate (DAHP), or ferric chloride (FeCl3), respectively. Each method has different reaction mechanisms according to the catalyst. The present methods have advantages, including one-pot synthesis, excellent yields, short reaction times, and easy isolation of product. All catalysts utilized in our study could be reused several times without losing their catalytic efficiency. All synthesized compounds were fully characterized and evaluated for their antibacterial activity. PMID:27563671

  5. New class of 2-aryl-6-chloro-3,4-dihydroisoquinolinium salts as potential antifungal agents for plant protection: synthesis, bioactivity and structure-activity relationships.

    PubMed

    Yang, Rui; Gao, Zhao-Feng; Zhao, Jie-Yu; Li, Wei-Bo; Zhou, Le; Miao, Fang

    2015-02-25

    Thirty-four new 2-aryl-6-chloro-3,4-dihydroisoquinolin-2-ium bromides were synthesized, and their structures were elucidated by spectroscopic analysis. Antifungal activities against Alternaria alternate, Curvularia lunata and Valsa mali were evaluated by the mycelium linear growth rate method. SAR was discussed also. All compounds showed some activity against each of the fungi at 25 μg/mL. Compared to azoxystrobin, a commercial fungicide, 31 out of 34 test compounds showed higher inhibition rates against C. lunata and 10 were more effective against A. alternate and V. mali. Compounds 5-4, 5-2 and 5-34 showed the highest activity against A. alternate (EC50 = 10.3 μg/mL), C. lunata (EC50 = 4.6 μg/mL) and V. mali (EC50 = 3.9 μg/mL), respectively, superior to azoxystrobin (EC50 = 12.8, 71.9, 37.2 μg/mL). Compound 5-4 displayed good activities against each of the fungi with EC50 of 10.3, 4.7, and 18.0 μg/mL while 5-34 displayed excellent activities against V. mali (EC50 = 3.9 μg/mL) and C. lunata (EC50 = 5.8 μg/mL). The SAR showed that the type and position of substituents on the C-ring had significant effects on the activity. Generally, the presence of 2'-F, 4'-F or 2'-CH3 could significantly improve the activities, whereas OH, OMe, NO2 or CF3 groups decreased the activities. Thus, it was concluded that the present research provided a new series of 2-aryl-6-chloro-3,4-dihydroisoquinolin-2-iums with excellent antifungal potency, and the results were of importance for the structure optimization design, synthesis and development of more potent isoquinoline antifungal agents. PMID:25645055

  6. Direct (Hetero)arylation Polymerization: Trends and Perspectives.

    PubMed

    Bura, Thomas; Blaskovits, J Terence; Leclerc, Mario

    2016-08-17

    Conjugated polymers have attracted much attention in recent years, as they can combine the best features of metals or inorganic semiconducting materials (excellent electrical and optical properties) with those of synthetic polymers (mechanical flexibility, simple processing, and low-cost production), thereby creating altogether new scientific synergies and technological opportunities. In the search for more efficient synthetic methods for the preparation of conjugated polymers, this Perspective reports advances in the field of direct (hetero)arylation polymerization. This recently developed polymerization method encompasses the formation of carbon-carbon bonds between simple (hetero)arenes and (hetero)aryl halides, reducing both the number of synthetic steps and the production of organometallic byproducts. Along these lines, we describe the most general and adaptable reaction conditions for the preparation of high-molecular-weight, defect-free conjugated polymers. We also discuss the bottleneck presented by the utilization of certain brominated thiophene units and propose some potential solutions. It is, however, firmly believed that this polymerization method will become a versatile tool in the field of conjugated polymers by providing a desirable atom-economical alternative to standard cross-coupling polymerization reactions. PMID:27463826

  7. Aryl sulfonates as neutral photoacid generators (PAGs) for EUV lithography

    NASA Astrophysics Data System (ADS)

    Sulc, Robert; Blackwell, James M.; Younkin, Todd R.; Putna, E. Steve; Esswein, Katherine; DiPasquale, Antonio G.; Callahan, Ryan; Tsubaki, Hideaki; Tsuchihashi, Tooru

    2009-03-01

    EUV lithography (EUVL) is a leading candidate for printing sub-32 nm hp patterns. In order for EUVL to be commercially viable at these dimensions, a continuous evolution of the photoresist material set is required to simultaneously meet the aggressive specifications for resolution, resist sensitivity, LWR, and outgassing rate. Alternative PAG designs, especially if tailored for EUVL, may aid in the formation of a material set that helps achieve these aggressive targets. We describe the preparation, characterization, and lithographic evaluation of aryl sulfonates as non-ionic or neutral photoacid generators (PAGs) for EUVL. Full lithographic characterization is reported for our first generation resist formulation using compound H, MAP-1H-2.5. It is benchmarked against MAP-1P-5.0, which contains the well-known sulfonium PAG, triphenylsulfonium triflate (compound P). Z-factor analysis indicates nZ32 = 81.4 and 16.8 respectively, indicating that our first generation aryl sulfonate formulations require about 4.8x improvement to match the results achieved with a model onium PAG. Improving the acid generation efficiency and use of the generated byproducts is key to the continued optimization of this class of PAGs. To that end, we believe EI-MS fragmentation patterns and molecular simulations can be used to understand and optimize the nature and efficiency of electron-induced PAG fragmentation.

  8. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

    PubMed Central

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T.; Evoy, Stephane

    2016-01-01

    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. PMID:26985910

  9. Steric Effects in the Reaction of Aryl Radicals on Surfaces

    SciTech Connect

    Combellas, Catherine; Jiang, Deen; Kanoufi, Frederic; Pinson, Jean; Podvorica, Fetah

    2009-01-01

    Steric effects are investigated in the reaction of aryl radicals with surfaces. The electrochemical reduction of 2-, 3-, 4-methyl, 2-methoxy, 2-ethyl, 2,6-, 2,4-, and 3,5-dimethyl, 4-tert-butyl, 3,5-bis-tert-butyl benzenediazonium, 3,5-bis(trifluoromethyl), and pentafluoro benzenediazonium tetrafluoroborates is examined in acetonitrile solutions. It leads to the formation of grafted layers only if the steric hindrance at the 2- or 2,6-position(s) is small. When the 3,5-positions are crowded with tert-butyl groups, the growth of the organic layer is limited by steric effects and a monolayer is formed. The efficiency of the grafting process is assessed by cyclic voltammetry, X-ray photoelectron spectroscopy, infrared, and ellipsometry. These experiments, together with density functional computations of bonding energies of substituted phenyl groups on a copper surface, are discussed in terms of the reactivity of aryl radicals in the electrografting reaction and in the growth of the polyaryl layer.

  10. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

    PubMed

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

    2016-03-01

    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. PMID:26985910

  11. The distribution of bromide in water in the Floridan aquifer system, Duval County, northeastern Florida

    USGS Publications Warehouse

    German, E.R.; Taylor, G.F.

    1995-01-01

    Although Duval County, Florida, has ample ground-water resources for public supply, the potential exists for a problem with excessive disinfectant by-products. These disinfectant by-products result from the treatment of raw water containing low concentrations of bromide and naturally occurring organic compounds. Because of this potential problem, the relation of bromide concentrations to aquifer tapped, well location and depth, and chemical characteristics of water in the Floridan aquifer system underlying Duval County were studied to determine if these relations could be applied to delineate water with low-bromide concentrations for future supplies. In 1992, water samples from 106 wells that tap the Floridan aquifer system were analyzed for bromide and major dissolved constituents. A comparison of bromide concentrations from the 1992 sampling with data from earlier studies (1979-80) indicates that higher bromide concentrations were detected during the earlier studies. The difference between the old and new data is probably because of a change in analytical methodology in the analysis of samples. Bromide concentrations exceeded the detection limit (0.10 milligrams per liter) in water from 28 of the 106 wells (26 percent) sampled in 1992. The maximum concentration was 0.56 milligrams per liter. There were no relations between bromide and major dissolved constituents, well depth, or aquifer tapped that would be useful for determining bromide concentrations. Areal patterns of bromide occurrence are not clearly defined, but areas with relatively high bromide concentrations tend to be located in a triangular area near the community of Sunbeam, Florida, and along the St. Johns River throughout Duval County.

  12. Validation of an automated fluorescein method for determining bromide in water

    USGS Publications Warehouse

    Fishman, M. J.; Schroder, L.J.; Friedman, L.C.

    1985-01-01

    Surface, atmospheric precipitation and deionized water samples were spiked with ??g l-1 concentrations of bromide, and the solutions stored in polyethylene and polytetrafluoroethylene bottles. Bromide was determined periodically for 30 days. Automated fluorescein and ion chromatography methods were used to determine bromide in these prepared samples. Analysis of the data by the paired t-test indicates that the two methods are not significantly different at a probability of 95% for samples containing from 0.015 to 0.5 mg l-1 of bromide. The correlation coefficient for the same sets of paired data is 0.9987. Recovery data, except for the surface water samples to which 0.005 mg l-1 of bromide was added, range from 89 to 112%. There appears to be no loss of bromide from solution in either type of container.Surface, atmospheric precipitation and deionized water samples were spiked with mu g l** minus **1 concentrations of bromide, and the solutions stored in polyethylene and polytetrafluoroethylene bottles. Bromide was determined periodically for 30 days. Automated fluorescein and ion chromatography methods were used to determine bromide in these prepared samples. Analysis of the data by the paired t-test indicates that the two methods are not significantly different at a probability of 95% for samples containing from 0. 015 to 0. 5 mg l** minus **1 of bromide. The correlation coefficient for the same sets of paired data is 0. 9987. Recovery data, except for the surface water samples to which 0. 005 mg l** minus **1 of bromide was added, range from 89 to 112%. Refs.

  13. Orthogonal Cu- and Pd-Based Catalyst Systems for the O- and N-Arylation of Aminophenols

    PubMed Central

    Maiti, Debabrata; Buchwald, Stephen L.

    2009-01-01

    O- or N-arylated aminophenol products constitute a common structural motif in various potentially useful therapeutic agents and/or drug candidates. We have developed a complementary set of Cu- and Pd-based catalyst systems for the selective O- and N-arylation of unprotected aminophenols using aryl halides. Selective O-arylation of 3- and 4-aminophenols is achieved with copper-catalyzed methods employing picolinic acid or CyDMEDA, trans-N,N′-dimethyl-1,2-cyclohexanediamine, respectively, as the ligand. The selective formation of N-arylated products of 3- and 4-aminophenols can be obtained with BrettPhos precatalyst, a biarylmonophosphine-based palladium catalyst. 2-Aminophenol can be selectively N-arylated with CuI, although no system for the selective O-arylation could be found. Coupling partners with diverse electronic properties and a variety of functional groups can be selectively transformed under these conditions. PMID:19899753

  14. Nickel-Mediated Hydrogenolysis of C-O Bonds of Aryl Ethers: What Is the Source of the Hydrogen?

    PubMed Central

    Kelley, Paul; Lin, Sibo; Edouard, Guy; Day, Michael W.; Agapie, Theodor

    2012-01-01

    Mechanistic studies of the hydrogenolysis of aryl ethers by nickel were undertaken with (diphosphine)aryl methyl ethers. A Ni(0) complex containing Ni-arene interactions adjacent to the aryl-O bond was isolated. Heating led to aryl-O bond activation and generation of a nickel-aryl-methoxide complex. Formal β-H elimination from this species produced a nickel-aryl-hydride which can undergo reductive elimination in the presence of formaldehyde to generate a carbon monoxide adduct of Ni(0). The reported complexes map out a plausible mechanism of aryl ether hydrogenolysis catalyzed by nickel. Investigations of a previously reported catalytic system using isotopically labeled substrates are consistent with the mechanism proposed in the stoichiometric system, involving β-H elimination from a nickel alkoxide rather than cleavage of the Ni-O bond by H2. PMID:22394331

  15. History of ball bearings

    NASA Technical Reports Server (NTRS)

    Dowson, D.; Hamrock, B. J.

    1981-01-01

    The familiar precision rolling-element bearings of the twentieth century are products of exacting technology and sophisticated science. Their very effectiveness and basic simplicity of form may discourage further interest in their history and development. Yet the full story covers a large portion of recorded history and surprising evidence of an early recognition of the advantages of rolling motion over sliding action and progress toward the development of rolling-element bearings. The development of rolling-element bearings is followed from the earliest civilizations to the end of the eighteenth century. The influence of general technological developments, particularly those concerned with the movement of large building blocks, road transportation, instruments, water-raising equipment, and windmills are discussed, together with the emergence of studies of the nature of rolling friction and the impact of economic factors. By 1800 the essential features of ball and rolling-element bearings had emerged and it only remained for precision manufacture and mass production to confirm the value of these fascinating machine elements.

  16. Hybrid superconductor magnet bearings

    SciTech Connect

    Chu, W.

    1995-04-01

    Hybrid superconductor magnet bearings (HSMB`s) utilize high temperature superconductors (HTS`s) together with permanent magnets to form a frictionless interface between relatively rotating parts. They are low mass, stable, and do not incur expenditure of energy during normal operation. There is no direct physical contact between rotor and stator, and hence there is no wear and tear. However, just as any other applications of HTS`s, it requires a very cold temperature to function. Whereas this might be perceived as a disadvantage on earth, it is of no great concern in space or on the moon. To astronomers, the moon is an excellent site for an observatory, but the cold and dusty vacuum environment on the moon precludes the use of mechanical bearings on the telescope mounts. Furthermore, drive mechanisms with very fine steps, and hence bearings with extremely low friction are needed to track a star from the moon, because the moon rotates very slowly. All aspects considered, the HSMB is about the only candidate that fits in naturally. Here, the authors present a design for one such bearing, capable of supporting a telescope that weighs about 3 lbs on Earth.

  17. Hybrid superconductor magnet bearings

    NASA Astrophysics Data System (ADS)

    Chu, Wei-Kan

    1995-04-01

    Hybrid superconductor magnet bearings (HSMB's) utilize high temperature superconductors (HTS's) together with permanent magnets to form a frictionless interface between relatively rotating parts. They are low mass, stable, and do not incur expenditure of energy during normal operation. There is no direct physical contact between rotor and stator, and hence there is no wear and tear. However, just as any other applications of HTS's, it requires a very cold temperature to function. Whereas this might be perceived as a disadvantage on earth, it is of no great concern in space or on the moon. To astronomers, the moon is an excellent site for an observatory, but the cold and dusty vacuum environment on the moon precludes the use of mechanical bearings on the telescope mounts. Furthermore, drive mechanisms with very fine steps, and hence bearings with extremely low friction are needed to track a star from the moon, because the moon rotates very slowly. All aspects considered, the HSMB is about the only candidate that fits in naturally. Here, we present a design for one such bearing, capable of supporting a telescope that weighs about 3 lbs on Earth.

  18. Magnetic Bearings For Turbopumps

    NASA Technical Reports Server (NTRS)

    Meeks, Crawford R.; Mendez, Antonio J.

    1995-01-01

    Report presents study of feasibility of magnetic bearings in turbopumps. Liquid-oxygen turbopump in space shuttle main engine selected for study. Other potential applications include manned and unmanned spacecraft, gas turbines for commercial and military aircraft, turbomachinery for petro-chemical and gas operations, suspension systems for precise machinery, and precise pointing and tracking systems.

  19. The Teddy Bears' Disc.

    ERIC Educational Resources Information Center

    Laurillard, Diana

    1985-01-01

    Reports an evaluation of the Teddy Bear disc, an interactive videodisc developed at the Open University for a second-level course in metallurgy and materials technology. Findings from observation of students utilizing the videodisc are reviewed; successful design features and design problems are considered; and development costs are outlined. (MBR)

  20. Hybrid superconductor magnet bearings

    NASA Technical Reports Server (NTRS)

    Chu, Wei-Kan

    1995-01-01

    Hybrid superconductor magnet bearings (HSMB's) utilize high temperature superconductors (HTS's) together with permanent magnets to form a frictionless interface between relatively rotating parts. They are low mass, stable, and do not incur expenditure of energy during normal operation. There is no direct physical contact between rotor and stator, and hence there is no wear and tear. However, just as any other applications of HTS's, it requires a very cold temperature to function. Whereas this might be perceived as a disadvantage on earth, it is of no great concern in space or on the moon. To astronomers, the moon is an excellent site for an observatory, but the cold and dusty vacuum environment on the moon precludes the use of mechanical bearings on the telescope mounts. Furthermore, drive mechanisms with very fine steps, and hence bearings with extremely low friction are needed to track a star from the moon, because the moon rotates very slowly. All aspects considered, the HSMB is about the only candidate that fits in naturally. Here, we present a design for one such bearing, capable of supporting a telescope that weighs about 3 lbs on Earth.

  1. Composite Bear Canister

    NASA Technical Reports Server (NTRS)

    Chung, W. Richard; Jara, Steve; Suffel, Susan

    2003-01-01

    To many national park campers and mountain climbers saving their foods in a safe and unbreakable storage container without worrying being attacked by a bear is a challenging task. In some parks, the park rangers have mandated that park visitors rent a bear canister for their food storage. Commercially available bear canisters are made of ABS plastic, weigh 2.8 pounds, and have a 180 cubic inch capacity for food storage. A new design with similar capacity was conducted in this study to reduce its weight and make it a stiffer and stronger canister. Two prototypes incorporating carbon prepreg with and without honeycomb constructions were manufactured using hand lay-up and vacuum bag forming techniques. A 6061-T6-aluminum ring was machined to dimensions in order to reinforce the opening area of the canister. Physical properties (weight and volume) along with mechanical properties (flexural strength and specific allowable moment) of the newly fabricated canisters are compared against the commercial ones. The composite canister weighs only 56% of the ABS one can withstand 9 times of the force greater. The advantages and limitations of using composite bear canisters will be discussed in the presentation.

  2. Optimal Synchronizability of Bearings

    NASA Astrophysics Data System (ADS)

    Araújo, N. A. M.; Seybold, H.; Baram, R. M.; Herrmann, H. J.; Andrade, J. S., Jr.

    2013-02-01

    Bearings are mechanical dissipative systems that, when perturbed, relax toward a synchronized (bearing) state. Here we find that bearings can be perceived as physical realizations of complex networks of oscillators with asymmetrically weighted couplings. Accordingly, these networks can exhibit optimal synchronization properties through fine-tuning of the local interaction strength as a function of node degree [Motter, Zhou, and Kurths, Phys. Rev. E 71, 016116 (2005)PLEEE81539-3755]. We show that, in analogy, the synchronizability of bearings can be maximized by counterbalancing the number of contacts and the inertia of their constituting rotor disks through the mass-radius relation, m˜rα, with an optimal exponent α=α× which converges to unity for a large number of rotors. Under this condition, and regardless of the presence of a long-tailed distribution of disk radii composing the mechanical system, the average participation per disk is maximized and the energy dissipation rate is homogeneously distributed among elementary rotors.

  3. Magnetically leviated superconducting bearing

    DOEpatents

    Weinberger, Bernard R.; Lynds, Jr., Lahmer

    1993-01-01

    A magnetically levitated superconducting bearing includes a magnet (2) mounted on a shaft (12) that is rotatable around an axis of rotation and a Type II superconductor (6) supported on a stator (14) in proximity to the magnet (2). The superconductor (6) is positioned so that when it is cooled to its superconducting state in the presence of a magnetic field, it interacts with the magnet (2) to produce an attractive force that levitates the magnet (2) and supports a load on the shaft (12). The interaction between the superconductor (6) and magnet(2) also produces surface screening currents (8) that generate a repulsive force perpendicular to the load. The bearing also has means for maintaining the superconductor at a temperature below its critical temperature (16, 18). The bearing could also be constructed so the magnet (2) is supported on the stator (14) and the superconductor (6) is mounted on the shaft (12). The bearing can be operated by cooling the superconductor (6) to its superconducting state in the presence of a magnetic field.

  4. Lubricant effects on bearing life

    NASA Technical Reports Server (NTRS)

    Zaretsky, Erwin V.

    1986-01-01

    Lubricant considerations for rolling-element bearings have within the last two decades taken on added importance in the design and operation of mechanical systems. The phenomenon which limits the useful life of bearings is rolling-element or surface pitting fatigue. The elastohydrodynamic (EHD) film thickness which separates the ball or roller surface from those of the raceways of the bearing directly affects bearing life. Chemical additives added to the lubricant can also significantly affect bearings life and reliability. The interaction of these physical and chemical effects is important to the design engineer and user of these systems. Design methods and lubricant selection for rolling-element bearings are presented and discussed.

  5. Magnetic-Bearing Test Fixture

    NASA Technical Reports Server (NTRS)

    Groom, Nelson J.; Poole, William L.

    1991-01-01

    Microcomputer-controlled magnetic-bearing test fixture used to develop approaches to design of controls for magnetic bearing actuators designed and constructed. Includes load cells connected to bar, in turn, connected through screw positioners to geared drive motors. Position of equivalent suspended element sensed by position sensors and controlled by drive motors. Provides control of gap in magnetic bearing and of current in electromagnet coil. Measurements made include magnetic-bearing gaps, magnetic flux in bearing gaps, and bearing forces. Approaches to linearization and control developed by use of fixture applicable to wide range of small-gap suspension systems.

  6. Flexure Bearing Reduces Startup Friction

    NASA Technical Reports Server (NTRS)

    Clingman, W. Dean

    1991-01-01

    Design concept for ball bearing incorporates small pieces of shim stock, wire spokes like those in bicycle wheels, or other flexing elements to reduce both stiction and friction slope. In flexure bearing, flexing elements placed between outer race of ball bearing and outer ring. Elements flex when ball bearings encounter small frictional-torque "bumps" or even larger ones when bearing balls encounter buildups of grease on inner or outer race. Flexure of elements reduce high friction slopes of "bumps", helping to keep torque between outer ring and inner race low and more nearly constant. Concept intended for bearings in gimbals on laser and/or antenna mirrors.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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. PMID:27317802

  9. Binding studies using Pichia pastoris expressed human aryl hydrocarbon receptor and aryl hydrocarbon receptor nuclear translocator proteins.

    PubMed

    Zheng, Yujuan; Xie, Jinghang; Huang, Xin; Dong, Jin; Park, Miki S; Chan, William K

    2016-06-01

    The aryl hydrocarbon receptor (AHR) is a transcription factor which activates gene transcription by binding to its corresponding enhancer as the heterodimer, which is consisted of AHR and the aryl hydrocarbon receptor nuclear translocator (ARNT). Human AHR can be rather difficult to study, when compared among the AHR of other species, since it is relatively unstable and less sensitive to some ligands in vitro. Overexpression of human AHR has been limited to the baculovirus expression, which is costly and tedious due to the need of repetitive baculovirus production. Here we explored whether we could generate abundant amounts of human AHR and ARNT in a better overexpression system for functional study. We observed that human AHR and ARNT can be expressed in Pichia pastoris with yields that are comparable to the baculovirus system only if their cDNAs are optimized for Pichia expression. Fusion with a c-myc tag at their C-termini seems to increase the expression yield. These Pichia expressed proteins can effectively heterodimerize and form the ternary AHR/ARNT/enhancer complex in the presence of β-naphthoflavone or kynurenine. Limited proteolysis using thermolysin can be used to study the heterodimerization of these human AHR and ARNT proteins. PMID:26923060

  10. An aryl dioxygenase shows remarkable double dioxygenation capacity for diverse bis-aryl compounds, provided they are carbocyclic.

    PubMed

    Overwin, Heike; González, Myriam; Méndez, Valentina; Seeger, Michael; Wray, Victor; Hofer, Bernd

    2016-09-01

    The bacterial dioxygenation of mono- or polycyclic aromatic compounds is an intensely studied field. However, only in a few cases has the repeated dioxygenation of a substrate possessing more than a single aromatic ring been described. We previously characterized the aryl-hydroxylating dioxygenase BphA-B4h, an artificial hybrid of the dioxygenases of the biphenyl degraders Burkholderia xenovorans LB400 and Pseudomonas sp. strain B4-Magdeburg, which contains the active site of the latter enzyme, as an exceptionally powerful biocatalyst. We now show that this dioxygenase possesses a remarkable capacity for the double dioxygenation of various bicyclic aromatic compounds, provided that they are carbocyclic. Two groups of biphenyl analogues were examined: series A compounds containing one heterocyclic aromatic ring and series B compounds containing two homocyclic aromatic rings. Whereas all of the seven partially heterocyclic biphenyl analogues were solely dioxygenated in the homocyclic ring, four of the six carbocyclic bis-aryls were converted into ortho,meta-hydroxylated bis-dihydrodiols. Potential reasons for failure of heterocyclic dioxygenations are discussed. The obtained bis-dihydrodiols may, as we also show here, be enzymatically re-aromatized to yield the corresponding tetraphenols. This opens a way to a range of new polyphenolic products, a class of compounds known to exert multiple biological activities. Several of the obtained compounds are novel molecules. PMID:27147529

  11. Aldol Reactions of Axially Chiral 5-Methyl-2-(o-aryl)imino-3-(o-aryl)-thiazolidine-4-ones.

    PubMed

    Erol Gunal, Sule; Dogan, Ilknur

    2016-01-01

    Axially chiral 5-methyl-2-(o-aryl)imino-3-(o-aryl)-thiazolidine-4-ones have been subjected to aldol reactions with benzaldehyde to produce secondary carbinols which have been found to be separable by HPLC on a chiral stationary phase. Based on the reaction done on a single enantiomer resolved via a chromatographic separation from a racemic mixture of 5-methyl-2-(α-naphthyl)imino-3-(α-naphthyl)-thiazolidine-4-one by HPLC on a chiral stationary phase, the aldol reaction was shown to proceed via an enolate intermediate. The axially chiral enolate of the thiazolidine-4-one was found to shield one face of the heterocyclic ring rendering face selectivity with respect to the enolate. The selectivities observed at C-5 of the ring varied from none to 11.5:1 depending on the size of the ortho substituent. Although the aldol reaction proceeded with a lack of face selectivity with respect to benzaldehyde, recrystallization returned highly diastereomerically enriched products. PMID:27322237

  12. Removal of bromide by aluminium chloride coagulant in the presence of humic acid.

    PubMed

    Ge, Fei; Shu, Haimin; Dai, Youzhi

    2007-08-17

    Bromide can form disinfection by-products (DBPs) in drinking water disinfection process, which have adverse effects on human health. Using aluminium chloride as a model coagulant, removal of bromide by coagulation was investigated in the absence or presence of humic acid (HA) in synthetic water and then was conducted in raw water. Results demonstrated that in synthetic water, 93.3-99.2% removal efficiency of bromide was achieved in the absence of HA with 3-15 mg/L coagulant, while 78.4-98.4% removal efficiency of bromide was obtained in the presence of HA with the same coagulant dosage and 86.8-98.8% HA was removed simultaneously. Bromide in raw water was removed 87.0% with 15 mg/L coagulant. HA apparently reduced the removal of bromide with low coagulant dosage or at high pH, while minor influence on removal of bromide was observed with high coagulant dosage or at low pH. Thus, bromide could be reduced effectively by enhanced coagulation in drinking water treatment. PMID:17289257

  13. Solid phase microextraction for active or passive sampling of methyl bromide during fumigations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The high diffusivity and volatility of methyl bromide make it an ideal compound for Solid Phase Micro Extraction (SPME)-based sampling of air prior to gas-chromatographic quantifications. SPME fibers can be used as active methyl bromide samplers, with high capacities and an equilibrium time of 1-2 m...

  14. Enthalpies of complex formation of boron and aluminum bromides with organic bases of high donor power

    SciTech Connect

    Grigor-ev, A.A.; Kondrat'ev, Y.V.; Suvorov, A.V.

    1986-11-20

    By the calorimetric method enthalpies of complex formation were determined for boron and aluminum bromides with piperidine and hexamethylphosphoric triamide in benzene solutions and for boron bromide with pyridine in dichloroethane, and also enthalpies of solution were determined for BBr/sub 3/ and the adducts AlBr/sub 3/ x PPy and BBr/sub 2/ x Py in benzene and pyridine.

  15. Destruction of methyl bromide sorbed to activated carbon by thiosulfate and electrolysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide is widely used as a fumigant for post-harvest and quarantine uses at port facilities due to the low treatment times required, but it is vented to the atmosphere after its use. Due to the potential contributions of methyl bromide to stratospheric ozone depletion, technologies for the c...

  16. Palladium-Catalyzed Selective α-Alkenylation of Pyridylmethyl Ethers with Vinyl Bromides.

    PubMed

    Yang, Xiaodong; Kim, Byeong-Seon; Li, Minyan; Walsh, Patrick J

    2016-05-20

    An efficient palladium-catalyzed α-alkenylation of pyridylmethyl ethers with vinyl bromides is presented. A Pd/NIXANTPHOS-based catalyst system enables a mild and chemoselective coupling between a variety of pyridylmethyl ethers and vinyl bromides in good to excellent yields. Under the mild conditions, β,γ-unsaturated products are obtained without isomerization or Heck byproducts observed. PMID:27160421

  17. 77 FR 48153 - Protection of Stratospheric Ozone: Request for Methyl Bromide Critical Use Exemption Applications...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-13

    ...On May 17, 2012, the EPA published a notice in the Federal Register requesting applications for the Critical Use Exemption from the phaseout of methyl bromide for 2015. On August 3, 2012, EPA received a letter from methyl bromide stakeholders requesting an extension to the August 15, 2012 deadline for submitting Critical Use Exemption applications. The letter requested a deadline of August 29,......

  18. 76 FR 34700 - Protection of Stratospheric Ozone: Request for Methyl Bromide Critical Use Exemption Applications...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-06-14

    ... AGENCY Protection of Stratospheric Ozone: Request for Methyl Bromide Critical Use Exemption Applications... exemption from the phaseout of methyl bromide for 2014. Critical use exemptions last only one year. All... interested parties to provide EPA with new data on the technical and economic feasibility of methyl...

  19. 75 FR 41177 - Protection of Stratospheric Ozone: Request for Methyl Bromide Critical Use Exemption Applications...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-07-15

    ... AGENCY Protection of Stratospheric Ozone: Request for Methyl Bromide Critical Use Exemption Applications... exemption from the phaseout of methyl bromide for 2013. Critical use exemptions last only one year. All... interested parties to provide EPA with new data on the technical and economic feasibility of methyl...

  20. In vivo and in vitro bromide equilibration time course in adults and sample handling effect

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Extracellular water is a major component of body weight and an indicator of nutritional status. Bromide dilution has been used to estimate this compartment. Recent evidence, however, indicates that the bromide equilibration time is longer than the 4 hr assumed in many studies. The aim of this stud...

  1. Methyl bromide fumigation of packed table grapes: Effect of shipping box on gas concentrations and phytotoxicity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Current methyl bromide schedules for table grapes to control mealybugs are approved for fruit packed in Toyon Kraft Veneer (TKV) boxes. The question arose concerning equivalence of exposure to methyl bromide if an Extruded Polystyrene (EPS) box was used in lieu of the TKV box for table grapes being ...

  2. Performance of soil solarization and methyl bromide in sites infested with root-knot nematodes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soil fumigation with methyl bromide has been the principal means of managing soil-borne pest problems on ornamental crops in the United States for many years. Interest in effective alternatives increased during the phase-out of methyl bromide, and will become more acute as existing stocks are deple...

  3. Synthesis of C-Homoaporphines via Microwave-Assisted Direct Arylation

    PubMed Central

    Chaudhary, Sandeep; Harding, Wayne W.

    2010-01-01

    Representatives of the C-homoaporphine class of alkaloids have shown interesting biological activities. To date the synthesis of these molecules has never been attempted via a direct arylation strategy. We report herein the first Pd-mediated intramolecular direct arylation in the synthesis of C-homoaporphines via the use of microwaves. Use of tricyclohexylphosphine tetrafluoroborate as ligand gave good percentage conversions and suppressed competing debromination with the substrates evaluated. This arylation strategy should be broadly useful in the synthesis of C-homoaporphine alkaloids as demonstrated herein in the synthesis of (±)-homonantenine. PMID:21399710

  4. STILLE CROSS-COUPLING REACTIONS OF ARYL MESYLATES AND TOSYLATES USING A BIARYLPHOSPHINE BASED CATALYST SYSTEM‡

    PubMed Central

    Naber, John R.; Fors, Brett P.; Wu, Xiaoxing; Gunn, Jonathon

    2013-01-01

    A catalyst system for the Stille cross-coupling reactions of aryl mesylates and tosylates is reported. Using the combination of Pd(OAc)2, XPhos, and CsF in t-BuOH an array of aryl and heteroaryl sulfonates were successfully employed in these reactions. Morever, heteroarylstannanes, such as furyl, thiophenyl, and N-methylpyrrole, which are often prone to decomposition, were efficiently coupled under these conditions. Ortho-substitution on the stannane coupling partner was well tolerated; however, the presence of ortho substituents on the aryl sulfonates greatly reduced the proficiency of these reactions. PMID:23596345

  5. Manganese(IV)-mediated hydroperoxyarylation of alkenes with aryl hydrazines and dioxygen from air.

    PubMed

    Kindt, Stephanie; Jasch, Hannelore; Heinrich, Markus R

    2014-05-19

    We report a new carbooxygenation-type version of the Meerwein arylation in which the introduction of oxygen is achieved by using dioxygen from the air. In this way, hydroperoxides were obtained from activated as well as non-activated alkenes by oxidizing aryl hydrazines with manganese dioxide. The best results were obtained with α-substituted acrylates. Importantly, the aryl hydrazine has to be added slowly to the reaction mixture to allow sufficient uptake of dioxygen from the air. Competition and labeling experiments revealed hydroperoxyl radicals as novel oxygen-centered radical scavengers. PMID:24737215

  6. Mechanistic Considerations in the Synthesis of 2-Aryl-Indole Analogues under Bischler-Mohlau Conditions

    PubMed Central

    MacDonough, Matthew T.; Shi, Zhe; Pinney, Kevin G.

    2015-01-01

    Mechanistic insight into the pathway of the Bischler-Mohlau indole formation reaction is provided by isotopic labeling utilizing judicious incorporation of a 13C atom within the α-bromoacetophenone analogue reactant. The resulting rearranged 2-aryl indole, isolated as the major product, located the 13C isotope label at the methine carbon of the fused five-membered heterocyclic ring, which suggested that the mechanistic pathway of cyclization, in this specific example, required two equivalents of the aniline analogue reactant partner and proceeded through an imine intermediate rather than by direct formation of the corresponding 3-aryl indole accompanied by a concomitant 1,2-aryl shift rearrangement. PMID:26973358

  7. Classifying the Basic Parameters of Ultraviolet Copper Bromide Laser

    NASA Astrophysics Data System (ADS)

    Gocheva-Ilieva, S. G.; Iliev, I. P.; Temelkov, K. A.; Vuchkov, N. K.; Sabotinov, N. V.

    2009-10-01

    The performance of deep ultraviolet copper bromide lasers is of great importance because of their applications in medicine, microbiology, high-precision processing of new materials, high-resolution laser lithography in microelectronics, high-density optical recording of information, laser-induced fluorescence in plasma and wide-gap semiconductors and more. In this paper we present a statistical study on the classification of 12 basic lasing parameters, by using different agglomerative methods of cluster analysis. The results are based on a big amount of experimental data for UV Cu+ Ne-CuBr laser with wavelengths 248.6 nm, 252.9 nm, 260.0 nm and 270.3 nm, obtained in Georgi Nadjakov Institute of Solid State Physics, Bulgarian Academy of Sciences. The relevant influence of parameters on laser generation is also evaluated. The results are applicable in computer modeling and planning the experiments and further laser development with improved output characteristics.

  8. Unveiling Residual Molecular Binding in Triply Charged Hydrogen Bromide

    SciTech Connect

    Penent, F.; Lablanquie, P.; Palaudoux, J.; Gamblin, G.; Carniato, S.; Andric, L.; Hikosaka, Y.; Ito, K.

    2011-03-11

    We present an experimental and theoretical study of triply charged hydrogen bromide ions formed by photoionization of the inner 3d shell of Br. The experimental results, obtained by detecting the 3d photoelectron in coincidence with the two subsequent Auger electrons, are analyzed using calculated potential energy curves of HBr{sup 3+}. The competition between the short-range chemical binding potential and the Coulomb repulsion in the dissociative process is shown. Two different mechanisms are observed for double Auger decay: one, a direct process with simultaneous ejection of two Auger electrons to final HBr{sup 3+} ionic states and the other, a cascade process involving double Auger decay characterized by the autoionization of Br*{sup +} ion subsequent to the HBr{sup 2+} fragmentation.

  9. Thermal parameters of carbon nanotubes and potassium bromide composites

    NASA Astrophysics Data System (ADS)

    Depriester, Michael; Hus, Philippe; Sahraoui, Abdelhak Hadj; Roussel, Frédérick

    2011-04-01

    Photothermal radiometry is employed to investigate the thermal parameters (diffusivity, effusivity, conductivity, and heat capacity) of carbon nanotubes [single-walled (SWNT) or multiple-walled (MWNT)] and potassium bromide (KBr) pressed pellets as a function of SWNT or MWNT mass fraction. A significant enhancement of the thermal conductivity for carbon nanotubes (CNTs) contents up to 2 wt. % was observed. Above 3 wt. % CNT, a morphological transition from a compacted to an unconsolidated granular media occurs leading to a sharp decrease of the thermal conductivity (k) caused by the presence of air interfaces. A geometrical model based on interpenetrating continua is applied to describe the unusual evolution of the thermal conductivity. The behavior of k is also discussed in regard to the latest theoretical reports.

  10. Timing resolution measurements of a 3 in. lanthanum bromide detector

    NASA Astrophysics Data System (ADS)

    Galli, L.; De Gerone, M.; Dussoni, S.; Nicolò, D.; Papa, A.; Tenchini, F.; Signorelli, G.

    2013-08-01

    Cerium-doped lanthanum bromide (LaBr3:Ce) is a scintillator that presents very good energy and timing resolutions and it is a perfect candidate for photon detector in future experiments to search for lepton flavor violation as in μ → eγ or μ → e conversion. While energy resolution was thoroughly investigated, timing resolution at several MeV presents some experimental challenge. We measured the timing resolution of a 3 in.×3 in. cylindrical LaBr3(Ce) crystal versus few reference detectors by means of a nuclear reaction from a Cockcroft-Walton accelerator that produces coincident γ-rays in the 4.4-11.6 MeV range. Preliminary results allow us to extrapolate the properties of a segmented γ-ray detector in the 50-100 MeV range.

  11. Tiotropium Bromide in Chronic Obstructive Pulmonary Disease and Bronchial Asthma

    PubMed Central

    Alvarado-Gonzalez, Alcibey; Arce, Isabel

    2015-01-01

    Inhaled bronchodilators are the mainstay of pharmacological treatment for stable chronic obstructive pulmonary disease (COPD), including β2-agonists and muscarinic antagonists. Tiotropium bromide, a long-acting antimuscarinic bronchodilator (LAMA), is a treatment choice for moderate-to-severe COPD; its efficacy and safety have been demonstrated in recent trials. Studies also point to a beneficial role of tiotropium in the treatment of difficult-to-control asthma and a potential function in the asthma-COPD overlap syndrome (ACOS). Combination of different bronchodilator molecules and addition of inhaled corticosteroids are viable therapeutic alternatives. A condensation of the latest trials and the rationale behind these therapies will be presented in this article. PMID:26491494

  12. Simultaneous electrochemical determination of three sunscreens using cetyltrimethylammonium bromide.

    PubMed

    Cardoso, Juliano Carvalho; Armondes, Bruna Milca Lenzi; Ferreira, João Bosco Galindo Júnior e Valdir Souza

    2008-05-01

    This paper proposes a methodology based on electrochemical reduction for the simultaneous determination of three sunscreen agents, namely 4-methylbenzylidene camphor (MBC), benzophenone-3 (BENZO) and 2-ethylhexyl-4-methoxycinnamate (EHMC) by differential-pulse polarography (DPP). The highest peak currents and optimal separation of reduction peaks were obtained by using a supporting electrolyte consisted of Britton-Robinson buffer-methanol (8:2) solution at pH 4.0 and cationic surfactant 3.0 x 10(-4)mol L(-1) cetyltrimethylammonium bromide (CTAB). The methodology was validated using four commercial sunscreen preparation as a sample and the results showed high recovery rates. The efficiency of the proposed methodology was demonstrated by comparing the results obtained by DPP with those obtained by the high-performance liquid chromatography (HPLC) method. PMID:18093812

  13. Absorption of Water Vapor into Aqueous Solutions of Lithium Bromide

    NASA Astrophysics Data System (ADS)

    Takahara, Tsutomu; Hayashida, Atsushi; Yabase, Hajime; Hihara, Eiji; Saito, Takamoto

    Heat and mass transfer processes are experimentally investigated for the case of water absorption into aqueous solutions of lithium bromide flowing over a flat plate. Variables considered are inlet solution flow rate,concentration of an additive,and inclination angle of the plate. The use of 2-ethyl-1-hexanol as an additive results in about a four to five fold improvement in absorption rate. The occurrence of surface distrbances dose not has a direct connection with the solubility limit of the additive. The cause of the surface disturbances in the presence of additives is investigated through experiments for pool absorption By regulating the flow of water vapor,the form of the Marangoni convection can be controlled. A qualitative discussion of addictives in the role of inducing surface disturbances is presented.

  14. Location of Bromide Ions in Tetragonal Lysozyme Crystals

    NASA Technical Reports Server (NTRS)

    Lim, Kap; Nadarajah, Arunan; Forsythe, Elizabeth L.; Pusey, Marc L.

    1998-01-01

    Anions have been shown to play a dominant role in the crystallization of chicken egg white lysozyme from salt solutions. Previous studies employing X-ray crystallography had found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystal grown in bromide and chloride solutions. Five possible anion binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four of these sites corresponded to four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion binding sites in lysozyme remain unchanged, even when different anions and different crystal forms of lysozyme are employed.

  15. Detecting Arbitrary DNA Mutations Using Graphene Oxide and Ethidium Bromide.

    PubMed

    Huang, Jiahao; Wang, Zhenyu; Kim, Jang-Kyo; Su, Xuefen; Li, Zhigang

    2015-12-15

    We propose a simple and fast method for detecting arbitrary DNA mutations. Single-stranded DNA probes labeled with fluorescein amidite (FAM-ssDNA), ethidium bromide (EB), and graphene oxide (GO) are employed in the sensing system. The detection is achieved in two steps. In the first step, the sensing system contains FAM-ssDNA probes and EB molecules. It exhibits different fluorescence emissions in the presence of perfectly matched, mismatched, and random DNA sequences. With the addition of GO in the second step, the fluorescence signal for perfectly matched and random DNA does not vary greatly, which, however, experiences a significant change for mismatched DNA targets. The signal ratio before and after the addition of GO can clearly distinguish mutations from normal and random DNA sequences. The detection method works well regardless of the mutation positions and only requires "mix-and-detect" steps, which are completed within 15 min. PMID:26559174

  16. N-(2-Bromo­benz­yl)cinchoninium bromide

    PubMed Central

    Skórska-Stania, Agnieszka; Jezierska-Zięba, Magdalena; Kąkol, Barbara; Fedoryński, Michał; Oleksyn, Barbara J.

    2012-01-01

    The title compound {systematic name: 1-(2-bromo­benz­yl)-5-ethenyl-2-[hy­droxy(quinolin-4-yl)meth­yl]-1-aza­bicyclo­[2.2.2]octan-1-ium bromide}, C26H28BrN2O+·Br−, is a chiral quater­nary ammonium salt of one of the Cinchona alkaloids. The planes of the quinoline and of the bromo­benzyl substituent are inclined to one another by 9.11 (9)°. A weak intra­molecular C—H⋯O hydrogen bond occurs. The crystal structure features strong O—H⋯Br hydrogen bonds and weak C—H⋯Br inter­actions. PMID:22969676

  17. Error Evaluation of Methyl Bromide Aerodynamic Flux Measurements

    USGS Publications Warehouse

    Majewski, M.S.

    1997-01-01

    Methyl bromide volatilization fluxes were calculated for a tarped and a nontarped field using 2 and 4 hour sampling periods. These field measurements were averaged in 8, 12, and 24 hour increments to simulate longer sampling periods. The daily flux profiles were progressively smoothed and the cumulative volatility losses increased by 20 to 30% with each longer sampling period. Error associated with the original flux measurements was determined from linear regressions of measured wind speed and air concentration as a function of height, and averaged approximately 50%. The high errors resulted from long application times, which resulted in a nonuniform source strength; and variable tarp permeability, which is influenced by temperature, moisture, and thickness. The increase in cumulative volatilization losses that resulted from longer sampling periods were within the experimental error of the flux determination method.

  18. Rejection of Bromide and Bromate Ions by a Ceramic Membrane

    PubMed Central

    Moslemi, Mohammadreza; Davies, Simon H.; Masten, Susan J.

    2012-01-01

    Abstract Effects of pH and the addition of calcium chloride (CaCl2) on bromate (BrO3−) and bromide (Br−) rejection by a ceramic membrane were investigated. Rejection of both ions increased with pH. At pH 8, the rejection of BrO3− and Br− was 68% and 63%, respectively. Donnan exclusion appears to play an important role in determining rejection of BrO3− and Br−. In the presence of CaCl2, rejection of BrO3− and Br− ions was greatly reduced, confirming the importance of electrostatic interactions in determining rejection of BrO3− and Br−. The effect of Ca2+ is so pronounced that in most natural waters, rejection of both BrO3− and Br− by the membrane would be extremely small. PMID:23236251

  19. Action of pinaverium bromide, a calcium-antagonist, on gastrointestinal motility disorders.

    PubMed

    Christen, M O

    1990-01-01

    1. The evidence reviewed here indicates that pinaverium bromide (Dicetel) relaxes gastrointestinal (GI) structures primarily by inhibiting Ca2+ influx through potential-dependent channels of surface membranes of smooth muscle cells. 2. The in vivo selectivity of pinaverium bromide for the GI tract appears to be due mainly to its pharmacokinetic properties. Because of its low absorption (typical for quaternary ammonium compounds) and marked hepatobiliary excretion, most of the orally-administered dose of pinaverium bromide remains in the GI tract. 3. Orally-administered pinaverium bromide does not elicit adverse cardiovascular side-effects at doses that effectively relieve GI spasm, pain, transit disturbances and other symptoms related to motility disorders. 4. Pinaverium bromide is the only Ca2(+)-antagonist with known therapeutic efficacy in the treatment of irritable bowel syndrome and certain other functional intestinal disorders. PMID:2177709

  20. Particle migration through sealed bearings

    SciTech Connect

    Sundvold, P.D.

    1993-08-01

    Tests were performed to determine the ability of various types of shielded bearings to isolate particulate from a clean environment in support of the Direct Optical Initiation (DOI) program. In the DOI firing system, a stronglink mechanism will share the same environment with a high-powered laser which needs uncontaminated optics to perform properly. Two commercially available shielded and sealed bearings were tested along with a sealed bearing designed at Allied Signal Inc., Kansas City Division (KCD). The KCD-designed bearing proved to be the best barrier, but the torque required to function the bearing was magnitudes above the commercial bearings. The commercial sealed bearing was an effective barrier, allowing a small fraction of particles to migrate through, and had a relatively low running torque. The shielded bearing was not acceptable as a particle barrier.

  1. Vygotsky and the Three Bears

    ERIC Educational Resources Information Center

    Kulczewski, Peggy

    2004-01-01

    Peggy Kulczewski, a kindergarten classroom teacher, remembers the day when students enjoyed a story she told them from the book "The Three Bears". The students' discussion about comparison of the bears was very helpful to the whole group.

  2. Magnetic bearings grow more attractive

    SciTech Connect

    Not Available

    1993-10-01

    Advances in materials and electronics have enabled designers to devise simpler, smaller magnetic bearings. As a result, costs have dropped, widening the applications for these very-low-friction devices. Avcon (Advanced Controls Technology) has patented a permanent-magnet bias actively controlled bearing. Here high-energy rare earth permanent-magnet materials supply the basic bearing load levitation, while servo-driven electromagnets generate stabilization and centering forces for motion contol. Previous heavy-duty magnetic bearings used electromagnets entirely for suspension and control, which led to large bearings and control systems with higher power requirements. Avcon has developed several types of permanent-magnet bias bearings. The simplest is the radial repulsion bearing. Avcon's homopolar permanent-magnet bias active bearing is the most versatile of the company's designs.

  3. Comparative mobility of sulfonamides and bromide tracer in three soils

    USGS Publications Warehouse

    Kurwadkar, S.T.; Adams, C.D.; Meyer, M.T.; Kolpin, D.W.

    2011-01-01

    In animal agriculture, sulfonamides are one of the routinely used groups of antimicrobials for therapeutic and sub-therapeutic purposes. It is observed that, the animals when administered the antimicrobials, often do not completely metabolize them; and excrete the partially metabolized forms into the environment. Due to the continued use of antimicrobials and disposal of untreated waste, widespread occurrence of partially metabolized antimicrobials in aquatic and terrestrial environments has been reported in various scientific journals. In this research, the mobility of two sulfonamides - sulfamethazine (SMN), sulfathiazole (STZ) and a conservative bromide tracer was investigated in three soils collected from regions in the United States with large number of concentrated animal-feed operations. Results of a series of column studies indicate that the mobility of these two sulfonamides was dependent on pH, soil charge density, and contact time. At low pH and high charge density, substantial retention of sulfonamides was observed in all three soils investigated, due to the increased fraction of cationic and neutral forms of the sulfonamides. Conversely, enhanced mobility was observed at high pH, where the sulfonamides are predominantly in the anionic form. The results indicate that when both SMN and STZ are predominantly in anionic forms, their mobility approximates the mobility of a conservative bromide tracer. This observation is consistent for the mobility of both SMN and STZ individually, and also in the presence of several other antimicrobials in all three soils investigated. Higher contact time indicates lower mobility due to increased interaction with soil material. ?? 2011.

  4. Cinchona Alkaloid Squaramide-Catalyzed Asymmetric Michael Addition of α-Aryl Isocyanoacetates to β-Trifluoromethylated Enones and Its Applications in the Synthesis of Chiral β-Trifluoromethylated Pyrrolines.

    PubMed

    Zhao, Mei-Xin; Zhu, Hui-Kai; Dai, Tong-Lei; Shi, Min

    2015-11-20

    Cinchona alkaloid squaramide can effectively catalyze the asymmetric Michael addition of α-aryl isocyanoacetates to β-trifluoromethylated enones, affording the corresponding adducts with an adjacent chiral tertiary carbon center bearing a CF3 group and a quaternary carbon center in moderate to good yields along with excellent stereoselectivities. The adduct can be easily transformed into biologically attractive chiral β-trifluoromethylated pyrroline carboxylate in high yield via an isocyano group hydrolysis/cyclization/dehydration cascade reaction by treating with acid. The one-pot enantioselective Michael addition/isocyano group hydrolysis/cyclization/dehydration sequential protocol has also been investigated. PMID:26523421

  5. 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.

    PubMed

    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

    2007-10-01

    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. PMID:17803291

  6. Unusual aryl-porphyrin rotational barriers in peripherally crowded porphyrins.

    SciTech Connect

    Shyr, David C.; Dooley, Neal R.; Haddad, Raid Edward; Shelnutt, John Allen; Muzzi, Cinzia M.; Ma, Jian-Guo; Olmstead, Marilyn M.; Jaquinod, Laurent A.; Nurco, Daniel J.; Medforth, Craig John; Smith, Kevin M.

    2003-06-01

    Previous studies of 5,10,15,20-tetraarylporphyrins have shown that the barrier for meso aryl-porphyrin rotation ({Delta}G{sub ROT}) varies as a function of the core substituent M and is lower for a small metal (M = Ni) compared to a large metal (M = Zn) and for a dication (M 4H{sup 2+}) versus a free base porphyrin (M = 2H). This has been attributed to changes in the nonplanar distortion of the porphyrin ring and the deformability of the macrocycle caused by the core substituent. In the present work, X-ray crystallography, molecular mechanics (MM) calculations, and variable temperature (VT) {sup 1}H NMR spectroscopy are used to examine the relationship between the aryl-porphyrin rotational barrier and the core substituent M in some novel 2,3,5,7,8,10,12,13,15,17,18,20-dodecaarylporphyrins (DArPs), and specifically in some 5,10,15,20-tetraaryl-2,3,7,8,12,13,17,18-octaphenylporphyrins (TArOPPs), where steric crowding of the peripheral groups always results in a very nonplanar macrocycle. X-ray structures of DArPs indicate differences in the nonplanar conformation of the macrocycle as a function of M, with saddle conformations being observed for M = Zn, 2H or M = 4H{sup 2+} and saddle and/or ruffle conformations for M = Ni. VT NMR studies show that the effect of protonation in the TArOPPs is to increase {Delta}G{sub ROT}, which is the opposite of the effect seen for the TArPs, and MM calculations also predict a strikingly high barrier for the TArOPPs when M = 4H{sup 2+}. These and other findings suggest that the aryl-porphyrin rotational barriers in the DArPs are closely linked to the deformability of the macrocycle along a nonplanar distortion mode which moves the substituent being rotated out of the porphyrin plane.

  7. Externally Pressurized Journal Gas Bearings

    NASA Technical Reports Server (NTRS)

    Laub, John H.

    1959-01-01

    Externally pressurized gas-lubricated bearings with multiple orifice feed are investigated. An analytical treatment is developed for a semi-cylindrical bearing with 9 orifices and for a cylindrical journal bearing with 192 radial and 24 axial orifices. Experiments are described on models of the two bearing configurations with specially designed fixtures which incorporate pneumatic loading and means for determining pressure profiles, gas flow and gap height. The correlation between theory and experiment is satisfactory.

  8. The developmental toxicity of 1-methyl-3-octylimidazolium bromide on Daphnia magna.

    PubMed

    Luo, Yan-Rui; Li, Xiao-Yu; Chen, Xiao-Xiao; Zhang, Bang-Jun; Sun, Zhen-Jun; Wang, Jian-Ji

    2008-12-01

    The developmental toxicity of 1-methyl-3-octylimidazolium bromide ([C(8)mim]Br) on Daphnia magna was investigated. The 24 and 48 h LC(50) values for [C(8)mim]Br in D. magna were 1.99 and 0.95 mg/L, respectively. A series of multigenerational toxicity tests were then used to explore [C(8)mim]Br effects in D. magna. [C(8)mim]Br significantly inhibited the body lengths of the F0 and F1 1st generations. After 21 days of exposure, [C(8)mim]Br lowered the reproductive ability of the F0 and F1 1st generations. In F1 3rd generation, 21 days of [C(8)mim]Br exposure prolonged the time to bear the first egg and the time to the first brood compared with the control, but the number of first-brood offspring and the number of broods produced by these animals were reduced. After the recovery period all the reproductive parameters returned to normal in F1 1st generation except for the number of broods. The dead neonates increased with prolonged exposure and increasing concentrations, and the dead neonates of the F1 3rd generation went far beyond that of the F1 1st and F0 generations. The intrinsic rate of natural increase (r) values of the three D. magna generations significantly decreased after exposure to higher concentrations of [C(8)mim]Br compared with control groups. Collectively, these results suggest that [C(8)mim]Br exerts a toxic effect on the development of D. magna. This study also highlights the importance of systematically evaluating the potential effects of aquatic ecosystems of ionic liquids that may be released into bodies of water. PMID:18442076

  9. Passive magnetic bearing system

    DOEpatents

    Post, Richard F.

    2014-09-02

    An axial stabilizer for the rotor of a magnetic bearing provides external control of stiffness through switching in external inductances. External control also allows the stabilizer to become a part of a passive/active magnetic bearing system that requires no external source of power and no position sensor. Stabilizers for displacements transverse to the axis of rotation are provided that require only a single cylindrical Halbach array in its operation, and thus are especially suited for use in high rotation speed applications, such as flywheel energy storage systems. The elimination of the need of an inner cylindrical array solves the difficult mechanical problem of supplying support against centrifugal forces for the magnets of that array. Compensation is provided for the temperature variation of the strength of the magnetic fields of the permanent magnets in the levitating magnet arrays.

  10. Magnetic bearing and motor

    NASA Technical Reports Server (NTRS)

    Studer, Philip A. (Inventor)

    1983-01-01

    A magnetic bearing assembly (10) has an intermediate rotatable section (33) having an outer cylindrical member (30) coaxially suspended by a torsion wire (72) around an axially polarized cylindrical magnet (32). Axial alignment between the pole faces (40-43) of the intermediate section (33) and end surfaces (50-53) of opposed end bells (20, 22) provides a path of least reluctance across intervening air gaps (60-63) for the magnetic flux emanating from magnet (32). Radial dislocation increases the reluctance and creates a radial restoring force. Substitution of radially polarized magnets 107 fixed to a magnetically permeable cylinder (32') and insertion of pairs of armature coil windings (109-112) between the cylinder pair (33') provides an integral magnetic bearing and torsion motor (100) able to provide arcuately limited rotational drive.

  11. Centrifugally decoupling touchdown bearings

    DOEpatents

    Post, Richard F

    2014-06-24

    Centrifugally decoupling mechanical bearing systems provide thin tensioned metallic ribbons contained in a support structure. This assembly rotates around a stationary shaft being centered at low speeds by the action of the metal ribbons. Tension springs are connected on one end to the ribbons and on the other end to the support structure. The ribbons pass through slots in the inner ring of the support structure. The spring preloading thus insures contact (or near-contact) between the ribbons and the shaft at rotation speeds below the transition speed. Above this speed, however, the centrifugal force on the ribbons produces a tensile force on them that exceeds the spring tensile force so that the ribbons curve outward, effectively decoupling them from mechanical contact with the shaft. They still remain, however, in position to act as a touchdown bearing in case of abnormally high transverse accelerations.

  12. Rotating plug bearing and seal

    DOEpatents

    Wade, Elman E.

    1977-01-01

    A bearing and seal structure for nuclear reactors utilizing rotating plugs above the nuclear reactor vessel. The structure permits lubrication of bearings and seals of the rotating plugs without risk of the lubricant draining into the reactor vessel below. The structure permits lubrication by utilizing a rotating outer race bearing.

  13. Frictionless Bearing Uses Permanent Magnets

    NASA Technical Reports Server (NTRS)

    1965-01-01

    The purpose of this innovation was to develop a frictionless bearing for high speed, light load applications. The device involves the incorporation of permanent magnets in the bearing design. The repulsion of like magnetic poles provides concentric support of the inner member so that no metallic contact occurs between the bearing surfaces.

  14. No-carrier-added (NCA) aryl [{sup 18}F]fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

    SciTech Connect

    Ding, Yu-Shin; Fowler, J.S.; Wolf, A.P.

    1991-12-31

    A method for synthesizing no-carrier-added (NCA) aryl [{sup 18}F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substituent on an electron rich ring. The reaction is carried out by nucleophilic aromatic substitution with a no-carrier-added (NCA) [{sup 18}F]fluoride ion. The method can be used to synthesize various no-carrier-added aryl [{sup 18}F]fluoride compositions, including 6-[{sup 18}F]fluoro-L-DOPA, 2-[{sup 18}F]fluorotyrosine, 6-[{sup 18}F]fluoronorepinephrine, and 6-[{sup 18}F]fluorodopamine. In those instances when a racemic mixture of enantiomers is produced by the present invention, such as in the synthesis of 6-[{sup 18}F]fluoronorepinephrine, a preferred method also includes resolution of the racemic mixture on a chiral HPLC column. This procedure results in a high yield of enantiomerically pure [{sup 18}F] labeled isomers, for example [-]-6-[{sup 18}F]fluoronorepinephrine and [+]-6-[{sup 18}F]fluoronorepinephrine.

  15. Highly efficient palladium precatalysts of homoscorpionate bispyrazolyl ligands for the more challenging Suzuki-Miyaura cross-coupling of aryl chlorides.

    PubMed

    John, Alex; Shaikh, Mobin M; Butcher, Ray J; Ghosh, Prasenjit

    2010-08-21

    Highly efficient palladium precatalysts {[RN{-(CH(2))(n)-pz(3,5-Me)(2)}(2)]PdCl(2)}(m) [m = n = 1; R = 2,6-Me(2)C(6)H(3) (1), 2,4,6-Me(3)C(6)H(2) (2), CH(2)Ph (3) and m = n = 2; R = CH(2)Ph (4)] of a series of homoscorpionate bispyrazolyl ligands for the Suzuki-Miyaura cross-coupling of the more challenging aryl chloride substrates are reported. In particular, the palladium 1-4 precatalysts carried out the Suzuki-Miyaura cross-coupling of a wide variety of aryl chloride substrates bearing electron withdrawing, electron donating and heteroaryl substituents. Remarkably enough, the molecular structure determination of the 1-4 precatalysts by X-ray diffraction studies revealed the presence of anagostic [C-H...Pd] type interactions in the mononuclear 1-3 complexes of methylene bridged bispyrazolyl ligands whereas the ethylene bridged analog 4 yielded an interesting dimeric 20-membered macrometallacyclic complex devoid of any such interaction. PMID:20607167

  16. Big Bear Solar Observatory

    NASA Astrophysics Data System (ADS)

    Murdin, P.

    2000-11-01

    Big Bear Solar Observatory (BBSO) is located at the end of a causeway in a mountain lake more than 2 km above sea level. The site has more than 300 sunny days a year and a natural inversion caused by the lake which makes for very clean images. BBSO is the only university observatory in the US making high-resolution observations of the Sun. Its daily images are posted at http://www.bbso.njit.e...

  17. Radium bearing waste disposal

    SciTech Connect

    Tope, W.G.; Nixon, D.A.; Smith, M.L.; Stone, T.J.; Vogel, R.A.; Schofield, W.D.

    1995-07-01

    Fernald radium bearing ore residue waste, stored within Silos 1 and 2 (K-65) and Silo 3, will be vitrified for disposal at the Nevada Test Site (NTS). A comprehensive, parametric evaluation of waste form, packaging, and transportation alternatives was completed to identify the most cost-effective approach. The impacts of waste loading, waste form, regulatory requirements, NTS waste acceptance criteria, as-low-as-reasonably-achievable principles, and material handling costs were factored into the recommended approach.

  18. Magnetic translator bearings

    NASA Technical Reports Server (NTRS)

    Hockney, Richard L. (Inventor); Downer, James R. (Inventor); Eisenhaure, David B. (Inventor); Hawkey, Timothy J. (Inventor); Johnson, Bruce G. (Inventor)

    1990-01-01

    A magnetic bearing system for enabling translational motion includes a carriage and a shaft for movably supporting the carriage; a first magnetic bearing fixed to one of the carriage and shaft and slidably received in a first channel of the other of the carriage and shaft. The first channel is generally U shaped with two side walls and a back wall. The magnetic bearing includes a pair of spaced magnetic pole pieces, each pole piece having a pair of electromagnetic coils mounted on poles on opposite ends of the pole piece proximate the side walls, and a third electromagnetic coil mounted on a pole of the pole piece proximate the backwall; a motion sensor for sensing translational motion along two axes and rotationally about three axes of the carriage and shaft relative to each other; and a correction circuit responsive to the sensor for generating a correction signal to drive the coils to compensate for any misalignment sensed between the carriage and the shaft.

  19. The series hybrid bearing - A new high speed bearing concept.

    NASA Technical Reports Server (NTRS)

    Anderson, W. J.; Fleming, D. P.; Parker, R. J.

    1971-01-01

    The series-hybrid bearing couples a fluid-film bearing with a rolling-element bearing such that the rolling-element bearing inner race runs at a fraction of shaft speed. A series-hybrid bearing was analyzed and experiments were run at thrust loads from 100 to 300 lb and speeds from 4000 to 30,000 rpm. Agreement between theoretical and experimental speed sharing was good. The lowest speed ratio (ratio of ball bearing inner-race speed to shaft speed) obtained was 0.67. This corresponds to an approximate reduction in DN value of 1/3. For a ball bearing in a 3 million DN application, fatigue life would theoretically be improved by a factor as great as 8.

  20. Organ specificity of aryl hydrocarbon hydroxylase induction by cigarette smoke

    SciTech Connect

    Yoshikawa, M.; Arashidani, K.; Kawamoto, T.; Kodama, Y. )

    1990-06-01

    Biotransformation of many chemicals found in cigarette smoke, such as PAHs and nitrosamines, is generally considered essential for the mutagenic, carcinogenic effects of these xenobiotics. In fact, the genotic action of these premutagens or precarcinogens is dependent on metabolic activation catalyzed by microsomal monooxygenases. The first enzymatic reaction of the PAHs metabolic pathway is catalyzed by a cytochrome P-450-dependent monooxygenase, the aryl hydrocarbon hydroxylase (AHH). AHH leads to the formation of reactive arene oxides, which are further metabolized by enzymatic and non-enzymatic reaction into many metabolites. AHH induction in laboratory animals exposed to cigarette smoke has also been reported, and the data show that this response is highly dependent on species and tissues. Exposure of small laboratory animals to cigarette smoke generally induces AHH in the kidney and lung, while the effect of cigarette smoke on the hepatic AHH activity appears variable.