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Sample records for azides

  1. Sodium Azide

    Science.gov (United States)

    ... Matters What's New A - Z Index Facts About Sodium Azide What sodium azide is Sodium azide is a rapidly acting, ... give people sufficient warning of the danger. Where sodium azide is found and how it is used ...

  2. Alkaline azide mutagenicity in cowpea

    International Nuclear Information System (INIS)

    Sodium azide is known as a potent mutagen in cereals and legumes. It is very effective in acidic medium in barley. Here an attempt is made to measure the effectiveness of sodium azide in alkaline medium (pH 7.4) on cowpea (Vigna unguiculata (L.) Walp., variety FS-68). Seeds pre-soaked in distilled water for 5 hours were treated with different concentrations (10-6, 10-5, 10-4 and 10-3M) of sodium azide (NaN3) for 4 hours at 28± 2 deg. C. Bottles were intermittently shaken, then the seeds were thoroughly washed in running tap water and subsequently planted in pots. The treatment caused significant biological damage such as reduction in seed germination, length of root and shoot, number of nodules and pods per plant and morphological leaf variations. Morphological, as well as chlorophyll mutants, were detected in M2

  3. In situ Fabrication of Monolithic Copper Azide

    Science.gov (United States)

    Li, Bing; Li, Mingyu; Zeng, Qingxuan; Wu, Xingyu

    2016-04-01

    Fabrication and characterization of monolithic copper azide were performed. The monolithic nanoporous copper (NPC) with interconnected pores and nanoparticles was prepared by decomposition and sintering of the ultrafine copper oxalate. The preferable monolithic NPC can be obtained through decomposition and sintering at 400°C for 30 min. Then, the available monolithic NPC was in situ reacted with the gaseous HN3 for 24 h and the monolithic NPC was transformed into monolithic copper azide. Additionally, the copper particles prepared by electrodeposition were also reacted with the gaseous HN3 under uniform conditions as a comparison. The fabricated monolithic copper azide was characterized by Fourier transform infrared (FTIR), inductively coupled plasma-optical emission spectrometry (ICP-OES), and differential scanning calorimetry (DSC).

  4. Controlling hazardous chemicals in microreactors: Synthesis with iodine azide

    Directory of Open Access Journals (Sweden)

    Johan C. Brandt

    2009-06-01

    Full Text Available Aromatic aldehydes have been converted into the corresponding carbamoyl azides using iodine azide. These reactions have been performed safely under continuous flow reaction conditions in microreactors.

  5. Towards the Synthesis of Graphene Azide from Graphene Oxide.

    Science.gov (United States)

    Halbig, Christian E; Rietsch, Philipp; Eigler, Siegfried

    2015-11-26

    In the last decades, organic azides haven proven to be very useful precursors in organic chemistry, for example in 1,3-dipolar cycloaddition reactions (click-chemistry). Likewise, azides can be introduced into graphene oxide with an almost intact carbon framework, namely oxo-functionalized graphene (oxo-G₁), which is a highly oxidized graphene derivative and a powerful precursor for graphene that is suitable for electronic devices. The synthesis of a graphene derivative with exclusively azide groups (graphene azide) is however still a challenge. In comparison also hydrogenated graphene, called graphene or halogenated graphene remain challenging to synthesize. A route to graphene azide would be the desoxygenation of azide functionalized oxo-G₁. Here we show how treatment of azide functionalized oxo-G₁ with HCl enlarges the π-system and removes strongly adsorbed water and some oxo-functional groups. This development reflects one step towards graphene azide.

  6. Synthesis of Azide-Functionalized Hydroxyl-Terminated Polybutadiene

    Science.gov (United States)

    Shekhar Pant, Chandra; Santosh Mada, S. S. N. M.; Mehilal; Banerjee, Shaibal; Khanna, Pawan K.

    2016-10-01

    This article reports ways to functionalize hydroxyl-terminated polybutadiene (HTPB) by azide groups to impart energetic properties to the polymer. Two different synthetic approaches were explored to synthesize azide-functionalized hydroxyl-terminated polybutadiene (azide-HTPB). The functionalized polymer was analyzed for structural confirmation and determination of important physical and thermal properties. Azide-HTPB obtained by azidation of 10% double bonds of HTPB showed viscosity of 11 Pa.s and a glass transition temperature of -66°C.

  7. Towards the Synthesis of Graphene Azide from Graphene Oxide

    OpenAIRE

    Halbig, Christian E.; Philipp Rietsch; Siegfried Eigler

    2015-01-01

    In the last decades, organic azides haven proven to be very useful precursors in organic chemistry, for example in 1,3-dipolar cycloaddition reactions (click-chemistry). Likewise, azides can be introduced into graphene oxide with an almost intact carbon framework, namely oxo-functionalized graphene (oxo-G1), which is a highly oxidized graphene derivative and a powerful precursor for graphene that is suitable for electronic devices. The synthesis of a graphene derivative with exclusively azide...

  8. Vapor pressures and enthalpies of vaporization of azides

    Energy Technology Data Exchange (ETDEWEB)

    Verevkin, Sergey P., E-mail: sergey.verevkin@uni-rostock.de [Department of Physical Chemistry, University of Rostock, Dr-Lorenz-Weg 1, D-18059 Rostock (Germany); Emel' yanenko, Vladimir N. [Department of Physical Chemistry, University of Rostock, Dr-Lorenz-Weg 1, D-18059 Rostock (Germany); Algarra, Manuel [Centro de Geologia do Porto, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal); Manuel Lopez-Romero, J. [Department of Organic Chemistry, University of Malaga. Campus de Teatinos s/n, 29071 Malaga (Spain); Aguiar, Fabio; Enrique Rodriguez-Borges, J.; Esteves da Silva, Joaquim C.G. [Centro de Investigacao em Quimica (CIQ-UP), Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal)

    2011-11-15

    Highlights: > We prepared and measured vapor pressures and vaporization enthalpies of 7 azides. > We examined consistency of new and available in the literature data. > Data for geminal azides and azido-alkanes selected for thermochemical calculations. - Abstract: Vapor pressures of some azides have been determined by the transpiration method. The molar enthalpies of vaporization {Delta}{sub l}{sup g}H{sub m} of these compounds were derived from the temperature dependencies of vapor pressures. The measured data sets were successfully checked for internal consistency by comparison with vaporization enthalpies of similarly structured compounds.

  9. [Reaction of 1,8-naphthyridine azides with ethyl acrylate].

    Science.gov (United States)

    Livi, O; Ferrarini, P L; Bertini, D; Tonetti, I

    1975-12-01

    The reaction of 1,8-naphthyridine azides with ethyl acrylate leads to the formation of 2-pyrazolines instead of 1,2,3-triazolines. Some of the compounds obtained have undergone pharmacological and microbiological (antibacterial) testing. PMID:1204828

  10. Azide Tripodal Dendrons from Behera's Amine and Their Clicked Dendrimers.

    Science.gov (United States)

    Barmare, Farhana; Abadjian, Marie-Caline Z; Wiener, Erik C; Grotjahn, Douglas B

    2016-08-01

    Diazo transfer reactions on Behera's amine and its next-generation analogue formed G0 and G1 azide dendrons bearing three and nine tert-butyl-protected esters, respectively. The utility of the new dendrons was demonstrated by copper-catalyzed azide-alkyne cycloaddition, with 1,3,5-triethynylbenzene, forming two novel dendrimers in a convergent manner. Acid-mediated dendrimer deprotection was successful, and the resulting carboxy-terminated dendrimers were analyzed by NMR and DOSY experiments. PMID:27454340

  11. Synthesis of benzofuranyl and indolyl methyl azides by tandem silver-catalyzed cyclization and azidation.

    Science.gov (United States)

    Ranjith Kumar, Gadi; Kiran Kumar, Yalla; Kant, Ruchir; Sridhar Reddy, Maddi

    2016-04-26

    Ag(i)-catalyzed synthesis of 2-azidomethyl benzofurans/indoles from linear and readily available hydroxyl/amino-phenyl propargyl alcohols is described via a highly regioselective C-O and C-N bond formation. Control experiments reveal that the reaction involves the sequential Ag(i)-catalyzed 5-exo-dig cyclization and a catalyst free γ-allylic azidation. The synthetic utility of this method has been demonstrated by using the azidomethyl unit of the above synthesized heterocycles as the base for a variety of other functionalizations, such as triazole-, tetrazole-, amide-, amine-, and pyrido-derivatives. PMID:27064507

  12. Self-assembly of azide containing dipeptides.

    Science.gov (United States)

    Yuran, Sivan; Razvag, Yair; Das, Priyadip; Reches, Meital

    2014-07-01

    Functional structures and materials are formed spontaneously in nature through the process of self-assembly. Mimicking this process in vitro will lead to the formation of new substances that would impact many areas including energy production and storage, biomaterials and implants, and drug delivery. The considerable structural diversity of peptides makes them appealing building blocks for self-assembly in vitro. This paper describes the self-assembly of three aromatic dipeptides containing an azide moiety: H-Phe(4-azido)-Phe(4-azido)-OH, H-Phe(4-azido)-Phe-OH, and H-Phe-Phe(4-azido)-OH. The peptide H-Phe(4-azido)-Phe(4-azido)-OH self-assembled into porous spherical structures, whereas the peptides H-Phe(4-azido)-Phe-OH and H-Phe-Phe(4-azido)-OH did not form any ordered structures under the examined experimental conditions. The azido group of the peptide can serve as a photo cross-linking agent upon irradiation with UV light. To examine the effect of this group and its activity on the self-assembled structures, we irradiated the assemblies in solution for different time periods. Using electron microscopy, we determined that the porous spherical assemblies formed by the peptide H-Phe(4-azido)-Phe(4-azido)-OH underwent a structural change upon irradiation. In addition, using FT-IR, we detected the chemical change of the peptide azido group. Moreover, using indentation experiments with atomic force microscopy, we showed that the Young's modulus of the spherical assemblies increased after 20 min of irradiation with UV light. Overall, irradiating the solution of the peptide assemblies containing the azido group resulted in a change both in the morphology and mechanical properties of the peptide-based structures. These ordered assemblies or their peptide monomer building blocks can potentially be incorporated into other peptide assemblies to generate stiffer and more stable materials. PMID:24889029

  13. Azidation of Polyvinyl Nitrate and Energy Related Studies

    Directory of Open Access Journals (Sweden)

    S.N. Mishra

    1997-04-01

    Full Text Available Partially substituted polyvinyl azide (PVAZ samples were prepared by reacting sodium azide with polyvinyl nitrate (PVN, containing 15.71 per cent N, in a solution of dimethyl formamide. Replacement of a large proportion of -ONO2 groups by - N3 groups in polymer chain ('azidation' of PVN enhanced reactivity, impact sensitivity and energetics, but reduced thermal stability of the products. The thermogravimetric analysis of PVN showed the onset of rapid decomposition at about 171 °C. The kinetic analysis of thermogravimetric results indicated the validity of random nucleation first-order reaction model. A differential scanning calorimetry thermogram of PVAZ showed a peak at 183.9 °c and heat of decomposition of 2732 J/g, which is lower than that for PVN.

  14. Azide- and alkyne-derivatised α-amino acids

    DEFF Research Database (Denmark)

    Johansson, Karl Henrik; Pedersen, D.S.

    2012-01-01

    for their synthesis. In this review we have compiled available methods for synthesising optically active azide- and alkyne-derivatised α-amino acids that can be prepared from readily available α-amino acids. We highlight a number of commonly overlooked problems associated with existing methods and direct attention......With the emergence of the copper-catalysed Huisgen cycloaddition the use of azide- and alkyne-derivatised α-amino acids has found widespread use within most chemistry disciplines. Despite a growing interest in these building blocks researchers are struggling to identify the best way...... to unexplored possibilities. Azide- and alkyne-derivatised α-amino acids are finding widespread use within most chemistry disciplines. However, it is far from clear what the best way for the synthesis of these useful building blocks is. Herein we show the available methods for synthesis of optically active...

  15. A practical one-pot synthesis of azides directly from alcohols

    Indian Academy of Sciences (India)

    Lalthazuala Rokhum; Ghanashyam Bez

    2012-05-01

    Alkyl/benzyl azides can be readily synthesized in excellent yields from their corresponding alcohols by stirring a solution of sodium azide in DMSO with a thoroughly ground equimolecular mixture of triphenylphosphine, iodine and imidazole.

  16. Perfluroaryl azides : Reactivities, Unique Reactions and their Applications in the Synthesis of Theranostic Agents

    OpenAIRE

    Xie, Sheng

    2015-01-01

    The work centersaround perfluoroaryl azides (PFAAs), and theirability to undergo certain fast and robusttransformations. The chemistry was furtherappliedfor biomedical applications. The first section focuses on the azide-aldehyde-amine cycloaddition using PFAAs. Experimental and computational investigations uncovered a fast azide-enamine cycloaddition to form triazolines, which spontaneously rearrange into stable amidine products. In addition, this transformation was explored in the formulati...

  17. Cyanogen Azide. Ionization Potentials and Ab Initio SCF MO Calculation

    DEFF Research Database (Denmark)

    Bak, Börge; Jansen, Peter; Stafast, Herbert

    1975-01-01

    The Ne(I) and He(I) photoelectron(PE) spectra of cyanogen azide, NCN3, have been recorded at high resolution. Their interpretation is achieved by comparison with the PE spectrum of HN3 and an ab initio LCGO SCF MO calculation. Deviations from Koopmans' theorem of quite different magnitudes are fo...

  18. Inorganic or organic azide-containing hypergolic ionic liquids.

    Science.gov (United States)

    Joo, Young-Hyuk; Gao, Haixiang; Zhang, Yanqiang; Shreeve, Jean'ne M

    2010-04-01

    Recently extensive research has focused on replacing toxic hydrazine, monomethylhydrazine, and unsymmetrical dimethylhydrazine as liquid propellant fuels. 2-Azido-N,N-dimethylethylamine (1) is a good candidate to replace hydrazine derivatives in certain hypergolic fuel applications. Energetic ionic liquids that contain the 2-azido-N,N,N-trimethylethylammonium cation with nitrocyanamide, dicyanamide, dinitramide, or azide anion have been successfully synthesized in good yields by metathesis reactions. Ionic liquids have received considerable attention as energetic materials. The replacement of hydrazine with tertiary ammonium salts is especially attractive since many ionic liquids are models for green chemistry. In this work, new azide-functionalized ionic liquids are demonstrated to exhibit hypergolic activity with such oxidizers as 100% nitric acid or nitrogen tetraoxide (NTO). PMID:20175509

  19. Synthesis, characterization and gas sensing performance of aluminosilicate azide cancrinite

    Indian Academy of Sciences (India)

    A V BORHADE; T A KSHIRSAGAR; S G WAKCHAURE; A G DHOLI

    2016-10-01

    The present investigation deals with synthesis and gas sensing performance of Na$_8$[AlSiO$_4$]$_6$(N$_3$)$_{2.4}$(H$_2$O)$_{4.6}$ cancrinite-based thick film. The product obtained was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, thermogravimetric analysis and magic-angle spin nuclear magneticresonance (MAS NMR). The crystal structure of the product was determined from X-ray powder diffraction data by applying Rietveld refinement. Refinement showed that azide cancrinite crystallize in the space group P6$_3$. Alternate arrangement of Si and Al atoms was confirmed by single intense peak of MAS NMR analysis. For the first time, this study reports the gas sensing performance of aluminosilicate azide cancrinite. The effect of annealing andoperating temperature on gas sensing characteristic of azide cancrinite thick film is investigated systematically for various gases at different operating temperatures. This sensor was observed to be highly sensitive and selective toammonia gas.

  20. Azidated Ether-Butadiene-Ether Block Copolymers as Binders for Solid Propellants

    Science.gov (United States)

    Cappello, Miriam; Lamia, Pietro; Mura, Claudio; Polacco, Giovanni; Filippi, Sara

    2016-07-01

    Polymeric binders for solid propellants are usually based on hydroxyl-terminated polybutadiene (HTPB), which does not contribute to the overall energy output. Azidic polyethers represent an interesting alternative but may have poorer mechanical properties. Polybutadiene-polyether copolymers may combine the advantages of both. Four different ether-butadiene-ether triblock copolymers were prepared and azidated starting from halogenated and/or tosylated monomers using HTPB as initiator. The presence of the butadiene block complicates the azidation step and reduces the storage stability of the azidic polymer. Nevertheless, the procedure allows modifying the binder properties by varying the type and lengths of the energetic blocks.

  1. Base-promoted reactions of bridged ketones and 1,3- and 1,4-haloalkyl azides: competitive alkylation vs azidation reactions of ketone enolates.

    Science.gov (United States)

    Yao, Lei; Smith, Brenton T; Aubé, Jeffrey

    2004-03-01

    The reactions of 1,3- and 1,4-haloalkyl azides with enolates of 2-norbornanone (and a ring-expanded analog) afford polycyclic 1,2,3-triazolines in good yields. The reaction occurs by the initial azidation of the ketone enolate, followed in order by triazoline formation and O-alkylation. An interesting element of this process is the preferential reaction of the alkyl azide with an enolate anion as opposed to the more familiar reaction of the alkyl halide (including Cl and I derivatives). Reactions of acyclic or monocyclic enolates generally lead to 1,2,3-triazoles but none of the alternative C-alkylation product. PMID:14987033

  2. Evolving Structural Diversity and Metallicity in Compressed Lithium Azide

    KAUST Repository

    Prasad, Dasari L. V. K.

    2013-10-10

    In pursuit of new stable nitrogen-rich phases and of a possible insulator-metal transition, the ground-state electronic structure of lithium azide, LiN3, is investigated from 1 atm to 300 GPa (∼2-fold compression) using evolutionary crystal structure exploration methods coupled with density functional theoretical calculations. Two new LiN3 phases, containing slightly reduced and well-separated N2 units, are found to be enthalpically competitive with the known lithium azide crystal structure at 1 atm. At pressures above 36 GPa nitrogen-rich assemblies begin to evolve. These incorporate NN bond formation beyond that in N2 or N3 -. N6 rings and infinite one-dimensional linear nitrogen chains (structural analogues to polyacetylene) appear. Above 200 GPa quasi-one- and two-dimensional extended puckered hexagonal and decagonal nitrogen layers emerge. The high-pressure phase featuring linear chains may be quenchable to P = 1 atm. With increasing pressure the progression in electrical conductivity is from insulator to metal. © 2013 American Chemical Society.

  3. Phase Transition and Structure of Silver Azide at High Pressure

    Energy Technology Data Exchange (ETDEWEB)

    D Hou; F Zhang; C Ji; T Hannon; H Zhu; J Wu; V Levitas; Y Ma

    2011-12-31

    Silver azide (AgN{sub 3}) was compressed up to 51.3 GPa. The results reveal a reversible second-order orthorhombic-to-tetragonal phase transformation starting from ambient pressure and completing at 2.7 GPa. The phase transition is accompanied by a proximity of cell parameters a and b, a 3{sup o} rotation of azide anions, and a change of coordination number from 4-4 (four short, four long) to eight fold. The crystal structure of the high pressure phase is determined to be in I4/mcm space group, with Ag at 4a, N{sub 1} at 4d, and N{sub 2} at 8h Wyckoff positions. Both of the two phases have anisotropic compressibility: the orthorhombic phase exhibits an anomalous expansion under compression along a-axis and is more compressive along b-axis than c-axis; the tetragonal phase is more compressive along the interlayer direction than the intralayer directions. The bulk moduli of the orthorhombic and tetragonal phases are determined to be K{sub OT} = 39{+-}5 GPa with K{sub OT'} = 10{+-}7 and K{sub OT} = 57 {+-}2 GPa with K{sub OT'} = 6.6{+-}0.2, respectively.

  4. Polymerization of nitrogen in cesium azide under modest pressure

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoli, E-mail: use126126@126.com, E-mail: lijianfu@lyu.edu.cn [Institute of Condensed Matter Physics, Linyi University, Linyi 276005 (China); Beijing Computational Science Research Center, Beijing 100084 (China); State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012 (China); Li, Jianfu, E-mail: use126126@126.com, E-mail: lijianfu@lyu.edu.cn [Institute of Condensed Matter Physics, Linyi University, Linyi 276005 (China); Department of Physics and Materials Science, City University of Hong Kong (Hong Kong); Zhu, Hongyang [State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012 (China); Chen, Li [Institute of Condensed Matter Physics, Linyi University, Linyi 276005 (China); Lin, Haiqing [Beijing Computational Science Research Center, Beijing 100084 (China)

    2014-07-28

    Alkali metal azides can be used as starting materials in the synthesis of polymeric nitrogen, a potential high-energy-density material. The structural evolutionary behaviors of nitrogen in CsN{sub 3} have been studied up to 200 GPa using particle swarm optimization structure search combining with density functional theory. Three stable new phases with C2/m, P2{sub 1}/m, and P-1 structure at pressure of 6, 13, and 51 GPa are identified for the first time. The phase transition to chain like structure (P-1 phase) occurs at a modest pressure 51 GPa, the azide ions N{sub 3}{sup −} (linear chains of three N atoms with covalent bonds and interact weakly with each other) begin to show remarkable polymeric N properties in the CsN{sub 3} system. Throughout the stable pressure range, the structure is metallic and consists of N atoms in sp{sup 2} hybridizations. Our study completes the structural evolution of CsN{sub 3} under pressure and reveals that the introduced Cs atoms are responsible for the decreased synthesis pressure comparing to pure molecular nitrogen under compression.

  5. Polarographic studies about indium (III) behaviour in aqueous media of sodium azide

    International Nuclear Information System (INIS)

    The present study shows some polarographic behavior of indium (III) in azide media that is close those observed in a thiocyanate solution. The presence of azide ligand decreases the overpotential in the discharge of indium whose catalytic character can be explained by formation of an azide bridge between electrode and indium (III) increasing the speed of electron transfer. The discharge of indium in azide media is diffusion controlled. As the azide concentration is increased the half wave potential displaces in the cathodic direction. This displacement is due to complex formation. The number of electrons, n, involved in the total process was estimates by the reversible polarographic equation to be 2,7. The potentiostatic coulometry of indium in azide/hydrazoic acid buffer showed a catalytic process where the chemistry regeneration was performed by reaction of hydrazoic acid and indium amalgam. The electrochemistry evidence was the constancy of current as the electrolysis proceeded. The chemistry aspect was the presence of ammonium cation in electrolysed solution. The catalytic process with chemistry regeneration and the formation of a bridge by azide could explain the higher value of current in azide media compared to perchlorate solution. (author)

  6. Study of photochemical transformations of organic azides by matrix isolation techniques and quantum chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Gritsan, N P [Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation)

    2007-12-31

    Results of investigations of organic azide photochemistry in inert gas matrices and the most important spectroscopic studies of the last decade, which formed the basis for the modern views on the photochemistry of azides, are analysed. The unique potential of the matrix isolation technique for the reliable identification of reaction intermediates is demonstrated.

  7. Reactions of Nitroso Hetero Diels-Alder Cycloadducts with Azides: Stereoselective Formation of Triazolines and Aziridines

    Science.gov (United States)

    Bodnar, Brian S.

    2011-01-01

    The addition of azides to acylnitroso hetero Diels-Alder cycloadducts derived from cyclopentadiene affords exo triazolines in excellent yield. The reaction is greatly affected by reducing the level of alkene strain, while sterically demanding azides do not hinder the reaction. Conversion of the triazolines to aziridines is also described. PMID:17429998

  8. Reactions of nitroso hetero-Diels-Alder cycloadducts with azides: stereoselective formation of triazolines and aziridines.

    Science.gov (United States)

    Bodnar, Brian S; Miller, Marvin J

    2007-05-11

    The addition of azides to acylnitroso hetero-Diels-Alder cycloadducts derived from cyclopentadiene affords exo-triazolines in excellent yield. The reaction is greatly affected by the level of alkene strain, while sterically demanding azides do not hinder the reaction. Conversion of the triazolines to aziridines is also described. PMID:17429998

  9. 1,3-Dipolar cycloaddition reactivities of perfluorinated aryl azides with enamines and strained dipolarophiles.

    Science.gov (United States)

    Xie, Sheng; Lopez, Steven A; Ramström, Olof; Yan, Mingdi; Houk, K N

    2015-03-01

    The reactivities of enamines and predistorted (strained) dipolarophiles toward perfluoroaryl azides (PFAAs) were explored experimentally and computationally. Kinetic analyses indicate that PFAAs undergo (3 + 2) cycloadditions with enamines up to 4 orders of magnitude faster than phenyl azide reacts with these dipolarophiles. DFT calculations were used to identify the origin of this rate acceleration. Orbital interactions between the cycloaddends are larger due to the relatively low-lying LUMO of PFAAs. The triazolines resulting from PFAA-enamine cycloadditions rearrange to amidines at room temperature, while (3 + 2) cycloadditions of enamines and phenyl azide yield stable, isolable triazolines. The 1,3-dipolar cycloadditions of norbornene and DIBAC also show increased reactivity toward PFAAs over phenyl azide but are slower than enamine-azide cycloadditions. PMID:25553488

  10. The counteracting effect of potassium cyanide in sodium azide-inhibited germination of Paulownia tomentosa  Steud. seeds

    OpenAIRE

    Živković Suzana; Grubišić Dragoljub V.; Giba Zlatko; Konjević Radomir

    2005-01-01

    The effect of some respiratory inhibitors on light-induced Paulownia tomentosa Steud. seed germination was studied. Millimolar solution of sodium azide was sufficient to completely prevent germination induced by a 5-min red light pulse. The inhibitory effect of azide was absent if seeds were rinsed before phytochrome activation by light. Sodium azide was effective only if present in the period of Pfr activity. The escape time from azide inhibition compared to the escape from far-red light act...

  11. Inactivation of Chikungunya virus by 1,5 iodonapthyl azide

    Directory of Open Access Journals (Sweden)

    Sharma Anuj

    2012-12-01

    Full Text Available Abstract Background Chikungunya virus (CHIKV is an arthropod borne alphavirus of the family Togaviridae. CHIKV is a reemerging virus for which there is no safe prophylactic vaccine. A live attenuated strain of CHIKV, CHIK181/25, was previously demonstrated to be highly immunogenic in humans, however, it showed residual virulence causing transient arthralgia. Findings In this study, we demonstrate the complete inactivation of CHIKV181/25 by 1,5 iodonapthyl azide (INA. No cytopathic effect and virus replication was observed in cells infected with the INA-inactivated CHIKV. However, a reduction in the INA-inactivated CHIK virus-antibody binding capacity was observed by western blot analysis. Conclusion INA completely inactivated CHIKV and can further be explored for developing an inactivated-CHIKV vaccine.

  12. Mutagenic metabolite synthesized by Salmonella typhimurium grown in the presence of azide is azidoalanine

    Energy Technology Data Exchange (ETDEWEB)

    Owais, W.M.; Rosichan, J.L.; Ronald, R.C.; Kleinhofs, A.; Nilan, R.A.

    1983-01-01

    A mutagenic azide metabolite was purified from the medium in which Salmonella typhimurium cells were grown in the presence of azide. This metabolite was identified to be azidoalanine based on infrared and mass spectroscopy and elemental analysis. This compound appeared to be identical to the mutagenic compound synthesized in vitro from azide and O-acetylserine by partially purified O-acetylserine sulfhydrylase. The metabolite (azidoalanine) mutagenic efficiency and spectrum in S. typhimurium was similar to that of inorganic azide. The compounds 2-azidoethylamine, 2-bromoethylamine, 3-bromopropionic acid and N-(azidomethyl) phthalimide were also mutagenic with a similar spectrum to azide and azidolanine, but with lower efficienty. The compounds 3-azidopropylamine, 4-azidobutylamine, 3-chloroalanine and ethylamine were only weakly or nonmutagenic. Numerous other chloro, bromo and azido phthalimide derivatives tested were nonmutagenic. It is suggested that the lack of azide mutagenicity (and perhaps carcinogenicity) in mammalian cells may be due to their inability to convert azide to azidoalanine. 36 references, 3 figures, 2 tables.

  13. Azide resistance in Rhizobium ciceri linked with superior symbiotic nitrogen fixation.

    Science.gov (United States)

    Bhaskar, V Vijay

    2004-12-01

    Isolated azide resistant (AzR) native R. ciceri strain 18-7 was resistant to sodium azide at 10 microg/ml. To find if nif-reiteration is responsible for azide resistance and linked to superior symbiotic nitrogen fixation, transposon (Tn5) induced azide sensitive mutants were generated. Using 4 kb nif-reiterated Sinorhizobium meliloti DNA, a clone C4 that complemented azide sensitivity was isolated by DNA hybridization from genomic library of chickpea Rhizobium strain Rcd301. EcoRI restriction mapping revealed the presence of 7 recognition sites with a total insert size of 19.17 kb. Restriction analysis of C4 clone and nif-reiterated DNA (pRK 290.7) with EcoRI and XhoI revealed similar banding pattern. Wild type strain 18-7, mutant M126 and complemented mutant M126(C4) were characterized for symbiotic properties (viz., acetylene reduction assay, total nitrogen content, nodule number and fresh and dry weight of the infected plants) and explanta nitrogenase activity. Our results suggested that azide resistance, nif-reiteration, and superior symbiotic effectiveness were interlinked with no correlation between ex-planta nitrogenase activity and azide resistance in R. ciceri.

  14. 1,3-Dipolar Cycloaddition Reactivities of Perfluorinated Aryl Azides with Enamines and Strained Dipolarophiles

    OpenAIRE

    Xie, Sheng; Lopez, Steven A.; Ramström, Olof; Yan, Mingdi; Houk, K. N.

    2015-01-01

    The reactivities of enamines and predistorted (strained) dipolarophiles toward perfluoroaryl azides (PFAAs) were explored experimentally and computationally. Kinetic analyses indicate that PFAAs undergo (3 + 2) cycloadditions with enamines up to 4 orders of magnitude faster than phenyl azide reacts with these dipolarophiles. DFT calculations were used to identify the origin of this rate acceleration. Orbital interactions between the cycloaddends are larger due to the relatively low-lying LUMO...

  15. Synthesis of guanidines from azides: a general and straightforward methodology in carbohydrate chemistry.

    Science.gov (United States)

    Santana, Andrés G; Francisco, Cosme G; Suárez, Ernesto; González, Concepción C

    2010-08-01

    The ability of the guanidinylating reagent N',N''-diBoc-N-triflyl-guanidine (GN-Tf) to react with in situ formed free amines from azides in carbohydrate scaffolds was explored. This reaction proved to be an efficient method to prepare guanidine derivatives in a one-pot manner with good to excellent yields, either with primary or secondary azides with different substitution patterns. Labile protecting groups such as benzyl ethers are not removed under these hydrogenolytic conditions.

  16. Accelerating Strain-Promoted Azide-Alkyne Cycloaddition Using Micellar Catalysis.

    Science.gov (United States)

    Anderton, Grant I; Bangerter, Alyssa S; Davis, Tyson C; Feng, Zhiyuan; Furtak, Aric J; Larsen, Jared O; Scroggin, Triniti L; Heemstra, Jennifer M

    2015-08-19

    Bioorthogonal conjugation reactions such as strain-promoted azide-alkyne cycloaddition (SPAAC) have become increasingly popular in recent years, as they enable site-specific labeling of complex biomolecules. However, despite a number of improvements to cyclooctyne design, reaction rates for SPAAC remain significantly lower than those of the related copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Here we explore micellar catalysis as a means to increase reaction rate between a cyclooctyne and hydrophobic azide. We find that anionic and cationic surfactants provide the most efficient catalysis, with rate enhancements of up to 179-fold for reaction of benzyl azide with DIBAC cyclooctyne. Additionally, we find that the presence of surfactant can provide up to 51-fold selectivity for reaction with a hydrophobic over hydrophilic azide. A more modest, but still substantial, 11-fold rate enhancement is observed for micellar catalysis of the reaction between benzyl azide and a DIBAC-functionalized DNA sequence, demonstrating that micellar catalysis can be successfully applied to hydrophilic biomolecules. Together, these results demonstrate that micellar catalysis can provide higher conjugation yields in reduced time when using hydrophobic SPAAC reagents.

  17. Pentagonal monolayer crystals of carbon, boron nitride, and silver azide

    Energy Technology Data Exchange (ETDEWEB)

    Yagmurcukardes, M., E-mail: mehmetyagmurcukardes@iyte.edu.tr; Senger, R. T., E-mail: tugrulsenger@iyte.edu.tr [Department of Physics, Izmir Institute of Technology, 35430 Urla, Izmir (Turkey); Sahin, H.; Kang, J.; Torun, E.; Peeters, F. M. [Department of Physics, University of Antwerp, Campus Groenenborgerlaan, 2020, Antwerp (Belgium)

    2015-09-14

    In this study, we present a theoretical investigation of structural, electronic, and mechanical properties of pentagonal monolayers of carbon (p-graphene), boron nitride (p-B{sub 2}N{sub 4} and p-B{sub 4}N{sub 2}), and silver azide (p-AgN{sub 3}) by performing state-of-the-art first principles calculations. Our total energy calculations suggest feasible formation of monolayer crystal structures composed entirely of pentagons. In addition, electronic band dispersion calculations indicate that while p-graphene and p-AgN{sub 3} are semiconductors with indirect bandgaps, p-BN structures display metallic behavior. We also investigate the mechanical properties (in-plane stiffness and the Poisson's ratio) of four different pentagonal structures under uniaxial strain. p-graphene is found to have the highest stiffness value and the corresponding Poisson's ratio is found to be negative. Similarly, p-B{sub 2}N{sub 4} and p-B{sub 4}N{sub 2} have negative Poisson's ratio values. On the other hand, the p-AgN{sub 3} has a large and positive Poisson's ratio. In dynamical stability tests based on calculated phonon spectra of these pentagonal monolayers, we find that only p-graphene and p-B{sub 2}N{sub 4} are stable, but p-AgN{sub 3} and p-B{sub 4}N{sub 2} are vulnerable against vibrational excitations.

  18. Strain-Promoted 1,3-Dipolar Cycloaddition of Cycloalkynes and Organic Azides.

    Science.gov (United States)

    Dommerholt, Jan; Rutjes, Floris P J T; van Delft, Floris L

    2016-04-01

    A nearly forgotten reaction discovered more than 60 years ago-the cycloaddition of a cyclic alkyne and an organic azide, leading to an aromatic triazole-enjoys a remarkable popularity. Originally discovered out of pure chemical curiosity, and dusted off early this century as an efficient and clean bioconjugation tool, the usefulness of cyclooctyne-azide cycloaddition is now adopted in a wide range of fields of chemical science and beyond. Its ease of operation, broad solvent compatibility, 100 % atom efficiency, and the high stability of the resulting triazole product, just to name a few aspects, have catapulted this so-called strain-promoted azide-alkyne cycloaddition (SPAAC) right into the top-shelf of the toolbox of chemical biologists, material scientists, biotechnologists, medicinal chemists, and more. In this chapter, a brief historic overview of cycloalkynes is provided first, along with the main synthetic strategies to prepare cycloalkynes and their chemical reactivities. Core aspects of the strain-promoted reaction of cycloalkynes with azides are covered, as well as tools to achieve further reaction acceleration by means of modulation of cycloalkyne structure, nature of azide, and choice of solvent. PMID:27573141

  19. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    International Nuclear Information System (INIS)

    The trivalent uranium compound, (MeC5H4)3U(thf), serves as a one- or two-electron reducing agent towards azides, RN3. These reactions produce either the uranium(IV) azide, (MeC5H4)3UN3, or uranium(V) imides, (MeC5H4)3UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me3XN3, the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph3XN3, the azide is produced when X = C or Sn. For Ph3-xCH3N3, the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC6H4N3, only the imides are produced. The magnetic properties of uranium diimides, [(MeC5H4)3U]2(μ-NRN), were investigated. Several uranium(III) amines, (MeC5H4)3U(NH2R), were produced from (MeC5H4)3U(thf) and RNH2, and NH3 was found to be a better ligand towards (MeC5H4)3U than is PMe3

  20. Synthesis, Characterization and Performance of P3HT-Azide-PCBM Microgel.

    Science.gov (United States)

    Wei, Guangmin; Li, Xinxin; Jia, Di; Cheng, He

    2016-06-01

    Spherical Poly(3-hexylthiophene)-azide-[6,61-phenyl-C61-butyric acid methyl ester (P3HT-azide-PCBM) microgel was synthesized by introducing an azide cross-linkable group into the conjugated polymer. Its UV-vis spectrum shifts blue as a result of the systematic disruption of planarity along the P3HT backbone and a reduction in long range conjugation. And the corresponding fluorescence spectrum also indicates that a strong intra-molecular photo-induced electron transfer is originated from the covalent linkage of PCBM moiety to the P3HT backbone via the hexyl bridge upon photoexcitation. Combined Gel Permeation Chromatography (GPC), dynamic and static light scattering (DLS and SLS) measurements prove that the resultant P3HT-azide-PCBM copolymer is a uniform spherical microgel with a hydrodynamic radius of 130 nm at room temperature. The spherical P3HT-azide-PCBM microgel can be used as electron donor or compatibilizer in bulk-heterojunction (BHJ) devices, but its introduction reduces the photovoltaic performance compared with the blend of P3HT/PCBM, because the hole mobility in the crosslinked polythiophene backbones is largely decreased. PMID:27427609

  1. A Double-Clicking Bis-Azide Fluorogenic Dye for Bioorthogonal Self-Labeling Peptide Tags.

    Science.gov (United States)

    Demeter, Orsolya; Fodor, Eszter A; Kállay, Mihály; Mező, Gábor; Németh, Krisztina; Szabó, Pál T; Kele, Péter

    2016-04-25

    Herein, we give the very first example for the development of a fluorogenic molecular probe that combines the two-point binding specificity of biarsenical-based dyes with the robustness of bioorthogonal click-chemistry. This proof-of-principle study reports on the synthesis and fluorogenic characterization of a new, double-quenched, bis-azide fluorogenic probe suitable for bioorthogonal two-point tagging of small peptide tags by double strain-promoted azide-alkyne cycloaddition. The presented probe exhibits remarkable increase in fluorescence intensity when reacted with bis-cyclooctynylated peptide sequences, which could also serve as possible self-labeling small peptide tag motifs. PMID:27010966

  2. Spectroscopic studies on unexpected complex azides of lanthanum(III) and neodymium(III)

    Science.gov (United States)

    Popitsch, A.; Mautner, A.; Fritzer, H. P.

    Solid azides of the types Cs 3La(N 3) 6, Cs 2Nd(N 3) 5, and Cs 4Nd(N 3) 7 can be prepared by metathetical reactions under special precautions. Electronic spectra in diffuse reflectance, infrared and Raman spectra, and magnetic susceptibilities versus temperature and field strength were measured on microcrystalline samples. The data of these new compounds are primarily discussed in view of vibrational properties of the azide ion N 3-, as ligand and in relation to first insights into the nature of the metal-nitrogen bonds within the coordination polyhedra of La(III) and Nd(III).

  3. Asymmetric azidation-cycloaddition with open-chain peptide-based catalysts. A sequential enantioselective route to triazoles.

    Science.gov (United States)

    Guerin, David J; Miller, Scott J

    2002-03-13

    A family of beta-substituted histidine-containing peptides has been synthesized to probe the effect of noncovalent conformational rigidification on catalyst enantioselectivity. Unambiguous enhancement of enantioselectivity in the conjugate addition of azide to alpha,beta-unsaturated carboxylate derivatives has been achieved, enabling application to a sequential asymmetric azidation/cycloaddition for the synthesis of optically enriched triazoles and triazolines. PMID:11878965

  4. Copper on Chitosan: A Recyclable Heterogeneous Catalyst for Azide-alkyne Cycloaddition Reactions in Water

    Science.gov (United States)

    Copper sulfate is immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with copper sulfate; the ensuing catalyst has been utilized for the azide-alkyne cycloaddition in aqueous media and it can be recycled and reused many time without loosing it...

  5. In situ generation of the Ohira-Bestmann Reagent from stable sulfonyl azide

    DEFF Research Database (Denmark)

    Jepsen, Tue Heesgaard; Kristensen, Jesper Langgaard

    2014-01-01

    We report an improved method for in situ generation of the Ohira-Bestmann reagent. Using the recently reported bench stable imidazole-1-sulfonyl azide as diazotransfer reagent, this new method represents a safe and scalable approach for the transformation of aldehydes into terminal alkynes. Furth...

  6. Phosphoramidite accelerated copper(I)-catalyzed [3+2] cycloadditions of azides and alkynes

    NARCIS (Netherlands)

    Campbell-Verduyn, Lachlan S.; Mirfeizi, Leila; Dierckx, Rudi A.; Elsinga, Philip H.; Feringa, Ben L.

    2009-01-01

    Monodentate phosphoramidite ligands are used to accelerate the copper(I)-catalyzed 1,3-dipolar cycloaddition of azides and alkynes (CuAAC) rapidly yielding a wide variety of functionalized 1,4-disubstituted-1,2,3-triazoles; Cu(I) and Cu(II) salts both function as the copper source in aqueous solutio

  7. Health hazard evaluation report HETA 95-0023-2531, American Azide Corporation, Cedar City, Utah

    Energy Technology Data Exchange (ETDEWEB)

    Esswein, E.; Trout, D.; Hales, T.

    1995-09-01

    In response to a confidential request, an investigation was begun into possible exposures to sodium-azide and hydrazoic-acid at the American Azide Corporation (SIC-5169), Cedar City, Utah. Personal breathing zone samples indicated that concentrations of sodium-azide ranged up to 1.7mg/m3. Hydrazoic-acid levels ranged up to 1.1 parts per million (ppm). Sodium-azide levels exceeded the NIOSH recommended exposure level (REL) of 0.3mg/m3 in 28% of the samples and hydrazoic-acid exceeded the REL of 0.1ppm in 14% of the samples. On one occasion the air sample taken inside a supplied air helmet showed a hydrazoic-acid level of 0.13ppm which was greater than the 0.05ppm level recorded from samples on the worker`s collar. The packaging and reblending operation appeared to be those in which workers were most at risk. Medical screening was performed on 11 workers, ten of whom reported headaches occurring in the production areas within 6 months of the evaluation. During that same time period, nine of the 11 reported low blood pressure episodes.

  8. Continuous flow hydrogenation of nitroarenes, azides and alkenes using maghemite-Pd nanocomposites

    Science.gov (United States)

    Maghemite-supported ultra-fine Pd (1-2 nm) nanoparticles, prepared by a simple co-precipitation method, find application in the catalytic continuous flow hydrogenation of nitroarenes, azides, and alkenes wherein they play an important role in reduction of various functional group...

  9. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    Energy Technology Data Exchange (ETDEWEB)

    Rosen, R.K.

    1989-12-01

    The trivalent uranium compound, (MeC{sub 5}H{sub 4}){sub 3}U(thf), serves as a one- or two-electron reducing agent towards azides, RN{sub 3}. These reactions produce either the uranium(IV) azide, (MeC{sub 5}H{sub 4}){sub 3}UN{sub 3}, or uranium(V) imides, (MeC{sub 5}H{sub 4}){sub 3}UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me{sub 3}XN{sub 3}, the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph{sub 3}XN{sub 3}, the azide is produced when X = C or Sn. For Ph{sub 3-x}CH{sub 3}N{sub 3}, the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC{sub 6}H{sub 4}N{sub 3}, only the imides are produced. The magnetic properties of uranium diimides, ((MeC{sub 5}H{sub 4}){sub 3}U){sub 2}({mu}-NRN), were investigated. Several uranium(III) amines, (MeC{sub 5}H{sub 4}){sub 3}U(NH{sub 2}R), were produced from (MeC{sub 5}H{sub 4}){sub 3}U(thf) and RNH{sub 2}, and NH{sub 3} was found to be a better ligand towards (MeC{sub 5}H{sub 4}){sub 3}U than is PMe{sub 3}.

  10. Determination of azide impurity in sartans using reversed-phase HPLC with UV detection.

    Science.gov (United States)

    Gričar, Maja; Andrenšek, Samo

    2016-06-01

    A simple and robust, gradient HPLC method was developed for determination of azide ppm (μgg(-1)) levels in different sartans (irbesartan, candesartan, valsartan). The sartan was dissolved in 0.1M NaOH. Then pH was adjusted to 4.5 with 20% H3PO4 followed by dilution with water. Precipitated API was removed by filtration using 0.45μm membrane PVDF (Polyvinylidene Fluoride) membrane filter, and supernatant was analyzed by gradient elution HPLC at room temperature with Hydro RP HPLC 250×4.6mm, 4μm column and UV detection at 205nm. The best sensitivity was achieved by UV detection cell with 60mm optical path length: LOD 0.17μgg(-1) and LOQ 0.84μgg(-1) for azide. The USP requirement for maximum azide content in irbesartan is 10μgg(-1). The analytical method was validated as per International Conference on Harmonization (ICH) guidelines with respect to system precision, intraday precision (repeatability), intermediate precision (ruggedness), linearity, quantitation limit, detection limit, accuracy, standard and sample solution stability, robustness and selectivity/specificity. The method was linear in the range from LOQ (0.84μgg(-1)) to 101μgg(-1) of azide. The correlation coefficient was 0.9999 and bias on y-axis for 84μgg(-1) test concentration was 0.33%. The accuracy of the method was established based on the recovery obtained between 94.0% and 103.0% for azide. Standard and sample solutions were stable for at least 48h at room temperature and in refrigerator. The method was found to be robust for variation in column temperature (±5°C) and mobile phase flow rate (±0.2mLmin(-1)) and selective for anions such as bromide, nitrate, nitrite, formate and acetate. PMID:26999319

  11. The counteracting effect of potassium cyanide in sodium azide-inhibited germination of Paulownia tomentosa  Steud. seeds

    Directory of Open Access Journals (Sweden)

    Živković Suzana

    2005-01-01

    Full Text Available The effect of some respiratory inhibitors on light-induced Paulownia tomentosa Steud. seed germination was studied. Millimolar solution of sodium azide was sufficient to completely prevent germination induced by a 5-min red light pulse. The inhibitory effect of azide was absent if seeds were rinsed before phytochrome activation by light. Sodium azide was effective only if present in the period of Pfr activity. The escape time from azide inhibition compared to the escape from far-red light action, was delayed for about 24 hours. When azide was applied after phytochrome activation, its effect depended on how long it was present in the incubation medium. The removal of azide allowed full restoration of germination by another red light pulse and the far-red escape time did not differ from the escape of untreated, i.e. water-imbibed seeds. Potassium cyanide alone did not produce any effect in light-stimulated germination of these seeds. However, it counteracted the inhibitory effect of azide in light-stimulated germination, if applied simultaneously at a concentration three times higher.

  12. Cellulose sulphuric acid as a biodegradable catalyst for conversion of aryl amines into azides at room temperature under mild conditions

    Indian Academy of Sciences (India)

    Firouzeh Nesmati; Ali Elhampour

    2012-07-01

    This article describes simple and efficient method for the diazotization and azidation of different aromatic amines over cellulose sulphuric acid, sodium nitrite and sodium azide under mild conditions at room temperature. Various aryl amines possessing electron-withdrawing groups or electron-donating groups have been converted into the corresponding aryl azides with 71-99% yields. The use of mild reaction conditions, avoids the use of harmful acids and toxic solvents and short reaction times are advantages of this methodology. The selected catalyst is found to be highly efficient and recyclable.

  13. Sequential One-Pot Ruthenium-Catalyzed Azide−Alkyne Cycloaddition from Primary Alkyl Halides and Sodium Azide

    KAUST Repository

    Johansson, Johan R.

    2011-04-01

    An experimentally simple sequential one-pot RuAAC reaction, affording 1,5-disubstituted 1H-1,2,3-triazoles in good to excellent yields starting from an alkyl halide, sodium azide, and an alkyne, is reported. The organic azide is formed in situ by treating the primary alkyl halide with sodium azide in DMA under microwave heating. Subsequent addition of [RuClCp*(PPh 3) 2] and the alkyne yielded the desired cycloaddition product after further microwave irradiation. © 2011 American Chemical Society.

  14. Environmental Friendly Azide-Alkyne Cycloaddition Reaction of Azides, Alkynes, and Organic Halides or Epoxides in Water: Efficient "Click" Synthesis of 1,2,3-Triazole Derivatives by Cu Catalyst

    Institute of Scientific and Technical Information of China (English)

    刘建明; 刘慕文; 岳园园; 姚美焕; 卓克垒

    2012-01-01

    An efficient click synthesis of 1,2,3-triazole derivatives from benzyl halides or alkyl halides, epoxides, terminal alkynes, and sodium azides in the presence of copper salts and relative benzimidazole salts have been developed. This procedure eliminates the need to handle potentially organic azides, which are generated in situ. A broad spec- trum of substrates can participate in the process effectively to produce the desired products in good yields.

  15. A combined experimental and theoretical study of the thermal cycloaddition of aryl azides with activated alkenes.

    Science.gov (United States)

    Zeghada, Sarah; Bentabed-Ababsa, Ghenia; Derdour, Aïcha; Abdelmounim, Safer; Domingo, Luis R; Sáez, José A; Roisnel, Thierry; Nassar, Ekhlass; Mongin, Florence

    2011-06-01

    Reactions were performed from aryl azides on the one hand, and activated alkenes coming from β-dicarbonyl compounds or malonodinitrile on the other hand, either with recourse to conventional heating or to microwave activation, to afford 1-aryl-1H-1,2,3-triazoles. The mechanism and the regioselectivity of the reactions involving β-dicarbonyl compounds have been theoretically studied using DFT methods at the B3LYP/6-31G* level: they are domino processes comprising a tautomeric equilibrium of the β-dicarbonyl compounds with their enol forms, a 1,3-dipolar cycloaddition of the enol forms with the aryl azides (high activation energy), and a dehydration process (lower activation energy). The effect of non-conventional activation methods on the degradation of 1,2,3-triazolines was next studied experimentally. Finally, some of the 1,2,3-triazoles such synthesized were evaluated for their bactericidal and cytotoxic activities. PMID:21494704

  16. Azide- and Alkyne-Functionalised α- and β3-Amino Acids

    DEFF Research Database (Denmark)

    Sminia, T.J.; Pedersen, Daniel Sejer

    2012-01-01

    The synthesis and full characterisation of bifunctional β -amino acids that have side chains functionalised with terminal azides (S)-4 and (R)-4 or acetylenes 5 and 6 is reported for the first time. The building blocks incorporate a turn-inducing β -segment and a side chain that can be functional......The synthesis and full characterisation of bifunctional β -amino acids that have side chains functionalised with terminal azides (S)-4 and (R)-4 or acetylenes 5 and 6 is reported for the first time. The building blocks incorporate a turn-inducing β -segment and a side chain that can...... be functionalised further, for example, through copper-catalysed Huisgen cycloaddition. Moreover, the corresponding α-amino acids 1 and 3 have been synthesised and characterised. All amino acid building blocks were of high optical purity as demonstrated by derivatisation and subsequent NMR analysis. © Georg Thieme...

  17. Azide-water intermolecular coupling measured by 2-color 2D IR spectroscopy

    Directory of Open Access Journals (Sweden)

    Perakis F.

    2013-03-01

    Full Text Available We present 2-color two-dimensional infrared spectroscopy of intermolecular coupling between azide ions and their solvation shell water molecules. The cross-peak between azide asymmetric stretch vibration and the OD-stretch vibration is a result of low- probability uphill population transfer. Narrow bleach/excited state absorption peak shows selectivity to solvation shell water molecules only and the characteristics of the cross-peak suggest that the solvation shell hydrogen bond potential has similar anharmonic properties as the hydrogen bond in ice Ih. Population and depopulation of the excited state of the OD-stretch vibration happen on 150 fs and 1.7 ps timescales, respectively, with early manifesting heating effects that limit the selectivity to population times up to 1 ps.

  18. Copper-catalyzed [3 + 2] cycloaddition of (phenylethynyl)di-p-tolylstibane with organic azides

    Science.gov (United States)

    Yamada, Mizuki; Matsumura, Mio; Uchida, Yuki; Kawahata, Masatoshi; Murata, Yuki; Kakusawa, Naoki; Yamaguchi, Kentaro

    2016-01-01

    Summary Trisubstituted 5-stibano-1H-1,2,3-triazoles were synthesized in moderate to excellent yields by the Cu-catalyzed [3 + 2] cycloaddition of a ethynylstibane with organic azides in the presence of CuBr (5 mol %) under aerobic conditions. The reaction of 5-stibanotriazole with HCl, I2, and NOBF4 afforded 1-benzyl-4-phenyltriazole, 1-benzyl-5-iodo-4-phenyltriazole, and a pentavalent organoantimony compound, respectively. PMID:27559379

  19. Stabilty Constants of Haemiglobin Cyanide and Azide Measured by Two-Wavelength Spectrophotometric Method

    OpenAIRE

    Franzini, C; G. Cattozzo; Besozzi, M.

    1987-01-01

    A two-wavelength spectrophotometric procedure for the simultaneous determination of haemiglobin and haemiglobin cyanide (HiCN( (or of haemiglobin and haemiglobin azide (HiN3)) concentrations in mixtures has been developed and applied to the determination of the stability constants of HiCN and HiN3. The analytically reliable procedure allowed stablity constants to be estimated with about 10% (relative standard deviation, coefficient of variation) uncertainty.

  20. Clinical and analytical problems of sodium azide poisonings as exemplified by a case of fatal suicidal poisoning

    Directory of Open Access Journals (Sweden)

    Sebastian Rojek

    2016-03-01

    Full Text Available Aim of the study: To present clinical and analytical aspects associated with sodium azide poisoning. The problems were verified on the basis of a case of sodium azide poisoning which was unique due to its circumstances and the development of an analytical method applied for medico-legal practice. Material and methods : The object of the study was a toxicological analysis of biological specimens collected from a woman who ingested two doses of sodium azide purchased over the Internet, in a suicide attempt. After the ingestion of the first dose, the clinical management in the form of symptomatic treatment indicated a possibility of recovery. However, the ingestion of a second dose of the xenobiotic, already in the hospital, caused death. Toxicological findings were obtained with the dedicated technique of gas chromatography-mass spectrometry (GC-EI-MS-MS after extraction combined with derivatization using pentafluorobenzyl bromide (PFBBr. Results : Post-mortem toxicological studies demonstrated sodium azide in the blood (0.18 mg/l and urine (6.50 mg/l samples collected from the woman. Conclusions : Cases of sodium azide poisoning are rare and difficult to treat, but a review of the literature over a longer interval of time shows that they continue to occur. Therefore, case studies of sodium azide poisoning, together with descriptions of research methodology, can be useful both in clinical terms and in the preparation of toxicological expert opinions for medico-legal purposes.

  1. Synthesis and Characterization of [60]Fullerene-Glycidyl Azide Polymer and Its Thermal Decomposition

    Directory of Open Access Journals (Sweden)

    Ting Huang

    2015-05-01

    Full Text Available A new functionalized [60]fullerene-glycidyl azide polymer (C60-GAP was synthesized for the first time using a modified Bingel reaction of [60]fullerene (C60 and bromomalonic acid glycidyl azide polymer ester (BM-GAP. The product was characterized by Fourier transform infrared (FTIR, ultraviolet-visible (UV-Vis, and nuclear magnetic resonance spectroscopy (NMR analyses. Results confirmed the successful preparation of C60-GAP. Moreover, the thermal decomposition of C60-GAP was analyzed by differential scanning calorimetry (DSC, thermogravimetric analysis coupled with infrared spectroscopy (TGA-IR, and in situ FTIR. C60-GAP decomposition showed a three-step thermal process. The first step was due to the reaction of the azide group and fullerene at approximately 150 °C. The second step was ascribed to the remainder decomposition of the GAP main chain and N-heterocyclic at approximately 240 °C. The final step was attributed to the burning decomposition of amorphous carbon and carbon cage at around 600 °C.

  2. A small azide-modified thiazole-based reporter molecule for fluorescence and mass spectrometric detection

    Directory of Open Access Journals (Sweden)

    Stefanie Wolfram

    2014-10-01

    Full Text Available Molecular probes are widely used tools in chemical biology that allow tracing of bioactive metabolites and selective labeling of proteins and other biomacromolecules. A common structural motif for such probes consists of a reporter that can be attached by copper(I-catalyzed 1,2,3-triazole formation between terminal alkynes and azides to a reactive headgroup. Here we introduce the synthesis and application of the new thiazole-based, azide-tagged reporter 4-(3-azidopropoxy-5-(4-bromophenyl-2-(pyridin-2-ylthiazole for fluorescence, UV and mass spectrometry (MS detection. This small fluorescent reporter bears a bromine functionalization facilitating the automated data mining of electrospray ionization MS runs by monitoring for its characteristic isotope signature. We demonstrate the universal utility of the reporter for the detection of an alkyne-modified small molecule by LC–MS and for the visualization of a model protein by in-gel fluorescence. The novel probe advantageously compares with commercially available azide-modified fluorophores and a brominated one. The ease of synthesis, small size, stability, and the universal detection possibilities make it an ideal reporter for activity-based protein profiling and functional metabolic profiling.

  3. Biocompatible Azide-Alkyne "Click" Reactions for Surface Decoration of Glyco-Engineered Cells.

    Science.gov (United States)

    Gutmann, Marcus; Memmel, Elisabeth; Braun, Alexandra C; Seibel, Jürgen; Meinel, Lorenz; Lühmann, Tessa

    2016-05-01

    Bio-orthogonal copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC) has been widely used to modify azide- or alkyne-bearing monosaccharides on metabolic glyco-engineered mammalian cells. Here, we present a systematic study to elucidate the design space for the cytotoxic effects of the copper catalyst on NIH 3T3 fibroblasts and on HEK 293-F cells. Monitoring membrane integrity by flow cytometry and RT-PCR analysis with apoptotic and anti-apoptotic markers elucidated the general feasibility of CuAAC, with exposure time of the CuAAC reaction mixture having the major influence on biocompatibility. A high labeling efficiency of HEK 293-F cells with a fluorescent alkyne dye was rapidly achieved by CuAAC in comparison to copper free strain-promoted azide-alkyne cycloaddition (SPAAC). The study details effective and biocompatible conditions for CuAAC-based modification of glyco-engineered cells in comparison to its copper free alternative. PMID:26818821

  4. Synthesis and Luminescence Properties of Iridium(III Azide- and Triazole-Bisterpyridine Complexes

    Directory of Open Access Journals (Sweden)

    Timothy W. Schmidt

    2013-07-01

    Full Text Available We describe here the synthesis of azide-functionalised iridium(III bisterpyridines using the “chemistry on the complex” strategy. The resulting azide-complexes are then used in the copper(I-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition “click chemistry” reaction to from the corresponding triazole-functionalised iridium(III bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III bisterpyridines, but this effect can be reversed by the addition of copper(II sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III bisterpyridines can be functionalized for use in “click chemistry” facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

  5. Induced mutation in some guar (Cyamopsis tetragonoloba (L.) taub.) lines using gamma irradiation and sodium azide

    International Nuclear Information System (INIS)

    A mutagenesis study was carried on seeds of two lines of guar L 18 and L 14, which were bombarded with doses of 150, 300,450 and 600 Gy gamma irradiation. Part of the irradiated seeds with the dose 300 Gy and untreated seeds were then soaked separately in 40 or 80 mM of sodium azide for 20 or 30 hours and germinated in vitro to evaluate germination %. Another part of the irradiated seeds with 450 and 600 Gy, were then treated separately with 20 or 40 mM of sodium azide for 10 or 20 hours. Germination of guar was not affected by gamma doses. On the other hand, treatment with sodium azide alone had a great effect on the germination of guar. The percentage of germination ranged between 13.3 and 34.7%. High effects were obtained on seeds treated with 300 Gy and sodium azide (40 and 80 mM) for either 20 or 30 hours, which recorded a range between 9.3 and 13.3%. This indicated that the combined treatment with gamma rays and sodium azide were more effective than sole treatment. Gamma irradiation doses showed no effect on survival of M1 generation, while the combined treatments caused a reduction of about 81.3%. In M2 generation, the growth of the treated plants was slower than the control and the rate of growth decreased with the increased of dose. Variable chlorophyll abnormalities were also detected. In M3 generation leaves with varying chlorophyll abnormalities were recorded, deformated leaves and flowers were recorded at very low rates. However, the effect of gamma rays and the combined treatment on the both guar lines 14 and 18 compared to the control was recorded for the following parameters, inter node length, number of node main stem, number of branches, number of fertile branches, the height of the first pod, number of pods, number of seeds/pod, seed yield, pollen fertility and seed colour change. The most suitable doses that produce maximum variability were 450 Gy and 450 Gy/20 mM/20 hours in line 18 and 150 Gy and 450 Gy/40 mM/10 hours in line 14.(Author)

  6. Pressure-induced phase transitions in rubidium azide: Studied by in-situ x-ray diffraction

    International Nuclear Information System (INIS)

    We present the in-situ X-ray diffraction studies of RbN3 up to 42.0 GPa at room temperature to supplement the high pressure exploration of alkali azides. Two pressure-induced phase transitions of α-RbN3 → γ-RbN3 → δ-RbN3 were revealed at 6.5 and 16.0 GPa, respectively. During the phase transition of α-RbN3 → γ-RbN3, lattice symmetry decreases from a fourfold to a twofold axis accompanied by a rearrangement of azide anions. The γ-RbN3 was identified to be a monoclinic structure with C2/m space group. Upon further compression, an orthogonal arrangement of azide anions becomes energetically favorable for δ-RbN3. The compressibility of α-RbN3 is anisotropic due to the orientation of azide anions. The bulk modulus of α-RbN3 is 18.4 GPa, quite close to those of KN3 and CsN3. By comparing the phase transition pressures of alkali azides, their ionic character is found to play a key role in pressure-induced phase transitions.

  7. Pressure-induced phase transitions in rubidium azide: Studied by in-situ x-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Li, Dongmei; Wu, Xiaoxin; Jiang, Junru; Zhang, Jian; Cui, Qiliang; Zhu, Hongyang, E-mail: hongyangzhu@jlu.edu.cn [State Key Laboratory of Superhard Materials, Jilin University, Changchun, Jilin 130012 (China); Wang, Xiaoli [State Key Laboratory of Superhard Materials, Jilin University, Changchun, Jilin 130012 (China); Institute of Condensed Matter Physics, Linyi University, Linyi 276005 (China)

    2014-08-18

    We present the in-situ X-ray diffraction studies of RbN{sub 3} up to 42.0 GPa at room temperature to supplement the high pressure exploration of alkali azides. Two pressure-induced phase transitions of α-RbN{sub 3} → γ-RbN{sub 3} → δ-RbN{sub 3} were revealed at 6.5 and 16.0 GPa, respectively. During the phase transition of α-RbN{sub 3} → γ-RbN{sub 3}, lattice symmetry decreases from a fourfold to a twofold axis accompanied by a rearrangement of azide anions. The γ-RbN{sub 3} was identified to be a monoclinic structure with C2/m space group. Upon further compression, an orthogonal arrangement of azide anions becomes energetically favorable for δ-RbN{sub 3}. The compressibility of α-RbN{sub 3} is anisotropic due to the orientation of azide anions. The bulk modulus of α-RbN{sub 3} is 18.4 GPa, quite close to those of KN{sub 3} and CsN{sub 3}. By comparing the phase transition pressures of alkali azides, their ionic character is found to play a key role in pressure-induced phase transitions.

  8. A combined experimental and theoretical study of the thermal cycloaddition of aryl azides with activated alkenes.

    OpenAIRE

    Zeghada, Sarah; Bentabed-Ababsa, Ghenia; Derdour, Aïcha; Abdelmounim, Safer; Domingo, Luis .R.; Sáez, José A.; Roisnel, Thierry; Nassar, Ekhlass; Mongin, Florence

    2011-01-01

    Reactions were performed from aryl azides on the one hand, and activated alkenes coming from β-dicarbonyl compounds or malonodinitrile on the other hand, either with recourse to conventional heating or to microwave activation, to afford 1-aryl-1H-1,2,3-triazoles. The mechanism and the regioselectivity of the reactions involving β-dicarbonyl compounds have been theoretically studied using DFT methods at the B3LYP/6-31G* level: they are domino processes comprising a tautomeric equilibrium of th...

  9. Azide-styrene resin negative deep UV resist for KrF excimer laser lithography

    International Nuclear Information System (INIS)

    The authors report a photosensitive composition, consisting of an aromatic azide compound (4,4'diazidodiphenyl methane) and a styrene resin (poly(styrene-co-maleic acid half-isoprapylate)), developed and evaluated as a negative deep ultra-violet (UV) resist for high-resolution KrF excimer laser lithography. Solubility of this resist in an aqueous developer decreases upon exposure to KrF excimer laser irradiation. The alkaline developer removes the unexposed areas of this resist. No swelling-induced pattern deformation occurs and high aspect ratio sub-half-micron patterns in 1.0 μm film thickness are obtained with high sensitivity

  10. DFT Study of Effects of Potassium Doping on Band Structure of Crystalline Cuprous Azide

    Institute of Scientific and Technical Information of China (English)

    ZHU,Wei-Hua; ZHANG,Xiao-Wen; WEI,Tao; XIAO,He-Ming

    2008-01-01

    The structure and defect formation energies of the K-doped CuN3 were studied using density functional theory within the generalized gradient approximation. The results show that the K-doping breaks the azide symmetry and causes asymmetric atomic displacement. As the K-doping level increases, the band gap of the doped system gradually increases. The K impurity is easily incorporated into the crystal thermodynamically. The Cu vacancy is easily created thermodynamically and the K impurity can serve as nucleation centers for vacancy clustering. Finally the effects of K-doping concentrations on the sensitivity of CuN3 were understood based on electronic structures.

  11. Metal azides under pressure: An emerging class of high energy density materials

    Indian Academy of Sciences (India)

    G Vaitheeswaran; K Ramesh Babu

    2012-11-01

    Metal azides are well-known for their explosive properties such as detonation or deflagration. As chemically pure sources of nitrogen, alkali metal azides under high pressure have the ability to form polymeric nitrogen, an ultimate green high energy density material with energy density three times greater than that of known high energetic materials. With this motive, in this present work, we try to address the high-pressure behaviour of LiN3 and KN3 by means of density functional calculations. All the calculations are performed with the inclusion of van derWaals interactions at semi empirical level, as these materials are typical molecular solids. We found that both LiN3 and KN3 are structurally stable up to the studied pressure range of 60 GPa and 16 GPa, respectively. At ambient conditions both the materials are insulators with a gap of 3.48 eV (LiN3) and 4.08 eV (KN3) and as pressure increases the band gap decreases and show semiconducting nature at high pressures.We also found that the compressibility of both the crystals is anisotropic which is in good agreement with experiment. Our theoretical study proved that the materials under study may have the ability to form polymeric nitrogen because of the decrease in interazide ion distance and possible overlapping of N atomic orbitals.

  12. Why do p-nitro-substituted aryl azides provide unintended dark reactions with proteins?

    Science.gov (United States)

    Popova, Tatyana V; Reinbolt, Joseph; Ehresmann, Bernard; Shakirov, Makhmut M; Serebriakova, Marina V; Gerassimova, Yulia V; Knorre, Dmitri G; Godovikova, Tatyana S

    2010-07-01

    Aryl azide-mediated photo cross-linking has been widely used to obtain structural features in biological systems, even though the reactive species generated upon photolysis in aqueous solution have not been well characterized. We have established a mechanistic framework for the formation of adducts between photoactivated 5-azido-2-nitrobenzoyl reagents and protein functional groups. Photolysis of the aryl azide tethered to biotin via an amide linkage yields a cross-link with streptavidin. The ability of the pre-irradiated reagent to form a similar cross-link indicates that it is the long-lived reactive intermediate that contributes to the cross-link formation. The reactive intermediate forms an adduct with tryptophan. The sequence of the labeled peptide is found to be GlyTrp(*)ThrValAlaTrp(*)LysAsn, corresponding to residues 74-81 of the streptavidin sequence, where Trp(*) designates the modified Trp-75 and Trp-79. A peak at m/z 1455.1 corresponding to the calculated [M(peptide)+aryl nitrene+2O](+) molecular ion value has been observed for the labeled peptide. Product structure identification experiments support the assignment that the long-lived reactive intermediate is a p-nitro-N-arylhydroxylamine, which undergoes a number of transformations in aqueous solution leading to nitroso derivatives. A plausible mechanism of the interaction between tryptophan and nitroso compound is discussed.

  13. Electrochemical functionalization of carbon surfaces by aromatic azide or alkyne molecules: a versatile platform for click chemistry.

    Science.gov (United States)

    Evrard, David; Lambert, François; Policar, Clotilde; Balland, Véronique; Limoges, Benoît

    2008-01-01

    The electrochemical reduction of phenylazide or phenylacetylene diazonium salts leads to the grafting of azido or ethynyl groups onto the surface of carbon electrodes. In the presence of copper(I) catalyst, these azide- or alkyne-modified surfaces react efficiently and rapidly with compounds bearing an acetylene or azide function, thus forming a covalent 1,2,3-triazole linkage by means of click chemistry. This was illustrated with the surface coupling of ferrocenes functionalized with an ethynyl or azido group and the biomolecule biotin terminated by an acetylene group.

  14. Room Temperature Activation of Aryloxysulfonyl Azides by [Co(II)(TPP)] for Selective Radical Aziridination of Alkenes via Metalloradical Catalysis

    Science.gov (United States)

    Subbarayan, Velusamy; Jin, Li-Mei; Xin, Cui; Zhang, X. Peter

    2015-01-01

    Aryloxysulfonyl azides can be effectively activated by commercially available cobalt(II) complex of meso-tetraphenylporphyrin ([Co(TPP)]) at room temperature under neutral and nonoxidative conditions for selective radical aziridination of alkenes via metalloradical catalysis. The [Co(TPP)]-catalyzed radical aziridination system is suitable for different combinations of olefin substrates and aryloxysulfonyl azides, producing various N-aryloxysulfonyl aziridine derivatives in good to excellent yields. In addition to generating the environmentally benign N2 as the only byproduct, this Co(II)-based metalloradical aziridination process features mild reaction conditions and operational simplicity. PMID:26139944

  15. Blue-light activated rapid polymerization for defect-free bulk Cu(i)-catalyzed azide-alkyne cycloaddition (CuAAC) crosslinked networks.

    Science.gov (United States)

    Shete, Abhishek U; El-Zaatari, Bassil M; French, Jonathan M; Kloxin, Christopher J

    2016-08-18

    A visible-light (470 nm wavelength) sensitive Type II photoinitiator system is developed for bulk Cu(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reactions in crosslinked networks. The accelerated photopolymerization eliminates UV-mediated azide decomposition allowing for the formation of defect-free glassy networks which exhibit a narrow glass transition temperature. PMID:27499057

  16. New potentiometric transducer based on a Mn(II) [2-formylquinoline thiosemicarbazone] complex for static and hydrodynamic assessment of azides.

    Science.gov (United States)

    Kamel, Ayman H

    2015-11-01

    A new potentiometric transducer for selective recognition of azide is characterized and developed. The PVC plasticized based sensor incorporates Mn(II) [2-formylquinoline thiosemicarbazone] complex in the presence of tri dodecyl methyl ammonium chloride (TDMAC) as a lipophilic cationic additive. The sensor displayed a near-Nernstian response for azide over 1.0×10(-2)-1.0×10(-5) mol L(-1), with an anionic slope of -55.8±0.6 mV decade(-1) and lower limit of detection 0.34 µg mL(-1). The sensor was pH independent in the range 5.5-9 and presented good selectivity features towards several inorganic anions, and it is easily used in a flow injection system and compared with a tubular detector. The intrinsic characteristics of the detector in a low dispersion manifold were determined and compared with data obtained under a hydrodynamic mode of operation. This simple and inexpensive automation, with a good potentiometric detector, enabled the analysis of ~33 samples h(-1) without requiring pre-treatment procedures. The proposed method is also applied to the analysis of trace levels of azide in primer mixtures. Significantly improved accuracy, precision, response time, stability and selectivity were offered by these simple and cost-effective potentiometric sensor compared with other standard techniques. The method has the requisite accuracy, sensitivity and precision to determine azide ions. PMID:26452931

  17. 1,3 Dipolar Cycloaddition Reactions of Substituted Benzyl Azides eith Tans-Dibenzoylethlene : Thermally Stable Trizoles Versus Unstable Triazolines

    International Nuclear Information System (INIS)

    Benzyl and Several Substituted benzyl azides Ιa-q reacted with trans -dibenzoylethylene 2 to give the thermaly unstable trizolinrs 3 which lose nitrogen molecule to yield either enamines 4 or enolimines 5. (Author's) 13 refs., 2 tabs., 4 strus., 1 sche., 2 figs

  18. Development of a general methodology for labelling peptide-morpholino oligonucleotide conjugates using alkyne-azide click chemistry.

    Science.gov (United States)

    Shabanpoor, Fazel; Gait, Michael J

    2013-11-11

    We describe a general methodology for fluorescent labelling of peptide conjugates of phosphorodiamidate morpholino oligonucleotides (PMOs) by alkyne functionalization of peptides, subsequent conjugation to PMOs and labelling with a fluorescent compound (Cy5-azide). Two peptide-PMO (PPMO) examples are shown. No detrimental effect of such labelled PMOs was seen in a biological assay.

  19. MORPHOLOGICAL CHARACTERS OF CHILLI PEPPER (Capsicum frutescens L. AS INFLUENCED BY SODIUM AZIDE AT GENERATIVE STAGE OF M1 GENERATION

    Directory of Open Access Journals (Sweden)

    I Gusti Agung Eka Saraswati

    2013-04-01

    Full Text Available Chili pepper (Capsicum frutescens L. is one vegetable crop that has high economic value.  There are several problems in cultivation of chili pepper, for examples limited land, bad weather, and pests and diseases, which result in low production. These problems can be solved by developing new cultivar which has superior quality.  New cultivars of chili pepper plants can be obtained through induced mutation using chemical mutagen. In this research sodium azide (NaN3 was used as mutagen in chili pepper in order to obtain genetic variations that are useful in  increasing its  production.  The research was designed in  randomized  block  design. The observations were made on the response of plant morphology at generative stage, including plant height, number of branch, number of leaf, leaf length and leaf width.  The results showed that sodium azide increased plant height, branch number, leaf number and leaf length.  Sodium azide at concentrations of 2 mM and 5 mM were most effective in increasing plant height, number of leaves and number of branches. Keywords: Capsicum frutescens L., morphology, mutation, sodium azide

  20. Solid-phase synthesis of NH-1,2,3-triazoles using 4,4′- bismethoxybenzhydryl azide

    DEFF Research Database (Denmark)

    Cohrt, Anders Emil O'Hanlon; Le Quement, Sebastian Thordal; Nielsen, Thomas Eiland

    2014-01-01

    Readily available 4,4′-bismethoxybenzhydryl azide was found to be a useful building block for the synthesis of NH-1,2,3-triazoles through copper(I)-catalyzed cycloaddition reactions with solid-supported terminal alkynes, followed by acid-mediated deprotection. Peptide-containing NH-1,2,3-triazole...

  1. A biomolecule-compatible visible-light-induced azide reduction from a DNA-encoded reaction-discovery system.

    Science.gov (United States)

    Chen, Yiyun; Kamlet, Adam S; Steinman, Jonathan B; Liu, David R

    2011-02-01

    Using a system that accelerates the serendipitous discovery of new reactions by evaluating hundreds of DNA-encoded substrate combinations in a single experiment, we explored a broad range of reaction conditions for new bond-forming reactions. We discovered reactivity that led to a biomolecule-compatible, Ru(II)-catalysed azide-reduction reaction induced by visible light. In contrast to current azide-reduction methods, this reaction is highly chemoselective and is compatible with alcohols, phenols, acids, alkenes, alkynes, aldehydes, alkyl halides, alkyl mesylates and disulfides. The remarkable functional group compatibility and mild conditions of the reaction enabled the azide reduction of nucleic acid and oligosaccharide substrates, with no detectable occurrence of side reactions. The reaction was also performed in the presence of a protein enzyme without the loss of enzymatic activity, in contrast to two commonly used azide-reduction methods. The visible-light dependence of this reaction provides a means of photouncaging functional groups, such as amines and carboxylates, on biological macromolecules without using ultraviolet irradiation.

  2. Fused triazoles via tandem reactions of activated Cinchona alkaloids with azide ion. Second Cinchona rearrangement exemplified.

    Science.gov (United States)

    Röper, S; Franz, M H; Wartchow, R; Hoffmann, H M R

    2003-08-01

    [reaction: see text] Intramolecular 1,3-dipolar cycloadditions of cinchona azides to the C10-C11 alkyne and C10-C11 olefin unit of the alkaloid have been designed via tandem strategy. A variety of fused triazoles and triazolines with a bis-azahomotwistane skeleton have been prepared. In trifluoroethanol, O-mesylcinchonidine 7-OMs and NaN(3) furnish triazole 8 as well as cage-expanded 1,5-diazatricyclo[4.4.1.0(3,8)]undecane derivative 10. Both fused triazoles 8 and 10 are formed with retention of configuration at C9 and C3, respectively. 1-Azabicyclo[3.2.2]cage expansion is shown to be reversible. PMID:12889871

  3. Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides

    KAUST Repository

    Hou, Duenren

    2010-11-01

    A combined experimental and theoretical study of ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) reactions is presented and various electronic analyses were conducted to provide a basis in understanding the observed regioselectivity of the 1,2,3-triazole products. Computational studies using density functional theory (DFT) and atoms in molecules quantum theory (AIM) further yield fresh details on the electronic factors that determine the regioselectivity in the RuAAC. It is found that the formation of 1,2,3-triazole products is irreversible and from the Hammett study, the pathway involving a vinyl cationic intermediate is ruled out. The electronic effect favors the formation of 5-electron-donating-group substituted-1,2,3-trizoles. © 2010 Elsevier Ltd. All rights reserved.

  4. Synthesis of Dendronized Poly(l-Glutamate via Azide-Alkyne Click Chemistry

    Directory of Open Access Journals (Sweden)

    Peter Perdih

    2016-03-01

    Full Text Available Poly(l-glutamate (PGlu was modified with a second-generation dendron to obtain the dendronized polyglutamate, P(Glu-D. Synthesized P(Glu-D exhibited a degree of polymerization (DPn of 46 and a 43% degree of dendronization. Perfect agreement was found between the P(Glu-D expected structure and the results of nuclear magnetic resonance spectroscopy (NMR and size-exclusion chromatography coupled to a multi-angle light-scattering detector (SEC-MALS analysis. The PGlu precursor was modified by coupling with a bifunctional building block (N3-Pr-NH2 in the presence of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl-4-methylmorpholinium chloride (DMTMM coupling reagent. The second-generation polyamide dendron was prepared by a stepwise procedure involving the coupling of propargylamine to the l-lysine carboxyl group, followed by attaching the protected 2,2-bis(methylolpropionic acid (bis-MPA building block to the l-lysine amino groups. The hydroxyl groups of the resulting second-generation dendron were quantitatively deprotected under mild acidic conditions. The deprotected dendron with an acetylene focal group was coupled to the pendant azide groups of the modified linear copolypeptide, P(Glu-N3, in a Cu(I catalyzed azide-alkyne cycloaddition reaction to form a 1,4-disubstituted triazole. The dendronization reaction proceeded quantitatively in 48 hours in aqueous medium as confirmed by 1H NMR and Fourier transform infrared spectroscopy (FT-IR spectroscopy.

  5. Azide protection of bacteroides superoxide dismutases from inactivation by hydrogen peroxide

    International Nuclear Information System (INIS)

    The anaerobes Bacteroides fragilis, B. distasonis and B. thetaiotaomicron produce an iron-containing superoxide dismutase (FeSOD). These FeSODs are reversibly inhibited by 1 mM azide (NaN3) and are irreversibly inactivated upon incubation with hydrogen peroxide (H2O2). H2O2 inactivation of the enzyme likely depends on a Fenton type reaction with the production of hydroxyl radical (OH). Addition of NaN3 to the enzyme solution decreased the rate of inactivation by H2O2. After 20 minutes incubation of purified B. distasonis FeSOD with 2.5 mM H2O2, 61% of the initial enzymatic activity remained when 1 mM NaN3 was also present compared with 29% activity without NaN3. Similar results were seen with FeSOD from B. fragilis and B. thetaiotaomicron. Metal analyses of the native, peroxidized, and NaN3 protected samples are consistent with loss of Fe from the enzyme upon peroxidation, but retention of Fe and enzymatic activity in the NaN3 protected sample. Protection of FeSOD activity from H2O2 inactivation was dependent on NaN3 concentration. Anionic hydroxyl radical scavengers, such as urate and xanthine did not significantly protect the enzyme. The results are consistent with binding of azide to the active site either preventing entry of H2O2 or altering Fe redox potential, preventing OH production

  6. CATIONIC POLYMERIZATION OF 1,3-PENTADIENE INITIATED BY ORGANIC AZIDE/Et2AlCl

    Institute of Scientific and Technical Information of China (English)

    PENG Yuxing; DAI Hansong; LIU Jialin; CUN Linfeng

    1995-01-01

    The cationic polymerization of 1,3-pentadiene was initiated by the organic azide/Et2AlCl initiating system in CH2Cl2 and n-hexane. The polymerizations were also carried out in parallel with organic chloride/Et2AlCl and Et2AlCl alone for comparison. The Et2AlCl- induced polymerization gives a low yield while the polymerization initiated by organic chloride/Et2AlCl produces mainly insoluble product. In contrast, the polymerization with azide/Et2AlCl has a high conversion and the resulting polymer having a high molecular weight is totally soluble. The SEC spectra of the polymers have clearly shown the differences between these initiating systems.

  7. Alkyne-Azide Cycloaddition Catalyzed by Silver Chloride and “Abnormal” Silver N-Heterocyclic Carbene Complex

    Directory of Open Access Journals (Sweden)

    Aldo I. Ortega-Arizmendi

    2013-01-01

    Full Text Available A library of 1,2,3-triazoles was synthesized from diverse alkynes and azides using catalytic amounts of silver chloride instead of copper compounds. In addition, a novel “abnormal” silver N-heterocyclic carbene complex was tested as catalyst in this process. The results suggest that the reaction requires only 0.5% of silver complex, affording 1,2,3-triazoles in good yields.

  8. Synthesis of novel bis(perfluorophenyl azides) coupling agents: Evaluation of their performance by crosslinking of poly(ethylene oxide)

    KAUST Repository

    Mehenni, Hakim

    2011-11-01

    Novel bis(perfluorophenyl azides) coupling agents, containing spacer arms from ethylene or ethylene glycol subunits, were successfully synthesized. Nitrenes photogenerated from these novel bis(PFPA) coupling agents were applied successfully to the cross-linking of poly(ethylene oxide) (PEO10,000) in either aqueous medium or at the solid state, thus, we demonstrated the potential of these bis(PFPA) molecules as promising coupling agents in surface engineering. © 2011 Elsevier Ltd. All rights reserved.

  9. Carboxylate-Assisted Iridium-Catalyzed C-H Amination of Arenes with Biologically Relevant Alkyl Azides.

    Science.gov (United States)

    Zhang, Tao; Hu, Xuejiao; Wang, Zhen; Yang, Tiantian; Sun, Hao; Li, Guigen; Lu, Hongjian

    2016-02-24

    An iridium-catalyzed C-H amination of arenes with a wide substrate scope is reported. Benzamides with electron-donating and -withdrawing groups and linear, branched, and cyclic alkyl azides are all applicable. Cesium carboxylate is crucial for both reactivity and regioselectivity of the reactions. Many biologically relevant molecules, such as amino acid, peptide, steroid, sugar, and thymidine derivatives can be introduced to arenes with high yields and 100 % chiral retention. PMID:26712274

  10. Ab initio molecular orbital characterization of dimethyl group-III azides as sources for photolytic production of free radical beams

    International Nuclear Information System (INIS)

    Use of a beam of biradicaloid such as dialkyl group-III nitrene produced by the method of photodissociation of energetic compound beams (PDECB) is expected to be advantageous to the low-temperature thin-film growth of stoichiometric group-III nitride. Through the clarification of fundamental processes involved in pyrolysis as well as photolysis of dimethylgallium azide [(CH3)2GaN3], dimethylaluminum azide [(CH3)2AlN3], and dimethylboron azide [(CH3)2BN3] based on post-self-consistent field ab initio molecular orbital methods, we discuss the suitability of these possible source compounds for the production of beams of dimethylgalliumnitrene [(CH3)2GaN], dimethylaluminumnitrene [(CH3)2AlN], and dimethylboronnitrene [(CH3)2BN] by the PDECB method. The theoretical results suggested that (CH3)2GaN3 is a promising PDECB source material in that this molecule possesses the nature of unimolecular metastable dye

  11. Fluorescent labelling of in situ hybridisation probes through the copper-catalysed azide-alkyne cycloaddition reaction.

    Science.gov (United States)

    Hesse, Susann; Manetto, Antonio; Cassinelli, Valentina; Fuchs, Jörg; Ma, Lu; Raddaoui, Nada; Houben, Andreas

    2016-09-01

    In situ hybridisation is a powerful tool to investigate the genome and chromosome architecture. Nick translation (NT) is widely used to label DNA probes for fluorescence in situ hybridisation (FISH). However, NT is limited to the use of long double-stranded DNA and does not allow the labelling of single-stranded and short DNA, e.g. oligonucleotides. An alternative technique is the copper(I)-catalysed azide-alkyne cycloaddition (CuAAC), at which azide and alkyne functional groups react in a multistep process catalysed by copper(I) ions to give 1,4-distributed 1,2,3-triazoles at a high yield (also called 'click reaction'). We successfully applied this technique to label short single-stranded DNA probes as well as long PCR-derived double-stranded probes and tested them by FISH on plant chromosomes and nuclei. The hybridisation efficiency of differently labelled probes was compared to those obtained by conventional labelling techniques. We show that copper(I)-catalysed azide-alkyne cycloaddition-labelled probes are reliable tools to detect different types of repetitive sequences on chromosomes opening new promising routes for the detection of single copy gene. Moreover, a combination of FISH using such probes with other techniques, e.g. immunohistochemistry (IHC) and cell proliferation assays using 5-ethynyl-deoxyuridine, is herein shown to be easily feasible. PMID:27095480

  12. Kinetics and mechanism of the sulfite-induced autoxidation of cobalt(II) in aqueous azide medium

    Energy Technology Data Exchange (ETDEWEB)

    Coichev, N.; Van Eldik, R. (Univ. of Witten, Herdecke (West Germany))

    1991-05-15

    The autoxidation of Co(II) in azide medium is accelerated by sulfur(IV) oxides at a concentration level of 10{sup {minus}5} M. The formation of Co(III) was followed spectrophotometrically under the following conditions: (Co(II)) = 5 {times} 10{sup {minus}4} M; initial (Co(III)) = (0{minus}3.6) {times} 10{sup {minus}5} M; (total S(IV)) = (1{minus}4) {times} 10{sup {minus}5} M; 4 < pH < 6; (total N{sub 3}{sup {minus}}) = 0.1 {minus} 0.5 M; temperature = 25C; ionic strength = 1.0 M. The autoxidation reaction exhibits typical autocatalytic behavior in which the induction period depends on the Co(III) concentration. A detailed kinetic study of both the autoxidation step and the reduction of Co(III) by sulfur(IV) oxides demonstrates that the same rate-determining step is operative in both cases. This step involves the reduction of Co(III) by sulfur(IV) oxide to produce the SO{sub 3}{sup {minus}} radical, which reacts with dissolved oxygen to produce SO{sub 5}{sup {minus}} and rapidly oxidizes Co(II) in at least two consecutive steps. The observed rate constant depends on the pH and azide concentration, since these control the speciation of the sulfur(IV) oxides and cobalt (II/III) azide complexes. The proposed mechanism is discussed in reference to available literature information. 29 refs., 8 figs.

  13. Sweet graphene I: toward hydrophilic graphene nanosheets via click grafting alkyne-saccharides onto azide-functionalized graphene oxide.

    Science.gov (United States)

    Namvari, Mina; Namazi, Hassan

    2014-09-19

    Water-soluble graphene nanosheets (GNS) were fabricated via functionalization of graphene oxide (GO) with mono and disaccharides on the basal plane and edges using Cu(I)-catalyzed Huisgen 1,3-dipolar cycloaddition of azides and terminal alkynes (Click chemistry). To graft saccharides onto the plane of GO, it was reacted with sodium azide to introduce azide groups on the plane. Then, it was treated with alkyne-modified glucose, mannose, galactose, and maltose. In the next approach, we attached 1,3-diazideoprop-2-ol onto the edges of GO and it was subsequently clicked with alkyne-glucose. The products were analyzed by Fourier-transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy, thermogravimetric analysis (TGA), and X-ray diffraction spectrometry. FTIR and TGA results showed both sugar-grafted GO sheets were reduced by sodium ascorbate during click-coupling reaction which is an advantage for this reaction. Besides, glycoside-grafted GNS were easily dispersed in water and stable for two weeks.

  14. Azide-based cross-linking of polymers of intrinsic microporosity (PIMs) for condensable gas separation

    KAUST Repository

    Du, Naiying

    2011-03-11

    Cross-linked polymers of intrinsic microporosity (PIM)s for gas separation membranes, were prepared by a nitrene reaction from a representative PIM in the presence of two different diazide cross-linkers. The reaction temperature was optimized using TGA. The homogenous membranes were cast from THF solutions of different ratios of PIM to azides. The resulting cross-linked structures of the PIMs membranes were formed at 175 °C after 7.5 h and confirmed by TGA, XPS, FT-IR spectroscopy and gel content analysis. These resulting cross-linked polymeric membranes showed excellent gas separation performance and can be used for O 2/N 2 and CO 2/N 2 gas pairs, as well as for condensable gases, such as CO 2/CH 4, propylene/propane separation. Most importantly, and differently from typical gas separation membranes derived from glassy polymers, the crosslinked PIMs showed no obvious CO 2 plasticization up to 20 atm pressure of pure CO 2 and CO 2/CH 4 mixtures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Many-body effects in the optical absorption of lithium azide (LiN3)

    Science.gov (United States)

    Gordienko, A. B.; Filippov, S. I.

    2016-07-01

    Until recently most of the understanding achieved for solid explosives has been obtained using various semi-empirical approaches due to a major role of excitonic effects in the mechanisms of decomposition. Nevertheless, during the last two decades, thanks to the ongoing progress in iterative computational methods, the inclusion of the electron-hole interaction in ab initio calculations has become a standard approach in solid-state theory. In this paper, the electronic structure and optical properties of bulk lithium azide are investigated, taking into account the electron-hole interaction via the Bethe-Salpeter equation (BSE). Here, we employ the kernel polynomial method (KPM), which significantly reduces the computational cost compared to direct diagonalization methods. The calculations of the imaginary part of the polarization dependent dielectric function including excitonic effects are reported for the first time. Then, we show a density map of the two-particle wave function and propose an alternative interpretation of the initial stages of the externally triggered chemical decomposition, based on the analysis of two-particle states near the absorption edge.

  16. The use of azide-alkyne click chemistry in recent syntheses and applications of polytriazole-based nanostructured polymers

    Science.gov (United States)

    Shi, Yi; Cao, Xiaosong; Gao, Haifeng

    2016-02-01

    The rapid development of efficient organic click coupling reactions has significantly facilitated the construction of synthetic polymers with sophisticated branched nanostructures. This Feature Article summarizes the recent progress in the application of efficient copper-catalyzed and copper-free azide-alkyne cycloaddition (CuAAC and CuFAAC) reactions in the syntheses of dendrimers, hyperbranched polymers, star polymers, graft polymers, molecular brushes, and cyclic graft polymers. Literature reports on the interesting properties and functions of these polytriazole-based nanostructured polymers are also discussed to illustrate their potential applications as self-healing polymers, adhesives, polymer catalysts, opto-electronic polymer materials and polymer carriers for drug and imaging molecules.

  17. Crosslinking of Kapok Cellulose Fiber via Azide Alkyne Click Chemistry as a New Material for Filtering System: A Preliminary Study

    Directory of Open Access Journals (Sweden)

    Nur Syazwani Abd Rahman

    2016-01-01

    Full Text Available A new class of green material has been elaborated by grafting the modified kapok fiber, by the means of azidated kapok fiber followed by “click-chemistry” reaction with the terminal alkyne crosslinker. The modified and synthesized product was characterized using Fourier transform infrared spectroscopy (FT-IR, and Scanning electron microscopy (SEM. The study also was undertaken to investigate the effect on the absorption of methylene blue from aqueous solution onto the click fiber prepared. The findings showed that the click kapok absorbed more compared to the untreated kapok. Based on the result, the reaction of click chemistry influenced the properties of the filter made from kapok fiber.

  18. Novel carbamoyl type quinine and quinidine based chiral anion exchangers implementing alkyne-azide cycloaddition immobilization chemistry.

    Science.gov (United States)

    Hettegger, Hubert; Kohout, Michal; Mimini, Vebi; Lindner, Wolfgang

    2014-04-11

    The synthesis and chromatographic evaluation of a series of new Cinchona derived chiral weak anion exchangers is presented. Huisgen Cu(I) mediated alkyne-azide cycloaddition, so-called click chemistry, was used as an immobilization strategy. In this way it was possible to immobilize about 90% of offered selector via 1,2,3-triazole linker, which displays a more efficient way of binding the selector to modified silica compared to common radical mediated thiol-ene addition. Problems associated with potential radical scavenging properties of chiral selectors thereby could be circumvented. The evaluation of the synthesized chiral stationary phases regarding chromatographic behavior was carried out using polar organic mode mobile phase composition and a set of representative chiral organic acids. Different loading densities revealed an optimum selector density of about 310μmol/g chiral stationary phase with respect to resolution and selectivity. A decrease of performance was observed for higher loading, indicating mutual spatial influence of selector units leading to sterical hindrance. In addition, we observed that the effect of free azide groups on retention is negligible and the overall chromatographic behavior is comparable to other Cinchona derived chiral stationary phases.

  19. Uncatalyzed thermal gas phase aziridination of alkenes by organic azides. Part I: Mechanisms with discrete nitrene species

    Indian Academy of Sciences (India)

    S PREMILA DEVI; TEJESHWORI SALAM; R H DUNCAN LYNGDOH

    2016-05-01

    Alkene aziridination by azides through uncatalyzed thermal gas phase routes has been studiedusing the DFT B3LYP/6-31G(d,p) method, where the possible role of discrete nitrene intermediates is emphasized.The thermal decomposition of azides is studied using the MP2/aug-cc-pVDZ strategy as well. The MP2(but not the B3LYP) results discount the existence of singlet alkylnitrenes where the alkyl group has an α-hydrogen. Addition of the lowest lying singlet and triplet nitrenes R-N (R = H, Me, Ac) to four different alkenesubstrates leading to aziridine formation was studied by the B3LYP method. Singlet nitrenes with alkenes canyield aziridines via a concerted mechanism, where H-N insertion takes place without a barrier, whereas Me-Nshows larger barriers than Ac-N. Methyl substitution in the alkene favors this reaction. Triplet nitrene additionto alkenes is studied as a two-step process, where the initially formed diradical intermediates cyclize to formaziridines by ISC (intersystem crossing) and collapse. Scope for C-C bond rotation in the diradical leads to lossof stereochemical integrity for triplet nitrene addition to cis- and trans-2-butenes. Geometries of the transitionstates in the various reaction steps studied here are described as “early” or “late” in good accordance with theHammond postulate.

  20. A theoretical DFT study on the structural parameters and azide-tetrazole equilibrium in substituted azidothiazole systems

    Science.gov (United States)

    Abu-Eittah, Rafie H.; El-Kelany, Khaled E.

    2012-12-01

    Azido-tetrazole equilibrium is sensitive to: substitution, solvent, temperature and phase. In this work, the effects of the type and position of substitution on the thiazole ring of azidothiazoles on its structural parameters and on the azido-tetrazole equilibrium have been theoretically investigated using the density functional procedures at the B3LYP/6-311G∗∗ level of theory. This study includes the investigation of the equilibrium geometry, the transformation of the trans-conformer to the cis one then the ring closure to the tetrazole isomer. The transition states of the two steps were located, confirmed and the structural parameters were calculated. In all the steps of calculations, geometry optimization was considered. The results obtained indicate that substitution by: -NO2 and -CN group shifts the equilibrium to the azide side and in some cases the tetrazole isomer is not obtained. On the other hand, substitution by: -NH2 and -OH groups shifts the equilibrium to the tetrazole side and in some cases the azide isomer is not obtained and if formed changes spontaneously to the tetrazole isomer. The decisive parameters which determine the position of the equilibrium are: charge density on atoms N3 and N8, rearrangement of bond length and bond angles during the process of cyclization and variation of dipole moment as a result of cyclization. Results of this work indicate that substitution on C5 is more efficient than substitution on C4 of the thiazole ring.

  1. Research on Synthesis of Trimethylsilane azide%三甲基叠氮硅烷的合成研究

    Institute of Scientific and Technical Information of China (English)

    常淑霞

    2012-01-01

    以三甲基氯硅烷和叠氮化钠为原料,二氯甲烷为溶剂,碘化锌为助催化剂,聚乙二醇400为相转移催化剂,在无水条件下制备三甲基叠氮硅烷。实验考察了滴加时间、保温反应时间、溶剂量、助催化剂量、相转移催化剂量、放大效应等因素对产品收率的影响。反应过程和产品质量通过气相色谱法进行分析、检测。%To' synthesize trimethylsilane azide under the anhydrous condition with trimethylsilane chloride and sodium azide as raw materials, methylene chloride as the resolvent, zinc iodide as catalyst, PTC PEG400 as phase transfer catalyst. To investigate the influencing factors on the yield,such as reaction time,the amount of resolvent,and catalysts (zinc iodide, PCT PEG400), amplification effect, and so on. To detemine the intermediate and final products by gas chromatography.

  2. Extraction behavior of metal-azide complexes with tri-n-octylamine-benzene . Application to impurities determination in thorium

    International Nuclear Information System (INIS)

    The extraction behavior of the complexes species of azide ions (N3-) with Cd, Cu, Co, Zn, Mn, Fe, Ni, Cr, Pb, Bi, Hg, Ag, Au, Tl, Sn, Pd, Pt, Ru, Eu, Zr, Hf, U and Th with a tertiary long-chain amine (tri-n-octylamine) diluted in benzene was extensively studied. The experiments were performed in nitric and perchloric media. A method for trace analysis of U, Fe, Cu, Zn, Ag, Pd, Pt and Au in grade thorium matrix was proposed . The extraction of uranium and development of methods for the determination of a few micrograms of this element were emphatically studied . Procedures for chemical separation among several elements were outlined in this work . The following experiments were also investigated : the effect of p H on the precipitation of thorium in azide medium ; pre-equilibrium of amine with HNO3; the use of thiourea as complexing agent and the respective cationic species not extractable by the amine; uranium and iron striping with Na2Co3 and HNO3 solutions; the use of EDTA or HCl to strip micrograms of thorium from the organic phase, methods for analysing trace amounts of uranium and thorium by molecular absorption spectrophotometry were developed. The main variables of the extraction procedure such as dilution agent, concentration of the extractant , contact time, and volumetric ratio of the phases were also studied. The analytical control of the experiments was done by atomic and molecular absorption spectrophotometry and gamma-ray spectrometry. (author)

  3. Development of an improved and early sowing potential variety of jute - binadeshipat-2 using chemical mutagen sodium azide

    International Nuclear Information System (INIS)

    Jute is the important agricultural and industrial resource of Bangladesh for earning foreign currency. Seeds of the widely cultivated variety, CVL-1 were treated with 4 mM to 20mM of sodium azide (NaN3). The treated seeds were grown in M1 to M10 generations. A single plant (selection number C-278) was selected from M2 segregating population on the basis of early sowing potential and late flowering. Ten fiber quality characters were tested and it was found that the fiber quality of the mutant had been improved. Hence, the mutagen sodium azide showed extra potentiality to induce fiber quality characters of jute. The strain C-278 was also tested through Preliminary, Advanced, Zonal Yield Trial and Farmers field trial at different locations of the jute growing area in Bangladesh. The field evaluation team of the National Seed Board (NSB) visited most of the trials and reported that at early sowing and overall performance of the strain C-278 was found best than that of the mother variety. Besides these the strain produced 7.5% and 20% higher fiber yield than the mother variety CVL-1 and a local cultivar, D-154, respectively. After evaluation of the Technical Committee of NSB recommended that the strain C-278 may be released as a variety. The National Seed Board released the strain C-278 as a National jute variety under the name Binadeshipat-2 for cultivation in Bangladesh

  4. Chronological comparison of root dentin moisture in extracted human teeth stored in formalin, sodium azide, and distilled water

    Science.gov (United States)

    Komabayashi, Takashi; Ahn, Chul; Zhang, Song; Zhu, Qiang

    2009-01-01

    This study quantified in vitro the root dentin moisture when 10% formalin (Group A), 3% sodium azide (Group B), and distilled water (Group C) were used as teeth storage media. The root dentin moisture of 66 extracted human mandibular single-rooted teeth was measured at baseline (day 0) and at 1, 3, 7, and 14 days using a digital grain moisture meter. The baseline dentin moisture value was used as a covariate in the generalized estimating equation (GEE) analysis. The mean dentin moisture values (%) ± standard deviation on days 0, 1, 3, 7, and 14 were 10.6±0.64, 14.3±0.71, 14.6±0.84, 14.4±0.64, and 14.7±0.75 (Group A); 11.4±0.94, 14.6±0.95, 14.6±0.76, 14.6±0.93, and 14.8±0.81 (Group B); and 10.2±0.95, 12.8±0.90, 13.3±0.95, 13.0±0.91, and 13.2±0.89 (Group C), respectively. The dentin moisture increased in all three groups; however, there was no overall significant difference in moisture between the formalin and sodium azide groups. PMID:19540443

  5. 叠氮二乙基铝的合成及其热分解%Synthesis of Diethyl Aluminum Azide and Its Pyrolysis

    Institute of Scientific and Technical Information of China (English)

    高占先; 冯立春; 张小航; 莫自如

    2001-01-01

    以氯化二乙基铝(DECA)和叠氮化钠为原料合成了叠氮二乙基铝(DEAA),报导了放大实验中遇到的问题和解决的方法,以及DEAA热分解的条件及产物。%Diethyl aluminum azide (DEAA) is synthesized by diethyl aluminum chlorode and sodoum azide. Problems arisen and methods soloved problems are reported on bench-scals research. The products and conditions of DEAA pyrolysis are also reported.

  6. Design and Synthesis of New Chacones Substituted with Azide/Triazole Groups and Analysis of Their Cytotoxicity Towards HeLa Cells

    Directory of Open Access Journals (Sweden)

    José A. F. P. Villar

    2012-08-01

    Full Text Available A series of new chalcones substituted with azide/triazole groups were designed and synthesized, and their cytotoxic activity was evaluated in vitro against the HeLa cell line. O-Alkylation, Claisen-Schmidt condensation and Cu(I-catalyzed cycloaddition of azides with terminal alkynes were applied in key steps. Fifteen compounds were tested against HeLa cells. Compound 8c was the most active molecule, with an IC50 value of 13.03 µM, similar to the value of cisplatin (7.37 µM.

  7. Comparative analysis of Cu (I)-catalyzed alkyne-azide cycloaddition (CuAAC) and strain-promoted alkyne-azide cycloaddition (SPAAC) in O-GlcNAc proteomics.

    Science.gov (United States)

    Li, Shanshan; Zhu, He; Wang, Jiajia; Wang, Xiaomin; Li, Xu; Ma, Cheng; Wen, Liuqing; Yu, Bingchen; Wang, Yuehua; Li, Jing; Wang, Peng George

    2016-06-01

    O-linked β-N-acetylglucosamine (O-GlcNAc) is emerging as an essential protein post-translational modification in a range of organisms. It is involved in various cellular processes such as nutrient sensing, protein degradation, gene expression, and is associated with many human diseases. Despite its importance, identifying O-GlcNAcylated proteins is a major challenge in proteomics. Here, using peracetylated N-azidoacetylglucosamine (Ac4 GlcNAz) as a bioorthogonal chemical handle, we described a gel-based mass spectrometry method for the identification of proteins with O-GlcNAc modification in A549 cells. In addition, we made a labeling efficiency comparison between two modes of azide-alkyne bioorthogonal reactions in click chemistry: copper-catalyzed azide-alkyne cycloaddition (CuAAC) with Biotin-Diazo-Alkyne and stain-promoted azide-alkyne cycloaddition (SPAAC) with Biotin-DIBO-Alkyne. After conjugation with click chemistry in vitro and enrichment via streptavidin resin, proteins with O-GlcNAc modification were separated by SDS-PAGE and identified with mass spectrometry. Proteomics data analysis revealed that 229 putative O-GlcNAc modified proteins were identified with Biotin-Diazo-Alkyne conjugated sample and 188 proteins with Biotin-DIBO-Alkyne conjugated sample, among which 114 proteins were overlapping. Interestingly, 74 proteins identified from Biotin-Diazo-Alkyne conjugates and 46 verified proteins from Biotin-DIBO-Alkyne conjugates could be found in the O-GlcNAc modified proteins database dbOGAP (http://cbsb.lombardi.georgetown.edu/hulab/OGAP.html). These results suggested that CuAAC with Biotin-Diazo-Alkyne represented a more powerful method in proteomics with higher protein identification and better accuracy compared to SPAAC. The proteomics credibility was also confirmed by the molecular function and cell component gene ontology (GO). Together, the method we reported here combining metabolic labeling, click chemistry, affinity-based enrichment, SDS

  8. Techniques in gas-phase thermolyses - Part 7. Direct surface participation in gas-phase Curie-point pyrolysis: The pyrolysis of phenyl azide

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Carlsen, Lars

    1986-01-01

    The possible direct participation of the hot reactor surface in the formation of pyrolysis products was elucidated through the pyrolytic decomposition of phenyl azide. It is demonstrated that the intermediate phenyl nitrene generated reacts with elemental carbon at the filament surface, leading...

  9. Explosives: Metal-Organic Framework Templated Synthesis of Copper Azide as the Primary Explosive with Low Electrostatic Sensitivity and Excellent Initiation Ability (Adv. Mater. 28/2016).

    Science.gov (United States)

    Wang, Qianyou; Feng, Xiao; Wang, Shan; Song, Naimeng; Chen, Yifa; Tong, Wenchao; Han, Yuzhen; Yang, Li; Wang, Bo

    2016-07-01

    On page 5837, L. Yang, B. Wang, and co-workers describe a metal-organic framework (MOF) templating method to synthesize copper azide uniformly anchored in a 3D interconnected carbon matrix and evenly spaced by the electron-conductive joints. This strategy sheds light on the preparation of powerful yet safe primary explosives and fulfills the need for controllable explosive systems.

  10. 1,5-Iodonaphthyl azide-inactivated V3526 protects against aerosol challenge with virulent venezuelan equine encephalitis virus.

    Science.gov (United States)

    Gupta, Paridhi; Sharma, Anuj; Spurgers, Kevin B; Bakken, Russell R; Eccleston, Lori T; Cohen, Jeffrey W; Honnold, Shelley P; Glass, Pamela J; Maheshwari, Radha K

    2016-05-27

    Venezuelan equine encephalitis virus (VEEV) is a New World alphavirus. VEEV is highly infectious in aerosolized form and has been identified as a bio-terrorism agent. There is no licensed vaccine for prophylaxis against VEEV. The current IND vaccine is poorly immunogenic and does not protect against an aerosol challenge with virulent VEEV. We have previously shown that VEEV inactivated by 1,5-iodonaphthyl azide (INA) protects against footpad challenge with virulent VEEV. In this study, we inactivated an attenuated strain of VEEV, V3526, with INA and evaluated its protective efficacy against aerosol challenge with wild type VEEV. We demonstrated that among three routes of immunization, intramuscular immunization with INA-inactivate V3526 (INA-iV3526) provided complete protection against aerosol challenge with virulent VEEV. Our data suggests that INA-iV3526 can be explored further for development as an effective vaccine candidate against aerosol challenge of virulent VEEV. PMID:27129427

  11. Density Functional Study on [3+2]-Dipolar Cycloaddition Reaction of the N-heterocyclic Carbene Boryl Azide with Olefins

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xinghui; Wang, Ketai; Niu, Teng; Li, Shanshan [Lanzhou Univ. of Arts and Science, Lanzhou (Korea, Republic of)

    2014-05-15

    The cycloaddition reactions of the N-heterocyclic carbene boryl azide with methyl acrylate, butenone, and hexafluoropropene have been investigated theoretically. Solvent effects on these reactions have been explored by calculation that included a polarizable continuum model (PCM) for the solvent (C6H6). The title reaction could produce 4- and 5-substituted 1,2,3-triazolines, respectively. The reaction systems have the higher chemical reactivity with the low barriers and could be favored. Yet the smaller differences have been found to occur in energetics, and the cycloaddition reactions occur for s-trans conformations over s-cis conformations. The calculations indicated that the cycloaddition reaction of the alkenes have certain regioselectivity.

  12. Density Functional Study on [3+2]-Dipolar Cycloaddition Reaction of the N-heterocyclic Carbene Boryl Azide with Olefins

    International Nuclear Information System (INIS)

    The cycloaddition reactions of the N-heterocyclic carbene boryl azide with methyl acrylate, butenone, and hexafluoropropene have been investigated theoretically. Solvent effects on these reactions have been explored by calculation that included a polarizable continuum model (PCM) for the solvent (C6H6). The title reaction could produce 4- and 5-substituted 1,2,3-triazolines, respectively. The reaction systems have the higher chemical reactivity with the low barriers and could be favored. Yet the smaller differences have been found to occur in energetics, and the cycloaddition reactions occur for s-trans conformations over s-cis conformations. The calculations indicated that the cycloaddition reaction of the alkenes have certain regioselectivity

  13. Synthesis, structure and electrochemistry behavior of a cobalt(III) compound with azide and methyl 2-pyridyl ketone semicarbazone ligands

    Science.gov (United States)

    Shaabani, Behrouz; Khandar, Ali Akbar; Mahmoudi, Farzaneh; Balula, Salete S.; Cunha-Silva, Luís

    2013-08-01

    An unprecedented cobalt(III) compound with methyl 2-pyridyl ketone semicarbazone (HL) and the auxiliary azide ligand, [Co(L)2] [Co(L)(N3)3] (1) was synthesized and further characterized crystallographically and spectroscopically. Compound 1 crystallizes in the triclinic system and space group of P-1 and its structure consists of two mononuclear crystallographic units with metal chromophore comprising two cobalt(III) centers revealing distorted octahedral geometries and formed by distinct ligands in the inner coordination spheres. Interestingly, compound 1 represents the first complex formed by two distinct mononuclear units involving this ligand. As consequence of various donor and acceptor groups in both crystallographic units, there are several strong Nsbnd H⋯N and Nsbnd H⋯O hydrogen bonding interactions interconnecting adjacent moieties, ultimately leading to a three-dimensional supramolecular network. Furthermore, the electrochemical behavior of the HL and compound 1 were investigated.

  14. Silver-catalysed azide-alkyne cycloaddition (AgAAC): assessing the mechanism by density functional theory calculations

    Science.gov (United States)

    Banerji, Biswadip; Chandrasekhar, K.; Killi, Sunil Kumar; Pramanik, Sumit Kumar; Uttam, Pal; Sen, Sudeshna; Maiti, Nakul Chandra

    2016-09-01

    `Click reactions' are the copper catalysed dipolar cycloaddition reaction of azides and alkynes to incorporate nitrogens into a cyclic hydrocarbon scaffold forming a triazole ring. Owing to its efficiency and versatility, this reaction and the products, triazole-containing heterocycles, have immense importance in medicinal chemistry. Copper is the only known catalyst to carry out this reaction, the mechanism of which remains unclear. We report here that the `click reactions' can also be catalysed by silver halides in non-aqueous medium. It constitutes an alternative to the well-known CuAAC click reaction. The yield of the reaction varies on the type of counter ion present in the silver salt. This reaction exhibits significant features, such as high regioselectivity, mild reaction conditions, easy availability of substrates and reasonably good yields. In this communication, the findings of a new catalyst along with the effect of solvent and counter ions will help to decipher the still obscure mechanism of this important reaction.

  15. Copper-free azide-alkyne cycloaddition of targeting peptides to porous silicon nanoparticles for intracellular drug uptake.

    Science.gov (United States)

    Wang, Chang-Fang; Mäkilä, Ermei M; Kaasalainen, Martti H; Liu, Dongfei; Sarparanta, Mirkka P; Airaksinen, Anu J; Salonen, Jarno J; Hirvonen, Jouni T; Santos, Hélder A

    2014-01-01

    Porous silicon (PSi) has been demonstrated as a promising drug delivery vector for poorly water-soluble drugs. Here, a simple and efficient method based on copper-free click chemistry was used to introduce targeting moieties to PSi nanoparticles in order to enhance the intracellular uptake and tumor specific targeting hydrophobic drug delivery. Two RGD derivatives (RGDS and iRGD) with azide-terminated groups were conjugated to bicyclononyne-functionalized PSi nanoparticles via copper-free azide-alkyne cycloaddition. The surface functionalization was performed in aqueous solution at 37 °C for 30 min resulting in conjugation efficiencies of 15.2 and 3.4% (molar ratios) and the nanoparticle size increased from 165.6 nm to 179.6 and 188.8 nm for RGDS and iRGD, respectively. The peptides modification enhanced the cell uptake efficiency of PSi nanoparticles in EA.hy926 cells. PSi-RGDS and PSi-iRGD nanoparticles loaded with sorafenib showed a similar trend for the in vitro antiproliferation activity compared to sorafenib dissolved in dimethyl sulfoxide. Furthermore, sorafenib-loaded PSi-RGDS deliver the drug intracellulary efficiently due to the higher surface conjugation ratio, resulting in enhanced in vitro antiproliferation effect. Our results highlight the surface functionalization methodology for PSi nanoparticles applied here as a universal method to introduce functional moieties onto the surface of PSi nanoparticles and demonstrate their potential active targeting properties for anticancer drug delivery.

  16. Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination.

    Science.gov (United States)

    Shin, Kwangmin; Kim, Hyunwoo; Chang, Sukbok

    2015-04-21

    Owing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon-nitrogen bonds. While metal-catalyzed C-N cross-coupling reactions have been established as one of the most general protocols for C-N bond formation, these methods require starting materials equipped with functional groups such as (hetero)aryl halides or their equivalents, thus generating stoichiometric amounts of halide salts as byproducts. To address this aspect, a transition-metal-catalyzed direct C-H amination approach has emerged as a step- and atom-economical alternative to the conventional C-N cross-coupling reactions. However, despite the significant recent advances in metal-mediated direct C-H amination reactions, most available procedures need harsh conditions requiring stoichiometric external oxidants. In this context, we were curious to see whether a transition-metal-catalyzed mild C-H amination protocol could be achieved using organic azides as the amino source. We envisaged that a dual role of organic azides as an environmentally benign amino source and also as an internal oxidant via N-N2 bond cleavage would be key to develop efficient C-H amination reactions employing azides. An additional advantage of this approach was anticipated: that a sole byproduct is molecular nitrogen (N2) under the perspective catalytic conditions. This Account mainly describes our research efforts on the development of rhodium- and iridium-catalyzed direct C-H amination reactions with organic azides. Under our initially optimized Rh(III)-catalyzed amination conditions, not only sulfonyl azides but also aryl- and alkyl azides could be utilized as facile amino sources in reaction with various types of C(sp(2))-H bonds bearing such directing groups as pyridine, amide, or ketoxime. More recently, a new

  17. Carboxymethyl glycoside lactone(CMGL) synthons:Scope of the method and preliminary results on step growth polymerization of α-azide-ω-alkyne glycomonomers

    Institute of Scientific and Technical Information of China (English)

    CHAMBERT; Stéphane; BERNARD; Julien; FLEURY; Etienne; QUENEAU; Yves

    2010-01-01

    Carboxymethyl glycoside lactones(CMGLs) are bicyclic synthons which open readily for accessing new types of pseudo-glycoconjugates,such as sugar-amino acid hybrids,neoglycolipids,pseudodisaccharides,and membrane imaging systems.After lactone opening,free OH-2 is available for further functionalization,leading to 1,2-bisfunctionalized derivatives.This strategy is illustrated herein with new polymerizable systems of the AB type bearing both azide and alkyne functions prepared from α or β gluco-CMGL synthons.After the reaction of lactones with propargylamine,an azido group was introduced by two different sequences leading to either the 2-manno-azido or the 6-gluco-azido products.The capability of these AB monomers to undergo step growth polymerization through copper(I) catalyzed alkyne-azide cycloaddition(CuAAC) and generate glycopolytriazoles was evidenced.

  18. γ-Fe2O3:A magnetic separable catalyst for synthesis of 5-substituted 1H-tetrazoles from nitriles and sodium azide

    Institute of Scientific and Technical Information of China (English)

    Gang Qi; Yong Dai

    2010-01-01

    An efficient route for the synthesis of 5-substituted 1H-tetrazole via[2+3]cycloaddition of nitriles and sodium azide is reported using γ-Fe2O3 nanoparticles as a magnetic separable catalyst.Under optimized conditions,the moderate to good yields(71-95%)can be obtained.The catalyst can be easily separated by a magnet and reused for several circles.

  19. Formation of 1,4- and 1,5-regioisomers of triazolines in reactions of 2-ethoxyethyl azide with monosubstituted ethylenes

    International Nuclear Information System (INIS)

    The structural specificity of the reactions of 2-ethoxyethyl azide with alkenes RCH=CH2 [R = CH2C6H5, CH2OC6H13, CH(OC2H5)2, C6H5] was studied. The formation of 1,4- and 1,5-substituted triazolines and the high stabilities of the latter were demonstrated by PMR spectroscopy, data from gas-liquid chromatography (GLC), and the kinetics of thermolysis

  20. Traceless Azido Linker for the Solid-Phase Synthesis of NH-1,2,3-Triazoles via Cu-Catalyzed Azide-Alkyne Cycloaddition Reactions

    DEFF Research Database (Denmark)

    Cohrt, Anders Emil; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

    2010-01-01

    A broadly useful acid-labile traceless azido linker for the solid-phase synthesis of NH-1,2,3-triazoles is presented. A variety of alkynes were efficiently immobilized on a range of polymeric supports by Cu(I)-mediated azide-alkyne cycloadditions. Supported triazoles showed excellent compatibilit...... with subsequent peptide chemistry. Release of pure material (typically >95%) from the solid support was readily achieved by treatment with aqueous TFA....

  1. CuAAC click functionalization of azide-modified nanodiamond with a photoactivatable CO-releasing molecule (PhotoCORM) based on [Mn(CO)3(tpm)]+.

    Science.gov (United States)

    Dördelmann, G; Meinhardt, Thomas; Sowik, Thomas; Krueger, Anke; Schatzschneider, Ulrich

    2012-12-01

    The copper-catalyzed 1,3-dipolar azide-alkyne cycloaddition (CuAAC) was used for the first time to attach a biologically active carbon monoxide delivery agent to modified nanodiamond (ND) as a highly biocompatible carrier. The [Mn(CO)(3)(tpm)](+) photoactivatable CO-releasing molecule (PhotoCORM) on the surface retained the carbon monoxide release properties of the parent compound as shown with the myoglobin assay.

  2. Facile synthesis of linear-dendritic cholesteryl-poly(epsilon-caprolactone)-b-(L-lysine)(G2) by thiol-ene and azide-alkyne "click" reactions

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Binder, W.H.; Tanner, S.;

    2010-01-01

    The construction of a linear-dendritic block copolymer consisting of terminal cholesteryl moiety, poly(epsilon-caprolactone), and a second generation L-lysine dendron has been accomplished by the combination of copper(I) catalyzed azide-alkyne and UV-triggered thiol-ene "click" reactions. Ring-op...... thiocholesterol. Near to quantitative functionalization of the intermediate and final products has been attained as confirmed by NMR spectroscopy and MALDI-TOF spectrometry....

  3. Synthesis of novel steroidal 17α-triazolyl derivatives via Cu(I)-catalyzed azide-alkyne cycloaddition, and an evaluation of their cytotoxic activity in vitro.

    Science.gov (United States)

    Frank, Éva; Molnár, Judit; Zupkó, István; Kádár, Zalán; Wölfling, János

    2011-01-01

    Regioselective Cu(I)-catalyzed 1,3-dipolar cycloaddition of steroidal 17α-azides with different terminal alkynes afforded novel 1,4-disubstituted triazolyl derivatives in good yields in both the estrone and the androstane series. The antiproliferative activities of the structurally related triazoles were determined in vitro on three malignant human cell lines (HeLa, MCF7 and A431), with the microculture tetrazolium assay. PMID:21600229

  4. Synthesis and post-synthetic modification of amine-, alkyne-, azide- and nitro-functionalized metal-organic frameworks based on DUT-5.

    Science.gov (United States)

    Gotthardt, Meike A; Grosjean, Sylvain; Brunner, Tobias S; Kotzel, Johannes; Gänzler, Andreas M; Wolf, Silke; Bräse, Stefan; Kleist, Wolfgang

    2015-10-14

    Functionalized 4,4'-biphenyldicarboxylic acid molecules with additional amine, alkyne, azide or nitro groups were prepared and applied in the synthesis of novel metal-organic frameworks and mixed-linker metal-organic frameworks isoreticular to DUT-5. The properties of the frameworks could be tuned by varying the number of functional groups in the materials and the amine groups were employed in post-synthetic modification reactions without changing the framework structure or significantly decreasing the porosity of the materials.

  5. Genetically Encoded Azide Containing Amino Acid in Mammalian Cells Enables Site-Specific Antibody-Drug Conjugates Using Click Cycloaddition Chemistry.

    Science.gov (United States)

    VanBrunt, Michael P; Shanebeck, Kurt; Caldwell, Zachary; Johnson, Jeffrey; Thompson, Pamela; Martin, Thomas; Dong, Huifang; Li, Gary; Xu, Hengyu; D'Hooge, Francois; Masterson, Luke; Bariola, Pauline; Tiberghien, Arnaud; Ezeadi, Ebele; Williams, David G; Hartley, John A; Howard, Philip W; Grabstein, Kenneth H; Bowen, Michael A; Marelli, Marcello

    2015-11-18

    Antibody-drug conjugates (ADC) have emerged as potent antitumor drugs that provide increased efficacy, specificity, and tolerability over chemotherapy for the treatment of cancer. ADCs generated by targeting cysteines and lysines on the antibody have shown efficacy, but these products are heterogeneous, and instability may limit their dosing. Here, a novel technology is described that enables site-specific conjugation of toxins to antibodies using chemistry to produce homogeneous, potent, and highly stable conjugates. We have developed a cell-based mammalian expression system capable of site-specific integration of a non-natural amino acid containing an azide moiety. The azide group enables click cycloaddition chemistry that generates a stable heterocyclic triazole linkage. Antibodies to Her2/neu were expressed to contain N6-((2-azidoethoxy)carbonyl)-l-lysine at four different positions. Each site allowed over 95% conjugation efficacy with the toxins auristatin F or a pyrrolobenzodiazepine (PBD) dimer to generate ADCs with a drug to antibody ratio of >1.9. The ADCs were potent and specific in in vitro cytotoxicity assays. An anti Her2/neu conjugate demonstrated stability in vivo and a PBD containing ADC showed potent efficacy in a mouse tumor xenograph model. This technology was extended to generate fully functional ADCs with four toxins per antibody. The high stability of the azide-alkyne linkage, combined with the site-specific nature of the expression system, provides a means for the generation of ADCs with optimized pharmacokinetic, biological, and biophysical properties. PMID:26332743

  6. Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry†

    KAUST Repository

    Alkayal, Nazeeha

    2016-03-30

    Novel well–defined polyethylene–based graft terpolymers were synthesized via the “grafting onto” strategy by combining nitroxide-mediated radical polymerization (NMP), polyhomologation and copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” chemistry. Three steps were involved in this approach: (i) synthesis of alkyne-terminated polyethylene-b-poly(ε-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE-b-PCL-OH was obtained by polyhomologation of dimethylsulfoxonium methylide to afford PE-OH, followed by ring opening polymerization of ε-caprolactone using the PE-OH as macroinitiator, (ii) synthesis of random copolymers of styrene (St) and 4-chloromethylstyrene (4-CMS) with various CMS contents, by nitroxide-mediated radical copolymerization (NMP), and conversion of chloride to azide groups by reaction with sodium azide (NaN3) (backbone) and (iii) “click” linking reaction to afford the PE-based graft terpolymers. All intermediates and final products were characterized by high-temperature size exclusion chromatography (HT-SEC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and differential scanning calorimetry (DSC).

  7. Synthesis of Two Furazano Azides%两种呋咱环叠氮化合物的合成

    Institute of Scientific and Technical Information of China (English)

    李战雄; 欧育湘; 陈博仁

    2001-01-01

    合成出5,5′-双(叠氮甲基)-3,3′-双(1,2,4-口恶二唑)(Ⅰ)和双(叠氮乙酰亚胺基)氧化偶氮呋咱(Ⅱ),利用元素分析、红外、核磁共振谱和质谱对两种化合物进行了结构鉴定. 通过将叠氮基引入呋咱衍生物中,得到了高氮含量、高生成焓的含能化合物,这两种化合物均有较高的密度,其中化合物Ⅰ为低熔点叠氮化物,可作为含能增塑剂应用.%5,5′-bis(azidomethyl)-3,3′-bis(1,2,4-oxadiazole)(Ⅰ) and bis(azidoacetamino)-oxazofurazan(Ⅱ) were synthesized. The structures of these two compounds have been identified by IR,1H NMR, MS and elemental analysis. Azido groups were introduced into furazan derivatives and energetic materials of high nitrogen content and high enthalpy of formation can be obtained. The densities of compound Ⅰ and Ⅱ are relatively high. Compound Ⅰ is an azide of lower melting point, it is hopeful to be applied as energetic plastic additives.

  8. Investigation on the key factors in the hydrothermal synthesis of BN:The way of introducing sodium azide

    Institute of Scientific and Technical Information of China (English)

    LI Kai; JIANG HaiHui; LIAN Gang; WANG QiLong; ZHAO Xian; CUI DeLiang; TAO XuTang

    2007-01-01

    The way of introducing sodium azide (NaN3) into the reaction solution played an important role in the preparation of cBN by hydrothermal synthesis method. The results showed that both cBN content and crystalline perfection of the samples improved with increasing RN value,and pure cBN could be obtained at 300℃ and 10 MPa when RN increased to 3:1. Here RN is defined as RN =NaN3(I)/NaN3(II),where NaN3(I) denotes the amount of NaN3 (in molar) that is added into the autoclave at the beginning of the reaction process,and NaN3(II) is the amount of NaN3 (also in molar) introduced into the autoclave at high temperature and high pressure (i.e. 300℃ and 10 MPa). In order to explain the experimental results,a preliminary model was proposed in this paper.

  9. Photosensitive Pt(IV)-azide prodrug-loaded nanoparticles exhibit controlled drug release and enhanced efficacy in vivo.

    Science.gov (United States)

    Xiao, Haihua; Noble, Gavin T; Stefanick, Jared F; Qi, Ruogu; Kiziltepe, Tanyel; Jing, Xiabin; Bilgicer, Basar

    2014-01-10

    Cisplatin has long been the first line of treatment for a variety of solid tumors. However, poor pharmacokinetics and high incidences of resistance in the clinic have motivated the production of numerous alternative Pt-based anticancer species. Recently, photosensitive Pt(IV) complexes have garnered much interest because they offer a method of selective induction of active Pt(II) at the tumor site by UVA irradiation. Here, we report the first synthesis, in vitro and in vivo characterization of a novel series of photosensitive Pt(IV)–azide prodrugs and micellar nanoparticle formulations thereof. Upon mild UVA irradiation, both free Pt(IV) complexes and micellar nanoparticles rapidly released biologically active Pt(II), capable of binding to 5′-GMP,while remaining extremely stable in the dark. In vitro, uptake of photosensitive Pt(IV) prodrugs by ovarian cancer SKOV-3 cells was greatly enhanced with the micellar nanoparticles compared to their free prodrug analogs, as well as cisplatin and oxaliplatin. Increased cytotoxicity was observed upon UVA treatment, with up to a 13-fold enhancement over oxaliplatin for the micellar nanoparticles. In vivo bioavailability of micellar nanoparticles was enhanced ~10 fold over free Pt(IV) prodrugs. Importantly, micellar nanoparticles demonstrated significantly improved efficacy against H22 murine hepatocarcinoma, showing decreased systemic toxicity and increased tumor growth inhibition relative to small molecule drugs. These findings establish that photosensitive Pt(IV) complexes, specifically when formulated into micellar nanoparticles, have the potential to offer a robust platform for the controlled delivery and selective activation of Pt-based anticancer therapeutics.

  10. Site-specific bioconjugation of a murine dihydrofolate reductase enzyme by copper(I-catalyzed azide-alkyne cycloaddition with retained activity.

    Directory of Open Access Journals (Sweden)

    Sung In Lim

    Full Text Available Cu(I-catalyzed azide-alkyne cycloaddition (CuAAC is an efficient reaction linking an azido and an alkynyl group in the presence of copper catalyst. Incorporation of a non-natural amino acid (NAA containing either an azido or an alkynyl group into a protein allows site-specific bioconjugation in mild conditions via CuAAC. Despite its great potential, bioconjugation of an enzyme has been hampered by several issues including low yield, poor solubility of a ligand, and protein structural/functional perturbation by CuAAC components. In the present study, we incorporated an alkyne-bearing NAA into an enzyme, murine dihydrofolate reductase (mDHFR, in high cell density cultivation of Escherichia coli, and performed CuAAC conjugation with fluorescent azide dyes to evaluate enzyme compatibility of various CuAAC conditions comprising combination of commercially available Cu(I-chelating ligands and reductants. The condensed culture improves the protein yield 19-fold based on the same amount of non-natural amino acid, and the enzyme incubation under the optimized reaction condition did not lead to any activity loss but allowed a fast and high-yield bioconjugation. Using the established conditions, a biotin-azide spacer was efficiently conjugated to mDHFR with retained activity leading to the site-specific immobilization of the biotin-conjugated mDHFR on a streptavidin-coated plate. These results demonstrate that the combination of reactive non-natural amino acid incorporation and the optimized CuAAC can be used to bioconjugate enzymes with retained enzymatic activity.

  11. Assessment of the Full Compatibility of Copper(I)-Catalyzed Alkyne-Azide Cycloaddition and Oxime Click Reactions for bis-Labelling of Oligonucleotides

    OpenAIRE

    Estalayo-Adriàn, Sandra; Lartia, Rémy; Meyer, Albert; Vasseur, Jean-Jacques; Morvan, François; Defrancq, Eric

    2014-01-01

    The conjugation of oligonucleotides with reporters is of great interest for improving their intrinsic properties or endowing new ones. In this context, we report herein a new procedure for the bis-labelling of oligonucleotides through oxime ligation (Click-O) and copper(I)-catalyzed alkyne–azide cycloaddition (Click-H). 5′-Azido and 3′-aldehyde precursors were incorporated into oligonucleotides, and subsequent coupling reactions through Click-O and Click-H (or vice versa) were successfully ac...

  12. Formation of 1,4- and 1,5-regioisomers of triazolines in reactions of 2-ethoxyethyl azide with monosubstituted ethylenes

    Energy Technology Data Exchange (ETDEWEB)

    Lanovaya, G.A.; Mishchenko, V.F.; Korniets, E.D.

    1987-12-01

    The structural specificity of the reactions of 2-ethoxyethyl azide with alkenes RCH=CH/sub 2/ (R = CH/sub 2/C/sub 6/H/sub 5/, CH/sub 2/OC/sub 6/H/sub 13/, CH(OC/sub 2/H/sub 5/)/sub 2/, C/sub 6/H/sub 5/) was studied. The formation of 1,4- and 1,5-substituted triazolines and the high stabilities of the latter were demonstrated by PMR spectroscopy, data from gas-liquid chromatography (GLC), and the kinetics of thermolysis.

  13. Synthesis and evaluation of an (125)I-labeled azide prosthetic group for efficient and bioorthogonal radiolabeling of cyclooctyne-group containing molecules using copper-free click reaction.

    Science.gov (United States)

    Choi, Mi Hee; Shim, Ha Eun; Nam, You Ree; Kim, Hye Rim; Kang, Jung Ae; Lee, Dong-Eun; Park, Sang Hyun; Choi, Dae Seong; Jang, Beom-Su; Jeon, Jongho

    2016-02-01

    Herein we report the radiosynthesis of a pyridine derived azide prosthetic group for iodine radioisotope labeling of dibenzocyclooctyne (DBCO) conjugated molecules. The radiolabeling of the stannylated precursor 2 was conducted using [(125)I]NaI and chloramine-T to give (125)I-labeled azide ([(125)I]1) with high radiochemical yield (72±8%, n=4) and radiochemical purity (>99%). Using (125)I-labeled azide ([(125)I]1), cyclic RGD peptide and near infrared fluorescent molecule were efficiently labeled with modest to good radiochemical yields. The biodistribution study and SPECT/CT images showed that [(125)I]1 underwent rapid renal clearance. These results clearly demonstrated that [(125)I]1 could be used as an useful radiotracer for in vivo pre-targeted imaging as well as efficient in vitro radiolabeling of DBCO containing molecules. PMID:26748695

  14. Radical substitution with azide

    DEFF Research Database (Denmark)

    Pedersen, Christian Marcus; Marinescu, Lavinia Georgeta; Bols, Mikael

    2005-01-01

    and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)2 and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with sigma+ constants giving with rho-values of -0.47 for TMSN3-PhI(OAc)2 and -0.......39 for IN3. On this basis a radical mechanism of the reaction was proposed....

  15. Gamma irradiation and sodium azide induced changes in growth, leaf protein patterns and genomic DNA of two strains of maize under drought stress

    International Nuclear Information System (INIS)

    Growth potentials of two pure strains (G4 and Rg11) of maize (Zea mays L.) were evaluated under normal irrigation and drought stress. It could be generally concluded that Rg 11 was more fitting under normal irrigation, whereby G4 strain coped better with drought stress. Grain treatment with gamma irradiation (60 Gy) or sodium azide (0.001 M) induced significantly enhanced growth in case of strain G4, under normal irrigation or drought condition, with a higher performance by gamma rays. Treatment with sodium azide gave better results with Rg11 plants. These changes were accompanied with a marked modulation in the protein patterns of leaves of both strains. The most interesting results were the induction of a least six new protein bands in strain G4 under drought stress and three in the Rg11 plants, as compared with those in corresponding control plants subjected to normal irrigation. Meanwhile, similar three proteins (MR: 74, 53, 41 KDa) were repressed in each strain in response to drought

  16. 非叠氮类气体发生剂的研究进展%Progress in Research of Non-azide Gas Generating Composition

    Institute of Scientific and Technical Information of China (English)

    刘影; 冯长根; 杨利

    2012-01-01

    非叠氮类气体发生剂具有的含氮量高、燃速快、安定性良好、无毒、绿色环保等优点,使其成为气体发生剂领域的研究热点,并在汽车安全气囊、航天器、消防灭火等方面有着广泛的应用前景.本文对比叠氮类气体发生剂的性能,详细介绍了唑类、嗪类、胍类和偶氮类非叠氮气体发生剂的性质;全面系统地综述了上述各类非叠氮气体发生剂国内外合成、表征与应用的研究进展;重点分析了各类典型非叠氮气体发生剂的配方及性能参数,并探讨配方内不同组分对发生剂不同性能的影响,为进一步研发新型非叠氮类气体发生剂配方提供参考.经研究发现,同传统的叠氮类气体发生剂相比,虽然非叠氮类气体发生剂在产气量、燃速等性能方面有较大的提高,但因其存在价格昂贵等问题,目前仍然没有完全取代叠氮类气体发生剂.因此,在现有研究基础上,还需积极研发更加环保、无毒、高效、廉价和实用的非叠氮类气体发生剂.%The non-azide gas generating composition is a hot research topic due to its many features, such as high nitrogen content, fast burning rate, good stability, non-toxicity, and green environmental protection. It is widely applied in airbag, spacecraft, fire fighting and other fields. In this paper, compared with the traditional azide gas generating composition, the properties of azole, azine, guanidine and azoic gas generating compositions are analyzed in detail: the progresses in the synthesis, the characterization and the application are reviewed: the formulas and characteristic parameters are discussed. It is found that the non-azide gas generating composition has not completely replaced the traditional azide gas generating composition, despite its superior properties in many aspects, because of factors like the high price, the excessive heat of combustion, and the high temperature. Therefore it is necessary to

  17. Poli (metil azoteto de glicidila - GAP. I: síntese e caracterização Glycidyl azide polymer (GAP. I: syntheses and characterization

    Directory of Open Access Journals (Sweden)

    Sandro P. Ribeiro

    2012-01-01

    Full Text Available O poli (metil azoteto de glicidila - GAP - é um material energético que pode ser utilizado como aglutinante (binder e como plastificante energético em compostos explosivos e propulsores de foguetes. Neste trabalho, foi abordada a síntese do (GAP através da conversão direta da epicloridrina (ECH a GAP. Os reagentes utilizados foram azida de sódio, epicloridrina e vários álcoois extensores de cadeias, o etanodiol, o 1,4-butanodiol, o dietilenoglicol e o glicerol. Alguns parâmetros de operação foram avaliados, como o tempo de reação, a proporção entre os reagentes, dois tipos de solvente e a ordem de adição dos reagentes. A variável observada para a análise foi a massa molecular do GAP. Todos os materiais sintetizados também foram caracterizados por análises de FTIR, UV, RMN, DSC, análise elementar e TGA. Uma maior massa molecular, maior rendimento e uma melhor conversão do grupo azida a GAP foram obtidos com a adição de epicloridrina sobre a azida de sódio e usando DMF como solvente.GAP is an aliphatic polyether that includes hydroxyl groups and highly energetic azide groups. Thus, it is an energetic material that can be used as binder or plasticizing agent in propellants and explosive mixtures. The glycidyl azide polymer (GAP was synthesized and characterized by direct conversion of epichlorohydrin. GAP was synthesized by reaction of sodium azide, epichlorohydrin, and some extensor alcohols. The investigation focused on the effects of some key reaction parameters including reagent proportions, reaction time and two different solvents. The product was characterized by FTIR, UV, NMR, DSC, elemental analysis, TGA and GPC. The species were also evaluated through molecular weight (GPC, glass transition temperature (DSC, ignition time and sensitivity.

  18. Rational design of azide-bridged bimetallic complexes. Crystal structure and magnetic properties of Fe(III)MFe(III) (M = Ni(II) and Cu(II)) trinuclear species.

    Science.gov (United States)

    Colacio, Enrique; Costes, Jean-Pierre; Domínguez-Vera, José M; Maimoun, Ikram Ben; Suárez-Varela, José

    2005-01-28

    The first examples of azide-bridged bimetallic trinuclear complexes ([M(cyclam)][FeL(N3)(mu1,5-N3)]2) (H2L = 4,5-dichloro-1,2-bis(pyridine-2-carboxamido) benzene) have been structurally and magnetically characterized.

  19. Synthesis and Proof of Diethylaluminum Azide being Lower Melting Point Crystal%低熔点晶体叠氮二乙基铝的合成和证明

    Institute of Scientific and Technical Information of China (English)

    张小航; 高占先

    2001-01-01

    Diethylaluminum azide (DEAA) is an important compound in organoaluminum azides. But the synthesis and property of DEAA were reported a little. The DEAA is a liquid compound in literature that was synthesed by the reaction of diethyl aluminum chloride (DEAC) and sodium azide. The solid product as a colorless crystal was first obtained by the reaction of DEAC and sodium azide in our work. The solid product was characterized as DEAA by IR spectrum and 1H NMR spectrum. The yield of crystal DEAA was increased as NaN3/DEAC (mol/mol) increased. When NaN3/DEAC=1.3 the yield of DEAA is increased from 74% in literature to 83%. The melting point of DEAA is 28~29℃ that was determined with two methods in the work. The DEAA containing trace DEAC (about 0. 2% of DEAC) is liquid which has been full proved by varied tests in this paper. The melting point of DEAA is-130℃ in literature because the DEAA is not pure that may contain DEAC. The-130℃ may be eutectic point of eutectic mixture forming of DEAA and DEAC. 27Al NMR of DEAA is determined. At 8=6.4 there is a peak that W1/2 of the peak is 834Hz.The structure of crystal DEAA is inferred from 27Al NMR.

  20. Click synthesis of 1,4-disubstituted-1,2,3-triazoles catalysed by CuO-CeO2 nanocomposite in the presence of amberlite-supported azide

    Indian Academy of Sciences (India)

    Jalal Albadi; Jafar Abbasi Shiran; Azam Mansournezhad

    2014-01-01

    A CuO-CeO2 nanocomposite in the presence of amberlite-supported azide has been used for the click synthesis of 1,4-disubstituted-1,2,3-triazoles in good yields. This catalyst can be reused several times without any significant decrease in the catalytic activity.

  1. The effects of duration of pre-soaking treatments on the frequency and spectrum of mutations induced by sodium azide in CES 14 Mungbean variety

    International Nuclear Information System (INIS)

    Seeds of mungbean variety CES 14 were treated with 10-3 sodium azide for 2 hours buffered at pH 3 after various pre-soaking treatment durations of 0, 4, 6, 8, 10, 12, 14 and 16 hours. The biological parameters that were significantly affected by the treatments in the M1 were germination, seedling height and survival. The chlorophyll and other morphological mutations in the M2 gradually increased with increasing pre-soaking time. The treatment that had the lowest mutation rate was the 16-hour pre-soaked seeds. No chlorophyll mutation was noted in both the water and buffer control. One variant was noted, however, in the buffer control. (author)

  2. Solvent-resistant small molecule solar cells by roll-to-roll fabrication via introduction of azide cross-linkable group

    DEFF Research Database (Denmark)

    Chen, Mei-Rong; Fan, Cong-Cheng; Andersen, Thomas Rieks;

    2014-01-01

    A novel cross-linkable azide-functionalized diketopyrrolopyrrole based compound DPP(BT-N-3)(2) was designed and synthesized via Stille coupling. Cross-linking of such molecule could help us fabricate insoluble film which could be used to fabricate heterostructures through solution processing......, without dissolving the pre-patterned layers. In order to investigate the photovoltaic performances of the newly synthesized compound, large area solar cells were produced by roll coating technique. Two set of devices were fabricated by employing DPP(BT-N-3)(2) as either an electron donor or acceptor....... A best power conversion efficiency of 0.067%, combined with an open circuit voltage of 0.53 V, and a fill factor of 37.6% were obtained for the device with DPP(BT-N-3)(2) as an electron acceptor. In addition, we could prove that the large area small molecule based organic solar cells could be fabricated...

  3. Cu-MCM-41 nanoparticles: An efficient catalyst for the synthesis of 5-substituted 1-tetrazoles via [3+2] cycloaddition reaction of nitriles and sodium azide

    Indian Academy of Sciences (India)

    Mohammad Abdollahi-Alibeik; Ali Moaddeli

    2016-01-01

    [3+2] cycloaddition reaction of various types of nitriles and sodium azide (NaN3) were studied in the presence of nano-sized Cu-MCM-41 as an efficient recoverable heterogeneous catalyst. Nano-sized Cu-MCM-41 mesoporous molecular sieves with various Si/Cu molar ratios were synthesized by direct insertion of metal ions at room temperature. The textural properties of the materials have been studied by means of XRD, FTIR, SEM and TEM techniques. Catalytic behavior of Cu-MCM-41 was also investigated by pyridine absorption and potentiometric titration. The reactions data verified characterization results and show that Cu-MCM-41 with Si/Cu molar ratio of 20 has considerably better catalytic activity compared to the other molar ratios. To investigate reusability, the catalyst was recovered by simple filtration and reused for several cycles with consistent activity.

  4. Synthesis of chiral N-phosphoryl aziridines through enantioselective aziridination of alkenes with phosphoryl azide via Co(II-based metalloradical catalysis

    Directory of Open Access Journals (Sweden)

    Jingran Tao

    2014-06-01

    Full Text Available The Co(II complex of a new D2-symmetric chiral porphyrin 3,5-DiMes-QingPhyrin, [Co(P6], can catalyze asymmetric aziridination of alkenes with bis(2,2,2-trichloroethylphosphoryl azide (TcepN3 as a nitrene source. This new Co(II-based metalloradical aziridination is suitable for different aromatic olefins, producing the corresponding N-phosphorylaziridines in good to excellent yields (up to 99% with moderate to high enantioselectivities (up to 85% ee. In addition to mild reaction conditions and generation of N2 as the only byproduct, this new metalloradical catalytic system is highlighted with a practical protocol that operates under neutral and non-oxidative conditions.

  5. Antioxidant activity and inhibition of aflatoxin B1-, nifuroxazide-, and sodium azide-induced mutagenicity by extracts from Rhamnus alaternus L.

    Science.gov (United States)

    Ammar, Rebai Ben; Sghaier, Mohamed Ben; Boubaker, Jihed; Bhouri, Wissem; Naffeti, Aicha; Skandrani, Ines; Bouhlel, Ines; Kilani, Soumaya; Ghedira, Kamel; Chekir-Ghedira, Leila

    2008-07-10

    The effect of extracts obtained from Rhamnus alaternus L. leaves on genotoxicity and SOS response induced by aflatoxin B(1) (10 microg/assay) as well as nifuroxazide (20 microg/assay) was investigated in a bacterial assay system, i.e., the SOS chromotest with Escherichia coli PQ37. The evaluation of the mutagenic and antimutagenic actions of the same extracts against the sodium azide (1.5 microg/plate)-induced mutagenicity was assayed using the Salmonella typhimurium assay system. The R. alaternus tested extracts exhibited no genotoxicity either with or without the external S9 activation mixture. However, all the extracts, particularly aqueous extract (A) and its chloroformic fraction (A(2)) significantly decreased the genotoxicity induced by aflatoxin B(1) and nifuroxazide. Moreover, the different extracts showed no mutagenicity when tested with Salmonella typhimurium strains TA1535 and TA1538 either with or without the S9 mix. Aqueous extract as well as its A(2) fraction exhibited the highest level of protection towards the direct mutagen, sodium azide-induced response in TA1535 strain with mutagenicity inhibition percentages of 83.6% and 91.4%, respectively, at a dose of 250 microg/plate. The results obtained by the Ames test assay confirm those of SOS chromotest. These same active extracts exhibited high xanthine oxidase (XOD) inhibiting with respective IC(50) values of 208 and 137 microg/ml, and superoxide anion-scavenging effects (IC(50) values of 132 and 117 microg/ml) when tested in the XOD enzymatic assay system. Our findings emphasize the potential of R. alaternus to prevent mutations and also its antioxidant effect. PMID:18511029

  6. Nano structure zinc (II) Schiff base complexes of a N3-tridentate ligand as new biological active agents: Spectral, thermal behaviors and crystal structure of zinc azide complex

    Science.gov (United States)

    Montazerozohori, M.; Mojahedi Jahromi, S.; Masoudiasl, A.; McArdle, P.

    2015-03-01

    In this work, synthesis of some new five coordinated zinc halide/pseudo-halide complexes of a N3-tridentate ligand is presented. All complexes were subjected to spectroscopic and physical methods such as FT-IR, UV-visible, 1H and 13C NMR spectra, thermal analyses and conductivity measurements for identification. Based on spectral data, the general formula of ZnLX2 (X = Cl-, Br-, I-, SCN- and N3-) was proposed for the zinc complexes. Zinc complexes have been also prepared in nano-structure sizes under ultrasonic irradiation. X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were applied for confirmation of nano-structure character for the complexes. Among the complexes, zinc azide complex structure was analyzed by X-ray crystallography. This complex crystallizes as a triplet in trigonal system with space group of P31. The coordination sphere around the zinc center is well shown as a distorted trigonal bipyramidal with three nitrogen atoms from Schiff base ligand and two terminal azide nitrogen atoms attached to zinc ion. Various intermolecular interactions such as Nsbnd H⋯N, Csbnd H⋯N and Csbnd H⋯π hydrogen bonding interactions stabilize crystalline lattice so that they causes a three dimensional supramolecular structure for the complex. In vitro screening of the compounds for their antimicrobial activities showed that ZnLI2, ZnL(N3)2, ZnLCl2 and ZnL(NCS)2 were found as the most effective compound against bacteria of Bacillus subtilis, Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli respectively. Also ZnLI2 and ZnLCl2 complexes were found more effective against two selected fungi than others. Finally, thermal behaviors of the zinc complexes showed that they are decomposed via 2-4 thermal steps from room temperature up to 1000 °C.

  7. Regioselective Sequential Modification of Chitosan via Azide-Alkyne Click Reaction: Synthesis, Characterization, and Antimicrobial Activity of Chitosan Derivatives and Nanoparticles.

    Directory of Open Access Journals (Sweden)

    Atif Sarwar

    Full Text Available Recently, the attention of researchers has been drawn toward the synthesis of chitosan derivatives and their nanoparticles with enhanced antimicrobial activities. In this study, chitosan derivatives with different azides and alkyne groups were synthesized using click chemistry, and these were further transformed into nanoparticles by using the ionotropic gelation method. A series of chitosan derivatives was successfully synthesized by regioselective modification of chitosan via an azide-alkyne click reaction. The amino moieties of chitosan were protected during derivatization by pthaloylation and subsequently unblocked at the end to restore their functionality. Nanoparticles of synthesized derivatives were fabricated by ionic gelation to form complexes of polyanionic penta-sodium tripolyphosphate (TPP and cationic chitosan derivatives. Particle size analysis showed that nanoparticle size ranged from 181.03 ± 12.73 nm to 236.50 ± 14.32 nm and had narrow polydispersity index and positive surface charge. The derivatives and corresponding nanoparticles were evaluated in vitro for antibacterial and antifungal activities against three gram-positive and gram-negative bacteria and three fungal strains, respectively. The minimum inhibitory concentration (MIC of all derivatives ranged from 31.3 to 250 µg/mL for bacteria and 188 to1500 µg/mL for fungi and was lower than that of native chitosan. The nanoparticles with MIC ranging from 1.56 to 25 µg/mLfor bacteria and 94 to 750 µg/mL for fungi exhibited higher activity than the chitosan derivatives. Chitosan O-(1-methylbenzene triazolyl carbamate and chitosan O-(1-methyl phenyl sulfide triazolyl carbamate were the most active against the tested bacterial and fungal strains. The hemolytic assay on erythrocytes and cell viability test on two different cell lines (Chinese hamster lung fibroblast cells V79 and Human hepatic cell line WRL68 demonstrated the safety; suggesting that these derivatives could be

  8. Regioselective Sequential Modification of Chitosan via Azide-Alkyne Click Reaction: Synthesis, Characterization, and Antimicrobial Activity of Chitosan Derivatives and Nanoparticles.

    Science.gov (United States)

    Sarwar, Atif; Katas, Haliza; Samsudin, Siti Noradila; Zin, Noraziah Mohamad

    2015-01-01

    Recently, the attention of researchers has been drawn toward the synthesis of chitosan derivatives and their nanoparticles with enhanced antimicrobial activities. In this study, chitosan derivatives with different azides and alkyne groups were synthesized using click chemistry, and these were further transformed into nanoparticles by using the ionotropic gelation method. A series of chitosan derivatives was successfully synthesized by regioselective modification of chitosan via an azide-alkyne click reaction. The amino moieties of chitosan were protected during derivatization by pthaloylation and subsequently unblocked at the end to restore their functionality. Nanoparticles of synthesized derivatives were fabricated by ionic gelation to form complexes of polyanionic penta-sodium tripolyphosphate (TPP) and cationic chitosan derivatives. Particle size analysis showed that nanoparticle size ranged from 181.03 ± 12.73 nm to 236.50 ± 14.32 nm and had narrow polydispersity index and positive surface charge. The derivatives and corresponding nanoparticles were evaluated in vitro for antibacterial and antifungal activities against three gram-positive and gram-negative bacteria and three fungal strains, respectively. The minimum inhibitory concentration (MIC) of all derivatives ranged from 31.3 to 250 µg/mL for bacteria and 188 to1500 µg/mL for fungi and was lower than that of native chitosan. The nanoparticles with MIC ranging from 1.56 to 25 µg/mLfor bacteria and 94 to 750 µg/mL for fungi exhibited higher activity than the chitosan derivatives. Chitosan O-(1-methylbenzene) triazolyl carbamate and chitosan O-(1-methyl phenyl sulfide) triazolyl carbamate were the most active against the tested bacterial and fungal strains. The hemolytic assay on erythrocytes and cell viability test on two different cell lines (Chinese hamster lung fibroblast cells V79 and Human hepatic cell line WRL68) demonstrated the safety; suggesting that these derivatives could be used in future

  9. Study on HNS-Ⅳ Initiated by Flyer Driven by Cupric Azide%叠氮化铜驱动飞片起爆HNS-Ⅳ的研究

    Institute of Scientific and Technical Information of China (English)

    郭俊峰; 曾庆轩; 李明愉; 李兵

    2015-01-01

    针对以叠氮化铜微装药为基础的MEMS起爆传爆序列,利用数值模拟的方法研究起爆序列结构对起爆性能的影响.研究结果表明:飞片的剪切形状与文献结果相符.在装药直径一定的情况下,随着装药厚度的增加,飞片速度增加;当装药厚度为0.5mm、装药直径大于0.7mm时,增加装药直径不能进一步增加飞片速度;当叠氮化铜的尺寸为Φ0.7mm×0.5mm、加速膛长度为0.56mm时,系统能够起爆HNS-IV炸药.利用文献数据拟合得到了HNS-IV炸药的冲击起爆判据,模拟结果符合HNS-Ⅳ的冲击起爆判据.%Aimed at MEMS booster train based on micro charge involving cupric azide, numerical simulation method was utilized to study the effect of the structure of booster train on shock-initiation performance. Simulation results indicate that the shear of flyer shape is consistent with literature results. To a certain charge diameter, the flyer velocity is increased as the charge thickness increasing. While the flyer velocity cannot continue to increase with the diameter increasing, when the charge thickness is 0.5 mm and the charge diameter exceeds 0.7mm. When the charge size of cupric azide is Φ 0.7mm×0.5 mm and the length of barrel is 0.56 mm, HNS-IV explosive can be initiated by this system. The shock-initiation criterion of HNS-Ⅳ explosive fitted by literature results is determined, which is consistent with the simulation results.

  10. A signal-on electrochemical DNA biosensor based on potential-assisted Cu(I)-catalyzed azide-alkyne cycloaddition mediated labeling of hairpin-like oligonucleotide with electroactive probe.

    Science.gov (United States)

    Hu, Qiong; Kong, Jinming; Li, Yajie; Zhang, Xueji

    2016-01-15

    A novel electrochemical biosensor was developed for the signal-on detection of sequence-specific DNA by exploiting potential-assisted Cu(I)-catalyzed azide-alkyne cycloaddition (φCuAAC) as an efficient approach for the labeling of hairpin-like oligonucleotide (hairpin) with electroactive probe. The hairpins, dually labeled with thiol and azide at either terminal, were firstly self-assembled on gold electrode and served as the capture probes for the specific recognition of target DNA. Upon hybridization with target DNA, the surface-confined hairpins were unfolded, liberating the azide-containing terminals away from electrode surface. Subsequently, the unfolded hairpins were conveniently and efficiently labeled with ethynylferrocene (EFC) via the φCuAAC. The quantitatively labeled EFC was finally measured via differential pulse voltammetry (DPV) for the signal-on electrochemical detection of sequence-specific DNA. The biosensor presented a good linear response over the range from 1pM to 1nM with a detection limit of 0.62pM. Results also revealed that it was highly specific and held a good detection capability in serum samples. Furthermore, the ability to chemoselectively label hairpin-like oligonucleotide with signal reporter by electrical addressing, together with the simplicity and efficiency of the φCuAAC, makes it compatible with microfluidic devices and microelectrode arrays to achieve the miniaturized and multiplexed detections.

  11. Electronic Structure of Manganese Complexes of the Redox-Non-innocent Tetrazene Ligand and Evidence for the Metal-Azide/Imido Cycloaddition Intermediate.

    Science.gov (United States)

    Vaddypally, Shivaiah; McKendry, Ian G; Tomlinson, Warren; Hooper, Joseph P; Zdilla, Michael J

    2016-07-18

    The first synthetic manganese tetrazene complexes are described as a redox pair comprising anionic [Mn(N4 Ad2 )2 ](-) (1) and neutral Mn(N4 Ad2 )2 (2) complexes (N4 Ad2 =[Ad-N-N=N-N-Ad](2-) ). Compound 1 is obtained in two forms as lithium salts, one as a cationic Li2 Mn cluster, and one as a Mn-Li 1D ionic polymer. Compound 1 is electronically described as a Mn(III) center with two [N4 Ad2 ](2-) ligands. The one-electron oxidized 2 is crystalized in two morphologies, one as pure 2 and one as an acetonitrile adduct. Despite similar composition, the behavior of 2 differs in the two morphologies. Compound 2-MeCN is relatively air and temperature stable. Crystalline 2, on the other hand, exhibits a compositional, dynamic disorder wherein the tetrazene metallacycle ring-opens into a metal imide/azide complex detectable by X-ray crystallography and FTIR spectroscopy. Electronic structure of 2 was examined by EPR and XPS spectroscopies and DFT calculations, which indicate 2 is best described as a Mn(III) ion with an anion radical delocalized across the two ligands through spin-polarization effects. PMID:27339316

  12. Preparation of Azidated Polybutadiene(Az-PBD)/Ethylene-Vinyl Acetate Copolymer(EVA) Blends for the Application of Energetic Thermoplastic Elastomer

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Sang Won; Choi, Myung Chan; Chang, Young-Wook; Noh, Si-Tae [Hanyang University, Ansan (Korea, Republic of); Kwon, Soon Kil [Agency for Defense Development, Daejeon (Korea, Republic of)

    2015-02-15

    A new energetic thermoplastic elastomer based on the azidated polybutadiene(Az-PBD)/ethylene vinyl acetate copolymer (EVA) blends was prepared, and structure and properties of the blends were investigated by SEM, DSC, DMA, tensile testing and combustion test. The Az-PBD was synthesized via a two-step process involving the addition reaction of commercially available 1,2-PBD with Br{sub 2} and subsequent nucleophilic substitution reaction of the brominated PBD with NaN{sub 3}. EVA/Az-PBD with 90/10, 80/20, 70/30 (wt/wt) was prepared by a solution blending. SEM, DSC, and DMA results revealed that the blends are partially compatible and Az-PBD is dispersed in continuous EVA matrix. Tensile test showed that modulus and tension set increased while elongation-at-break of the blends decreased with increasing Az-PBD content in the blends, but all the blends showed a elongation at break as high as 700% and a tension set of less than 5%, indicating that the blends are typically elastomeric. Combustion test showed that, with increasing Az-PBD content in the blend, higher energy can be released.

  13. Phlomis mauritanica extracts reduce the xanthine oxidase activity, scavenge the superoxide anions, and inhibit the aflatoxin B1-, sodium azide-, and 4-nitrophenyldiamine-induced mutagenicity in bacteria.

    Science.gov (United States)

    Limem, Ilef; Bouhlel, Ines; Bouchemi, Meriem; Kilani, Soumaya; Boubaker, Jihed; Ben-Sghaier, Mohamed; Skandrani, Ines; Behouri, Wissem; Neffati, Aicha; Ghedira, Kamel; Chekir-Ghedira, Leila

    2010-06-01

    Four extracts were prepared from the leaves of Phlomis mauritanica: lyophilized infusion, total oligomer flavonoids, methanol, and ethyl acetate extracts. The antimutagenic properties of these extracts were investigated by assessing the inhibition of the mutagenic effects of direct-acting mutagens such as sodium azide and 4-nitrophenylenediamine and indirect-acting mutagens like aflatoxin B1 (AFB1) using the Ames assay. The four extracts prepared from P. mauritanica strongly inhibit the mutagenicity induced by AFB1 in both Salmonella typhimurium TA 100 and TA 98 assay systems. Lyophilized infusion and methanol extracts at the dose of 250 microg per plate reduced AFB1 mutagenicity by 93% and 91%, respectively, in S. typhymurium strain TA 100. We examined also the antioxidant effect of these extracts by the enzymatic xanthine/xanthine oxidase assay. Result indicated that total oligomer flavonoids and ethyl acetate and methanol extracts were potent inhibitors of xanthine oxidase activity. In contrast, lyophilized infusion, total oligomer flavonoids, and methanol extracts exhibited a high degree of superoxide anion scavenging. Our findings emphasize the potential of P. mauritanica extracts to prevent mutations and oxidant effects. Furthermore, the results presented here could be an additional argument to support the use of this species as a medicinal and dietary plant. PMID:20406134

  14. Anti-inflammatory drugs interacting with Zn (II) metal ion based on thiocyanate and azide ligands: Synthesis, spectroscopic studies, DFT calculations and antibacterial assays

    Science.gov (United States)

    Chiniforoshan, Hossein; Tabrizi, Leila; Hadizade, Morteza; Sabzalian, Mohammad R.; Chermahini, Alireza Najafi; Rezapour, Mehdi

    2014-07-01

    Zinc (II) complexes with non-steroidal anti-inflammatory drugs (NSAIDs) naproxen (nap) and ibuprofen (ibu) were synthesized in the presence of nitrogen donor ligands (thiocyanate or azide). The complexes were characterized by elemental analysis, FT-IR, 1H NMR and UV-Vis spectroscopes. The binding modes of the ligands in complexes were established by means of molecular modeling of the complexes, and calculation of their IR, NMR and absorption spectra at DFT (TDDFT)/B3LYP level were studied. The experimental and calculated data verified monodentate binding through the carboxylic oxygen atoms of anti-inflammatory drugs in the zinc complexes. The calculated 1H, FT-IR and UV-Vis data are in better agreement with the experimental results, and confirm the predicted tetrahedral structures for the Zn (II) complexes. In addition to DFT calculations of complexes, natural bond orbital (NBO) was performed at B3LYP/6-31+G(d,p) level of theory. Biological studies showed the antibacterial activity of zinc complexes against Gram-positive and Gram-negative bacterial strains.

  15. Circular DNA by "Bis-Click" Ligation: Template-Independent Intramolecular Circularization of Oligonucleotides with Terminal Alkynyl Groups Utilizing Bifunctional Azides.

    Science.gov (United States)

    Yang, Haozhe; Seela, Frank

    2016-01-22

    A highly effective and convenient "bis-click" strategy was developed for the template-independent circularization of single-stranded oligonucleotides by employing copper(I)-assisted azide-alkyne cycloaddition. Terminal triple bonds were incorporated at both ends of linear oligonucleotides. Alkynylated 7-deaza-2'-deoxyadenosine and 2'-deoxyuridine residues with different side chains were used in solid-phase synthesis with phosphoramidite chemistry. The bis-click ligation of linear 9- to 36-mer oligonucleotides with 1,4-bis(azidomethyl)benzene afforded circular DNA in a simple and selective way; azido modification of the oligonucleotide was not necessary. Short ethynyl side chains were compatible with the circularization of longer oligonucleotides, whereas octadiynyl residues were used for short 9-mers. Compared with linear duplexes, circular bis-click constructs exhibit a significantly increased duplex stability over their linear counterparts. The intramolecular bis-click ligation protocol is not limited to DNA, but may also be suitable for the construction of other macrocycles, such as circular RNAs, peptides, or polysaccharides.

  16. Detection of nearest neighbors to specific fluorescently tagged ligands in rod outer segment and lymphocyte plasma membranes by photosensitization of 5-iodonaphthyl 1-azide

    Energy Technology Data Exchange (ETDEWEB)

    Raviv, Y.; Bercovici, T.; Gitler, C.; Salomon, Y. (Weizmann Institute of Science, Rehovot (Israel))

    1989-02-07

    Lima bean agglutinin-fluorescein 5-isothiocyanate conjugate (FluNCS-lima bean lectin) interacts with specific receptor molecules on membranes both from the rod outer segment (ROS) of the frog retina and from S49 mouse lymphoma cells. When (125I)-5-iodonaphthyl 1-azide (125I-INA), which freely and randomly partitions into the lipid bilayer, is added to membranes and the suspension is irradiated at 480 nm, the FluNCS-conjugated lectin photosensitizes the (125I)INA but only at discrete sites. This results in the selective labeling of specific proteins: an 88-kDa protein on ROS membranes and a 56-kDa protein on S49 plasma membranes. Labeling is dependent upon the interaction of the FluNCS-lectin with glycosylated receptor sites, since N-acetylgalactosamine, but not methyl alpha-mannoside, blocked labeling of the 56-kDa protein on S49 membranes. In contrast, a random labeling pattern of membrane proteins was observed upon irradiation at 480 nm using other fluorescein conjugates, such as FluNCS-bovine serum albumin (FluNCS-BSA) or FluNCS-soybean trypsin inhibitor (FluNCS-STI), which interact with cell membranes in a nonselective manner, or with N-(fluorescein-5-thiocarbamoyl)-n-undecyclamine (FluNCS-NHC11), which is freely miscible in the membrane lipid. Random labeling was also obtained by direct photoexcitation of (125I)INA at 314 nm, with no distinct labeling of the 88- and 56-kDa proteins in the respective membranes. These results suggest that protein ligands can be used to guide sensitizers to discrete receptor sites and lead to their selective labeling by photosensitized activation of (125I)INA.

  17. Utilizing copper(I) catalyzed azide-alkyne Huisgen 1,3-dipolar cycloaddition for the surface modification of colloidal particles with electroactive and emissive moieties

    Science.gov (United States)

    Rungta, Parul

    " chemistry; Aqueous-phase 83 nm poly(propargyl acrylate) (PA) nanoparticles were surface-functionalized with sparingly water soluble fluorescent moieties through a copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) (i.e., "click" transformation) to produce fluoroprobes with a large Stokes shift. For moieties which could not achieve extensive surface coverage on the particles utilizing a standard click transformation procedure, the presence of beta-cyclodextrin (beta-CD) during the transformation enhanced the grafting density onto the particles. For an oxadiazole containing molecule (AO), an azide-modified coumarin 6 (AD1) and a polyethylene glycol modified naphthalimide-based emitter (AD2), respectively, an 84%, 17% and 5% increase in the grafting densities were observed, when the transformation was performed in the presence of beta-CD. In contrast, a carbazolyl-containing moiety (AC) exhibited a slight retardation in the final grafting density when beta-CD was employed. Photoluminescence studies indicated that AC & AO when attached to the particles form an exciplex. An efficient energy transfer from the exciplex to the surface attached AD2 resulted in a total Stokes shift of 180 nm for the modified particles. (3) The synthesis and characterization of near-infrared (NIR) emitting particles for potential applications in cancer therapy. PA particles were surface modified through the "click" transformation of an azide-terminated indocyanine green (azICG), an NIR emitter, and poly(ethylene glycol) (azPEG) chains of various molecular weights. The placement of azICG onto the surface of the particles allowed for the chromophores to complex with bovine serum albumin (BSA) when dispersed in PBS that resulted in an enhancement of the dye emission. In addition, the inclusion of azPEG with the chromophores onto the particle surface resulted in a synergistic nine-fold enhancement of the fluorescence intensity, with azPEGs of increasing molecular weight amplifying the response

  18. 叠氮化钠中毒临床及神经电生理特点%Clinical and nerve electrophysiological features of sodium azide poisoning

    Institute of Scientific and Technical Information of China (English)

    何燕霞; 翁小健; 胡宁

    2015-01-01

    Objective To observe the clinical and nerve electrophysiological features of sodium azide poisonin. Method The clinical data of 11 patients with sodium azide poisonin were analyzed retrospectively.Results In this group, the first symptoms was numbness in 4 cases, weakness in 3 cases, walking instability in 2 cases, dizziness and nausea in 2 cases.The major clinical manifestations were numbness in 8 cases, weakness in 6 cases, walking instability in 4 cases, dizziness and nausea in 3 cases, leptophonia in 2 cases, diplopia in 2 cases, limb muscle strength loss in 7 cases, reducing muscle tension in 3 cases, weakened tendon reflex in 3 cases, skin needle drops in 3 cases.Electrophysiological examination showed motor nerve conduction velocity ( MCV) was slower, distal latency ( DML) and amplitude ( AMP) were reduced; the sensory nerve conduction velocity ( SCV) was slower, and AMP was reduced.The latency (Lat) and wave interval of brainstem auditory evoked potential (BAEP) and visual evoked potential ( VEP) , somatosensory evoked potentials ( SEP) were prolonged, and AMP was reduced.Compared with pre-treatment, the abnormal rates of MCV, AMP, DML of median nerve, ulnar nerve, deep peroneal nerve and SCV, AMP of median nerve, ulnar nerve, superficial peroneal nerve, sural nerve and AMP of SEP after treatment had no statistically significant (all P>0.05).Compared with pre-treatment, the abnormal rates of Lat of BAEP, VEP, SEP andⅢ-Ⅴof BAEP and AMP of BAEP, VEP had no statistically significant (P<0.05-0.01).Conclusions The major clinical symptoms of sodium azide poisoning are numbness, weakness, unstable walking, dizziness, diplopia. Electrophysiological examination showed MCV is slower, DML and AMP are reduced; SCV is slower, and AMP is reduced.The Lat and wave interval of evoked potential are prolonged, and AMP is reduced.%目的:探讨叠氮化钠中毒的临床及神经电生理特点。方法回顾性分析11例叠氮化钠中毒患者的临床资料。结果

  19. Synthesis, characterization and crystal structure determination of Mn (II) ion based 1D polymer constructed from 2, 2‧ bipyridyl and azide group, its thermal stability, magnetic properties and Hirshfeld surface analysis

    Science.gov (United States)

    Mudsainiyan, R. K.; Jassal, Amanpreet Kaur; Chawla, S. K.

    2015-05-01

    The 1-D polymeric complex (I) is having formula [Mn(2,2‧-BP).(N3)2]n, which has been crystallized in distilled water and characterized by elemental analyses, FT-IR spectrum, powder X-ray diffraction analyses and single-crystal diffraction analysis. This polymer possesses 1D helical chains or coils where Mn-azide-Mn forms the base of the coil which is alternatively garlanded by rigid bi-pyridine rings, where coordinates are in anti-fashion. The Mn (II) ions in the repeating units are linked by two end-on azide groups which extend through the two end-to-end azide ligands to the next unit forming a 1-D polymeric chain. The present study suggests that the use of this rigid and neutral building block leads to give better arrangement of the polymeric motif with [010] chains in 2-c uninodal net. During investigation of strong or weak intermolecular interactions, X-ray diffraction analysis and Hirshfeld surface analysis give rise to comparable results but in Hirshfeld surface analysis, two-third times more results of close contacts are obtained. The fingerprint plots demonstrate that these weak non-bonding interactions are important for stabilizing the crystal packing. Magnetic properties of the complex (I) were analyzed on the basis of an alternating ferro- and antiferromagnetic Heisenberg chain of Mn (II) ions. The J-exchange parameters found are J1=64.3 K (45.3 cm-1), and J2=-75.7 K (-53.3 cm-1). Magnetic properties are discussed in comparison with those of other similar molecular magnets of [Mn(L-L)(N3)2]n type.

  20. Synthesis of novel 17-(5'-iodo)triazolyl-3-methoxyestrane epimers via Cu(I)-catalyzed azide-alkyne cycloadditon, and an evaluation of their cytotoxic activity in vitro.

    Science.gov (United States)

    Schneider, Gyula; Görbe, Tamás; Mernyák, Erzsébet; Wölfling, János; Holczbauer, Tamás; Czugler, Mátyás; Sohár, Pál; Minorics, Renáta; Zupkó, István

    2015-06-01

    The regioselective Cu(I)-catalyzed 1,3-dipolar cycloaddition of 3-methoxyestrane 17α- and 17β-azide epimers (3 and 5) with different terminal alkynes afforded novel 1,4-substituted triazolyl derivatives (8a-f and 11a-f). If the Ph3P in the classical CuAAC process was replaced by Et3N, the formation of small quantities of 5-iodotriazoles (9a-f and 11a-f) was observed. For the preparation of 5-iodo-1,2,3-triazoles (9a-f and 11a-f), an improved method was developed, directly from steroidal azides and terminal alkynes, in reactions mediated by CuI and ICl as iodinating agents. The antiproliferative activities of the structurally related triazoles were determined in vitro with the microculture tetrazolium assay on six malignant human cell lines of gynecological origin (HeLa, A2780, MCF7, MDA-MB-231, MDA-MB-361 and T47D). X-ray analysis revealed the presence of the iodo substituent on the 1,2,3-triazole ring. PMID:25732071

  1. Layer-by-Layer Fabrication of Porphyrin Multilayer Films via Copper(I)-Catalyzed Azide-Alkyne Cycloaddition: Film Properties and Applications in Dye-Sensitized Solar Cells

    Science.gov (United States)

    Palomaki, Peter Karl Bunk

    Solar energy may be the only renewable source of energy available to the human race that could provide the energy we require while at the same time minimizing negative impacts on the planet and population. These characteristics may be instrumental in diminishing the potential for societal conflict. In order for photovoltaic devices to succeed on a global scale, research and development must lead to reduced costs and/or increased efficiency. Dye-Sensitized Solar Cells (DSSCs) are one class of nextgeneration photovoltaic technologies with the potential to realize these goals. Herein, I describe efforts towards developing a new light harvesting array of chromophores assembled on oxide substrates using copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC or ‘click’ chemistry) that could prove useful in improving DSCC performance while maintaining low cost and simple fabrication. Specifically, molecular multilayers of porphyrin-based chromophores have been fabricated via sequential selflimiting CuAAC reactions to generate multilayered light harvesting films. Films of synthetic porphyrins, perylenes, and mixtures of the two are constructed in order to highlight the versatility of this molecular layer-by-layer (LbL) technique. Characterization in the form of electrochemical techniques, UV-Visible spectroscopy, infrared spectroscopy (IR), and water contact angle all indicate that the films are reacting as expected. Film thickness and morphology are investigated using X-ray reflectivity showing that film growth displays a high degree of linearity, while the roughness increases with thickness. Growth angles based on the porphyrin plane are estimated via a comparison of molecular models and experimentally determined thickness measurements. A more finite measurement of growth angle (and as a result the primary bonding mode) is determined by grazing angle IR spectroscopy. Blocking layer studies suggest that the films could be useful as a self-passivating layer in DSSCs to

  2. Synthesis, characterization and crystal structure determination of Mn (II) ion based 1D polymer constructed from 2, 2′ bipyridyl and azide group, its thermal stability, magnetic properties and Hirshfeld surface analysis

    International Nuclear Information System (INIS)

    The 1-D polymeric complex (I) is having formula [Mn(2,2′-BP).(N3)2]n, which has been crystallized in distilled water and characterized by elemental analyses, FT-IR spectrum, powder X-ray diffraction analyses and single-crystal diffraction analysis. This polymer possesses 1D helical chains or coils where Mn–azide–Mn forms the base of the coil which is alternatively garlanded by rigid bi-pyridine rings, where coordinates are in anti-fashion. The Mn (II) ions in the repeating units are linked by two end-on azide groups which extend through the two end-to-end azide ligands to the next unit forming a 1-D polymeric chain. The present study suggests that the use of this rigid and neutral building block leads to give better arrangement of the polymeric motif with [010] chains in 2-c uninodal net. During investigation of strong or weak intermolecular interactions, X-ray diffraction analysis and Hirshfeld surface analysis give rise to comparable results but in Hirshfeld surface analysis, two-third times more results of close contacts are obtained. The fingerprint plots demonstrate that these weak non-bonding interactions are important for stabilizing the crystal packing. Magnetic properties of the complex (I) were analyzed on the basis of an alternating ferro- and antiferromagnetic Heisenberg chain of Mn (II) ions. The J-exchange parameters found are J1=64.3 K (45.3 cm−1), and J2=−75.7 K (−53.3 cm−1). Magnetic properties are discussed in comparison with those of other similar molecular magnets of [Mn(L–L)(N3)2]n type. - - Highlights: • Synthesized 1-D polymeric complex of Mn (II) ions with 2, 2′ bipyridyl and azide group. • X-ray data of complex (I) is in a good agreement with TGA and other spectroscopic techniques. • DFT calculations were done and compared with the parameter of experimental and theoretical data. • Intermolecular interactions calculated by Hirshfeld surface analysis compared with X-ray data

  3. Synthesis, characterization and crystal structure determination of Mn (II) ion based 1D polymer constructed from 2, 2′ bipyridyl and azide group, its thermal stability, magnetic properties and Hirshfeld surface analysis

    Energy Technology Data Exchange (ETDEWEB)

    Mudsainiyan, R.K., E-mail: mudsainiyanrk@gmail.com; Jassal, Amanpreet Kaur; Chawla, S.K., E-mail: sukhvinder.k.chawla@gmail.com

    2015-05-15

    The 1-D polymeric complex (I) is having formula [Mn(2,2′-BP).(N{sub 3}){sub 2}]{sub n}, which has been crystallized in distilled water and characterized by elemental analyses, FT-IR spectrum, powder X-ray diffraction analyses and single-crystal diffraction analysis. This polymer possesses 1D helical chains or coils where Mn–azide–Mn forms the base of the coil which is alternatively garlanded by rigid bi-pyridine rings, where coordinates are in anti-fashion. The Mn (II) ions in the repeating units are linked by two end-on azide groups which extend through the two end-to-end azide ligands to the next unit forming a 1-D polymeric chain. The present study suggests that the use of this rigid and neutral building block leads to give better arrangement of the polymeric motif with [010] chains in 2-c uninodal net. During investigation of strong or weak intermolecular interactions, X-ray diffraction analysis and Hirshfeld surface analysis give rise to comparable results but in Hirshfeld surface analysis, two-third times more results of close contacts are obtained. The fingerprint plots demonstrate that these weak non-bonding interactions are important for stabilizing the crystal packing. Magnetic properties of the complex (I) were analyzed on the basis of an alternating ferro- and antiferromagnetic Heisenberg chain of Mn (II) ions. The J-exchange parameters found are J{sub 1}=64.3 K (45.3 cm{sup −1}), and J{sub 2}=−75.7 K (−53.3 cm{sup −1}). Magnetic properties are discussed in comparison with those of other similar molecular magnets of [Mn(L–L)(N{sub 3}){sub 2}]{sub n} type. - - Highlights: • Synthesized 1-D polymeric complex of Mn (II) ions with 2, 2′ bipyridyl and azide group. • X-ray data of complex (I) is in a good agreement with TGA and other spectroscopic techniques. • DFT calculations were done and compared with the parameter of experimental and theoretical data. • Intermolecular interactions calculated by Hirshfeld surface analysis

  4. Kinetics Studies of the Reaction of Co(bpb) with the Azide Ion in Binary Methanol-Water Mixtures%甲醇-水二元混合物中Co(bpb)与叠氮离子反应的动力学研究

    Institute of Scientific and Technical Information of China (English)

    HASHEMI Javad; ALIZADEH Naader; MEGHDADI Soraia; AMIRNASR Mehdi

    2009-01-01

    Co(bpb)[bpbH2 is N,N'-o-phenylenebis(pyridine-2-carboxamide),C18H12N4O2] complex has active axial sites like a porphyrin complex.We studied the coordination of azide ion (N3-) to Co(bpb) in binary methanol-water mixtures by spectropbotometric method at the temperature range of 283-303 K.From the temperature dependence of the rate constant,activation parameters (Ea,△H#,△S#,and △G# were obtained.An isokinetic temperature at about 302 K was observed at which the formation rate of Co(bpb)-N3- was more or less independent of the solvent composition.The resulting △H against TAS plot showed a good linear correlation,indicating the existence of enthalpy-entropy compensation in azide complexation process.Under optimum conditions and based on the absorbance of Co(bpb)-N3- produced through complex formation,a spectrophotometric method for the determination of N3- in solution was developed.A linear relationship between the absorbance and N3- concentration was obtained in the range of (0.85-5.00)× was applied to the determination of N3- anion in real water samples.Key Words: Spectrophotometric;Kinetics;Binary mixture;Azide determination;Water sample

  5. Synthesis of {sup 14}C-labelled hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4,6-trinitrotoluene (TNT), nitrocellulose (NC) and glycidyl azide polymer (GAP) for use in assessing the biodegradation potential of these energetic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ampleman, G.; Thiboutot, S.; Lavigne, J.; Marois, A. [Defence Research Establishment Valcartier, Courcelette, PQ (Canada); Hawari, J.; Jones, A.M.; Rho, D. [National Research Council of Canada, Ottawa, ON (Canada)

    1995-06-01

    Within the framework of an R and D project on bioremediation of soils contaminated with energetic compounds, the biodegradation of energetic products such as hexogen (RDX), trinitrotoluene (TNT), nitrocellulose (NC) and glycidyl azide polymer (GAP) is under study. Microcosm assays must be performed with radioactive carbon-14 labelled products in order to follow the biodegradation process. {sup 14}C-RDX was prepared by nitration of hexamethylenetetramine (HMTA) according to the Hale process. {sup 14}C-ring and methyl labelled TNTs synthesized according to the Dorey and Carper procedure. {sup 14}C-cellulose was synthesized from {sup 14}C-glucose by Acetobacter xylinum. Nitration of the {sup 14}C-cellulose yielded {sup 14}C-nitrocellulose. {sup 14}C-glycidyl azide polymer was obtained by polymerization and azidation of {sup 14}C-epichlorohydrin (ECH) which was synthesized from {sup 14}C-glycerol. Hydrochlorination of {sup 14}C-glycerol and epoxidation of the resulting {sup 14}C-1,3-dichloro 2-propanol yielded {sup 14}C-ECH. The syntheses of these {sup 14}C-labelled explosives are described in this paper. (Author).

  6. Síntese e caracterização do polímero energético Metil Azoteto de Glicidila (GAP via análises instrumentais Characterization of energetic Methyl Glycidyl Azide Polymer

    Directory of Open Access Journals (Sweden)

    Jairo Sciamareli

    2009-06-01

    Full Text Available Na área aeroespacial é constante a pesquisa em busca de novos materiais que permitam um melhor desempenho de foguetes, mísseis e explosivos. Entre outros, compostos mais energéticos, de maior estabilidade térmica e/ou química, menos agressivos ao meio ambiente, de menor custo e de mais fácil manuseio. Um destes materiais é o metil azoteto de glicidila (GAP, que pode ser utilizado para produzir propelentes mais energéticos e/ou sem fumaça, bem como composições explosivas de baixa sensibilidade. O GAP foi sintetizado e caracterizado por análises FT-IR, elementar, cromatográfica de permeação de gel e térmica.To obtain more energetic, safe propellants, with improved performance, better mechanical properties and low cost, new materials have been researched and tested. One of these materials is Methyl Glycidyl Azide Polymer (GAP. It can be used to make energetic and/or smokeless propellants as well as composite explosives with low sensitivity. GAP was synthesized and characterized by FT-IR, elemental analysis, gel permeation chromatography (GPC and thermal analysis.

  7. Synthesis, Spectroscopy, Theoretical, and Electrochemical Studies of Zn(II, Cd(II, and Hg(II Azide and Thiocyanate Complexes of a New Symmetric Schiff-Base Ligand

    Directory of Open Access Journals (Sweden)

    Morteza Montazerozohori

    2013-01-01

    Full Text Available Synthesis of zinc(II/cadmium(II/mercury(II thiocyanate and azide complexes of a new bidentate Schiff-base ligand (L with general formula of MLX2 (M = Zn(II, Cd(II, and Hg(II in ethanol solution at room temperature is reported. The ligand and metal complexes were characterized by using ultraviolet-visible (UV-visible, Fourier transform infrared (FT-IR, 1H- and 13C-NMR spectroscopy and physical characterization, CHN analysis, and molar conductivity. 1H- and 13C-NMR spectra have been studied in DMSO-d6. The reasonable shifts of FT-IR and NMR spectral signals of the complexes with respect to the free ligand confirm well coordination of Schiff-base ligand and anions in an inner sphere coordination space. The conductivity measurements as well as spectral data indicated that the complexes are nonelectrolyte. Theoretical optimization on the structure of ligand and its complexes was performed at the Becke’s three-parameter hybrid functional (B3 with the nonlocal correlation of Lee-Yang-Parr (LYP level of theory with double-zeta valence (LANL2DZ basis set using GAUSSIAN 03 suite of program, and then some theoretical structural parameters such as bond lengths, bond angles, and torsion angles were obtained. Finally, electrochemical behavior of ligand and its complexes was investigated. Cyclic voltammograms of metal complexes showed considerable changes with respect to free ligand.

  8. Ligand Synthesis Catalyst and Complex Metal Ion: Multicomponent Synthesis of 1,3-Bis(4-phenyl-[1,2,3]triazol-1-yl-propan-2-ol Copper(I Complex and Application in Copper-Catalyzed Alkyne-Azide Cycloaddition

    Directory of Open Access Journals (Sweden)

    María Teresa Ramírez-Palma

    2016-01-01

    Full Text Available A new bistriazole copper complex was synthesized by direct treatment of an alkyne, an azide, and CuI as copper salt through in situ ligand formation under a multicomponent reaction process. This complex was analyzed by XPS, TGA, DSC, and SEM techniques and revealed a triangular-shaped morphology, high thermal stability, and catalytic power in CuAAC reactions, requiring only 2.5% mol catalyst to afford 1,2,3-triazoles in good yields which can be reused at least for 4 cycles.

  9. FT-IR Study on the Catalytic Reaction Kinetics of Glycidyl Azide Polymer with N100%FT-IR 法研究 GAP 与 N100的催化反应动力学

    Institute of Scientific and Technical Information of China (English)

    申飞飞; Abbas Tanver; 罗运军

    2014-01-01

    The reaction kinetics of glycidyl azide polymer (GAP)with polyisocyanate (N100)was studied by the FT-IR method.Using triphenyl bismuth(TPB)and di-n-butyltin dilaurate (T12)as catalysts,the reaction mecha-nism function and activation energies of the two systems at 60,70,80 and 90℃ were obtained.The results show that the curing reaction of GAP/N100 system is determined as first order reaction.When the content of TPB and T12 is 0.015%,respectively,the whole curing reaction process using TPB as catalyst obeys the first-order kinetic law,the system using T12 as catalyst obeys the first-order kinetic law and the reaction mechanism function is g(α)=-ln(1 -α)when the degree of conversation is less than 80%,while the system obeys three-dimensional (spheri-cal symmetric)diffusion and the reaction mechanism function is g(α)=[1 -(1-α)1/3 ]2 when the degree of conver-sation is over 80%.The curing reaction time of GAP/N100 using T12 as catalyst is much less than that of GAP/N100 using TPB as catalyst.%采用傅里叶变换红外(FT-IR)研究了聚叠氮缩水甘油醚(GAP)与多异氰酸酯(N100)之间的反应动力学。得到60、70、80、90℃下分别用 TPB(三苯基铋)和 T12(二月桂酸二丁基锡)作催化剂时体系的反应机理函数和表观活化能。结果表明,GAP/N100体系的固化反应为一级动力学反应;当两种固化催化剂质量分数均为0.015%,以TPB 为催化剂时体系整个固化过程遵循一级动力学规律;以 T12为催化剂时,在转化率达80%之前,体系遵循一级反应规律,反应机理函数为 g(α)=-ln(1-α),之后反应机理函数转变为三维(球对称)扩散 g(α)=[1-(1-α)1/3]2;用 T12作催化剂时,GAP/N100固化反应结束时间远低于用 TPB 作催化剂时所用时间。

  10. Glycidyl Azide Polymer-based Enhanced Energy LOVA Gun Propellant

    Directory of Open Access Journals (Sweden)

    R. R. Sanghavi

    2006-07-01

    Full Text Available In this study, cyclotrimethylene trinitramine propellants with triacetin (TA-plasticisedcellulose acetate (CA and nitrocellulose (NC combination as binders were evaluated for lowvulnerable ammunition (LOVA. Triacetin was replaced by energetic plasticiser; glycidyl azidepolymer (GAP in increments to enhance the performance in terms of force constant . In additionto ballistics, parameters like vulnerability, mechanical and thermal properties of GAP-basedpropellants in comparison to those of TA-based propellants, were also determined. The studybrings out that the incorporation of 2-6 per cent GAP in place of TA resulted in the enhancementof force constant by 22-70 J/g and improved overall combustion characteristics. DSC revealedthat thermal decomposition of GAP-LOVA propellants evolved more energy than TA-LOVApropellants. GAP-based LOVA propellant similar to TA-plasticised LOVA propellant, was foundsuperior to NQ propellant in vulnerability tests as well as in hot fragment conductive ignition(HFCI studies. As regards mechanical properties, incorporation of GAP resulted in improvedcompression strength.

  11. Glycidyl Azide Polymer-based Enhanced Energy LOVA Gun Propellant

    OpenAIRE

    R. R. Sanghavi; P. J. Kamale; M.A.R. Shaikh; T. K. Chakraborthy; S. N. Asthana; Amarjit Singh

    2006-01-01

    In this study, cyclotrimethylene trinitramine propellants with triacetin (TA)-plasticisedcellulose acetate (CA) and nitrocellulose (NC) combination as binders were evaluated for lowvulnerable ammunition (LOVA). Triacetin was replaced by energetic plasticiser; glycidyl azidepolymer (GAP) in increments to enhance the performance in terms of force constant . In additionto ballistics, parameters like vulnerability, mechanical and thermal properties of GAP-basedpropellants in comparison to those o...

  12. Synthesis of Quinoxaline Derivatives via Tandem Oxidative Azidation/Cyclization Reaction of N-Arylenamines.

    Science.gov (United States)

    Ma, Haichao; Li, Dianjun; Yu, Wei

    2016-02-19

    A new method was developed for the synthesis of quinoxalines. This method employs N-arylenamines and TMSN3 as the starting materials and implements two oxidative C-N bond-forming processes in a tandem pattern by using (diacetoxyiodo)benzene as the common oxidant. The present reaction conditions are mild and simple and thus are useful in practical synthesis.

  13. DFT Study of Dimethylaluminum Azide Clusters:Structures, Energies, Frequencies and Thermodynamic Properties

    Institute of Scientific and Technical Information of China (English)

    XIA, Qi-Ying(夏其英); XIAO, He-Ming(肖鹤鸣); JU, Xue-Hai(居学海); GONG, Xue-Dong(贡雪东)

    2004-01-01

    DFT/B3LYP method with SDD basis set has been applied to the systems of (Me2AlN3)n (n=1-3). (Me2AlN3)2 was found to exhibit the planar Al2N2 ring structure. (Me2AlN3)3 involving a six-membered Al3N3 ring was found to exhibit two minima with very similar binding energies(—265.52 and —256.10 kJ·mol-1).Compared to the monomer, both the structural changes and charge transfers for the clusters are large. Frequency calculations were carried out on each optimized structure and its IR spectra were discussed. Thermodynamic properties reveal that the dimer is the main component in the systems of the (Me2AlN3)n (n= 1-3).

  14. Catalytic behavior of surfactant-containing-MCM-41 mesoporous materials for cycloaddition of 4-nitrophenyl azide

    OpenAIRE

    Boukoussa, Bouhadjar; Zeghada, Sarah; Bentabed-Ababsa, Ghenia; Hamacha, Rachida; Derdour, Aïcha; BENGUEDDACH Abdelkader; Mongin, Florence

    2014-01-01

    Si-MCM-41, Ga-MCM-41 and Al-MCM-41 mesoporous catalysts (with Si/Al = 80 and Si/Ga = 80) were prepared by direct synthesis under hydrothermal crystallization method using sodium aluminate or gallium sulfate and tetraethyl orthosilicate (TEOS) as aluminum or gallium and silica sources, respectively. The structural features of the materials were determined by various physico-chemical techniques such as X-ray diffraction (XRD), nitrogen sorption at 77 K, Fourier transform infrared spectroscopy (...

  15. Synthesis of Dendronized Poly(l-Glutamate) via Azide-Alkyne Click Chemistry

    OpenAIRE

    Peter Perdih; Andrej Kržan; Ema Žagar

    2016-01-01

    Poly(l-glutamate) (PGlu) was modified with a second-generation dendron to obtain the dendronized polyglutamate, P(Glu-D). Synthesized P(Glu-D) exhibited a degree of polymerization (DPn) of 46 and a 43% degree of dendronization. Perfect agreement was found between the P(Glu-D) expected structure and the results of nuclear magnetic resonance spectroscopy (NMR) and size-exclusion chromatography coupled to a multi-angle light-scattering detector (SEC-MALS) analysis. The PGlu precursor was modifie...

  16. Azide binding to the trinuclear copper center in laccase and ascorbate oxidase

    DEFF Research Database (Denmark)

    Gromov, I; Marchesini, A; Farver, O;

    1999-01-01

    distance between the dipolar coupled Cu(II) pair is shorter in laccase than in AO. The proximity of T2 Cu(II) to the S = 1 Cu(II) pair enhances its relaxation rate, reducing its signal intensity relative to that of native protein. The disruption of the T3 anti-ferromagnetic coupling occurs only in part of...

  17. Energetic polymers and plasticizers based on organic azides, nitro groups and tetrazoles

    OpenAIRE

    Hartdegen, Vera

    2016-01-01

    The aim of this thesis was the development and investigation of new energetic polymers and plasticizers, on the basis of different polymer backbones or organic compounds with varying energetic or nitrogen-rich functional groups, along with the syntheses of suitable precursors for further (polymeric) processing. One of the main requirements of the newly developed compounds was their suitability as energetic binder or plasticizer, respectively, which includes high thermal and physical stabil...

  18. Molecular and electronic structure of chromium(V) nitrido complexes with azide and isothiocyanate ligands

    DEFF Research Database (Denmark)

    Bendix, Jesper; Birk, Torben; Weyhermüller, Thomas

    2005-01-01

    .223 A between the axial and equatorial ligators from the phenanthroline ligand. The absorption band with lowest energy in these pseudo-linear complexes is assigned as the electric dipole forbidden transition d(xy) --> d(x-y) based on intensities and its variation with the nature of the equatorial ligators...

  19. Construction of a Multifunctional Enzyme Complex via the Strain-Promoted Azide-Alkyne Cycloaddition

    NARCIS (Netherlands)

    Schoffelen, S.; Beekwilder, M.J.; Debets, M.F.; Bosch, H.J.; Hest, van J.C.M.

    2013-01-01

    Inspired by the multienzyme complexes occurring in nature, enzymes have been brought together in vitro as well. We report a co-localization strategy milder than nonspecific cross-linking, and free of any scaffold and affinity tags. Using non-natural amino acid incorporation, two heterobifunctional l

  20. Synthesis of alpha-tetrasubstituted triazoles by copper-catalyzed silyl deprotection/azide cycloaddition

    Directory of Open Access Journals (Sweden)

    Zachary L. Palchak

    2015-08-01

    Full Text Available Propargylamines are popular substrates for triazole formation, but tetrasubstituted variants have required multistep syntheses involving stoichiometric amounts of metal. A recent cyclohexanone–amine–silylacetylene coupling forms silyl-protected tetrasubstituted propargylamines in a single copper-catalyzed step. The development of the tandem silyl deprotection–triazole formation reported herein offers rapid access to alpha-tetrasubstituted triazoles. A streamlined two-step approach to this uncommon class of hindered triazoles will accelerate exploration of their therapeutic potential. The superior activity of copper(II triflate in the formation of triazoles from sensitive alkyne substrates extends to simple terminal alkynes.

  1. Photo-activation of d(0) niobium imido azides: en route to nitrido complexes.

    Science.gov (United States)

    Camp, Clément; Grant, Lauren N; Bergman, Robert G; Arnold, John

    2016-04-25

    We report the synthesis and photo-reactivity of d(0) niobium imido azido complexes supported by β-diketiminate ligands, which leads to the unprecedented formation of nitrides through a photo-assisted intramolecular rearrangement. This provides a new entry to metal nitrides that does not require low-valent metal centers and is a rare example in which the metal-imido moiety in group 5 complexes participates in reactivity. PMID:27033145

  2. Cobalt azide complexes with a tris(carbene)borate ligand scaffold.

    Science.gov (United States)

    Scepaniak, Jeremiah J; Margarit, Charles G; Bontchev, Ranko P; Smith, Jeremy M

    2013-09-01

    The four-coordinate Co(II) complex, (azido-κN)[1,1,',1''-(phenylboranetriyl)tris(3-tert-butyl-1H-imidazol-2-ylidene)]cobalt(II), [Co(C27H38BN6)(N3)], (1), denoted PhB(t-BuIm)3CoN3, was prepared by the reaction of the corresponding chloride complex with NaN3. One-electron oxidation results in the isolation of the five-coordinate Co(III) complex, bis(azido-κN)[1,1,',1''-(phenylboranetriyl)tris(3-tert-butyl-1H-imidazol-2-ylidene)]cobalt(III), [Co(C27H38BN6)(N3)2], (2), denoted PhB(t-BuIm)3Co(N3)2. Attempts to prepare cobalt nitrides by thermolysis or photolysis of these complexes were unsuccessful. PMID:24005501

  3. Reactivity studies of eta sup (6)-p-cymene ruthenium(II) carboxylato complexes towards azide some neutral ligands

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Kollipara, M.R.

    Mono and di-nuclear eta sup (6)-p-cymene ruthenium(II) complexes containing carboxylato ligand of formulation [(eta sup (6)-p-cymene)Ru(pa)Cl] and [{(eta sup (6)-p-cymene)RuCl}2 (mu-LL)] [where, pa = O sub (2)CC sub (6)H sub (4)-p-OMe (1), LL = C...

  4. Azide derivatized anticancer agents of Vitamin K 3: X-ray structural, DSC, resonance spectral and API studies

    Science.gov (United States)

    Badave, Kirti; Patil, Yogesh; Gonnade, Rajesh; Srinivas, Darbha; Dasgupta, Rajan; Khan, Ayesha; Rane, Sandhya

    2011-12-01

    Compound 1 [1-imino (acetyl hydrazino)-Vitamin K 3], displays valence tautomerically related electronic isomers as Form I and Form II. Form I exhibits 2D packing fragment with 1D ribbon chains of N-H⋯O hydrogen bonds and shows EPR silent features. While Form II is EPR active and exhibits biradical nature with double quantum transitions at g = 2.0040. 1H NMR of compound 2, [1-imino (hydrazino carboxylate)-Vitamin K 3] and Form II exhibit π delocalization via resonance assisted H-bonding [RAHB] effect compared to Form I. Molecular interactions in Form I and II are visualized by DSC. The electronic structures of compounds 1 and 2 have been correlated to their API values by measuring anticancer activities, mitochondrial potentials and DNA shearing patterns. Form II and compound 2 indicate mitochondria mediated apoptosis (˜75% cell death) while Form I causes 35% cell death.

  5. Solvent Composition Directing Click-Functionalization at the Surface or in the Bulk of Azide-Modified PEDOT

    DEFF Research Database (Denmark)

    Lind, Johan Ulrik; Hansen, Thomas Steen; Daugaard, Anders Egede;

    2011-01-01

    Thin films of the conducting polymer poly(3,4-(1-azidomethylethylene)dioxythiophene) tosylate (PEDOT−N3) can be functionalized by reaction with alkynated reagents in aqueous solutions. Reaction in pure water resulted in surface specific modification of PEDOT−N3 films, whereas both surface and bul...

  6. Continuous metal scavenging and coupling to one-pot copper-catalyzed azide-alkyne cycloaddition click reaction in flow

    NARCIS (Netherlands)

    Vural - Gursel, Dr. Iris; Aldiansyah, Ferry; Wang, Qi; Noël, Timothy; Hessel, Volker

    2015-01-01

    Increasing usage of catalytic chemistry calls for efficient removal of metal traces. This paper describes the development and optimization of a scavenger-based extraction in flow to remove metal catalysts. It enables liquid-liquid extraction with slug flow and phase separation with a porous fluoropo

  7. Copper-Free Click Biofunctionalization of Silicon Nitride Surfaces via Strain-Promoted Alkyne-Azide Cycloaddition Reactions

    NARCIS (Netherlands)

    Manova, R.K.; Pujari, S.P.; Weijers, C.A.G.M.; Zuilhof, H.; Beek, van T.A.

    2012-01-01

    Cu-free "click" chemistry is explored on silicon nitride (Si3N4) surfaces as an effective way for oriented immobilization of biomolecules. An omega-unsaturated ester was grafted onto Si3N4 using UV irradiation. Hydrolysis followed by carbodiimide-mediated activation yielded surface-bound active succ

  8. A Versatile Strategy to Synthesize Perfluoropolyether-Based Thermoplastic Fluoropolymers by Alkyne-Azide Step-Growth Polymerization.

    Science.gov (United States)

    Lopez, Gérald; Ameduri, Bruno; Habas, Jean-Pierre

    2016-04-01

    Perfluoropolyether (PFPE)-based thermoplastic fluoropolymers are synthesized by A2 + B2 step-growth polymerization between PFPE-diyne and fluorinated diazides. This versatile method allows synthesizing PFPE-based materials with tunable physicochemical properties depending on the exact nature of the fluorinated segment of the diazide precursor. Semicrystalline or amorphous materials endowed with high thermostability (≈300 °C under air) and low glass transition temperature (≈-100 °C) are obtained, as confirmed by differential scanning calorimetry, thermogravimetry, and rheometry. Step-growth polymerizations can be copper-catalyzed but also thermally activated in some cases, thus avoiding the presence of copper residues in the final materials. This strategy opens up new opportunities to easily access PFPE-based materials on an industrial scale. Furthermore, a plethora of developments can be envisioned (e.g., by adding a third trifunctional component to the formulations for the synthesis of PFPE-based elastomers).

  9. Metal-Organic Framework Templated Synthesis of Copper Azide as the Primary Explosive with Low Electrostatic Sensitivity and Excellent Initiation Ability.

    Science.gov (United States)

    Wang, Qianyou; Feng, Xiao; Wang, Shan; Song, Naimeng; Chen, Yifa; Tong, Wenchao; Han, Yuzhen; Yang, Li; Wang, Bo

    2016-07-01

    A powerful yet safe primary explosive, embedded in a conductive carbon scaffold, is prepared by using a metal-organic framework as precursor. It simultaneously possesses low electrostatic sensitivity, good flame sensitivity, and excellent initiation ability. This method is simple, scalable, and provides a new platform for the development of energetic materials especially those employed in miniaturized explosive systems.

  10. Synthesis of Triaminoguanidinum Azide in Non-aquious Medium%三氨基胍叠氮酸盐的非水相合成研究

    Institute of Scientific and Technical Information of China (English)

    余天祥; 杨发福; 杨海鸥; 李常青

    2000-01-01

    在非水介质中用游离三氨基胍(TAG)与通过离子交换树脂新生成的HN3进行中和反应,制备了三氨基胍叠氮酸盐(TAZ).实验证明,在甲醇中磺酸树脂与NaN3可定量生成HN3,且易分离,可避免将无机盐带入TAZ产品中.

  11. In situ construction of three anion-dependent cu(i) coordination networks as promising heterogeneous catalysts for azide-alkyne "click" reactions.

    Science.gov (United States)

    Xu, Zhenghu; Han, Lu Lu; Zhuang, Gui Lin; Bai, Jing; Sun, Di

    2015-05-18

    Three Cu(I) coordination networks, namely, {[Cu2(bpz)2(CN)X]·CH3CN}n, (X = Cl, 1; I, 3), {[Cu6(bpz)6(CH3CN)3(CN)3Br]·2OH·14CH3CN}n, (2, bpz = 3,3',5,5'-tetramethyl-4,4'-bipyrazole), were prepared by using solvothermal method. The cyanide ligands in these networks were generated in situ by cleavage of C-C bond of MeCN under solvothermal condition. The structures of these networks are dependent on halogen anions. Complex 1 is a ladderlike structure with μ2-CN(-) as rung and μ2-bpz as armrest. The Cl(-) in 1 is at terminal position but does not extend the one-dimensional (1D) ladder to higher dimensionalities. Complex 2 is a three-dimensional (3D) framework comprised of novel planar [Cu3Br] triangle and single Cu nodes, which are extended by μ2-bpz and μ2-CN(-) to form a novel (3,9)-connected gfy network. Density functional theory calculations showed that single-electron delocalization of Br atom induces the plane structure of [Cu3Br]. Complex 3 also possesses a similar ladderlike subunit as in 1, but the I(-) acts as bidentate bridge to extend the ladder to 3D framework with a four-connected sra topology. The three networks show notable catalytic activity on the click reaction. The compared catalytic results demonstrate that complex 2 possesses the best catalysis performance among three complexes, which is ascribed to the largest solvent-accessible void (porosity: 2 (29.4%) > 1 (25.7%) > 3 (17.6%)) and the more Cu(I) active sites in 2. The present combined structure-property studies provide not only a new synthetic route to obtain a new kind of catalyst for click reaction but also the new insights on catalyst structure-function relationships. PMID:25941881

  12. Revisiting the mechanism of the mono nuclear copper-catalyzed cycloaddition of azide and alkynes (CuAAC) by the topology of ....

    OpenAIRE

    Calvo-Losada, Saturnino; Pino-González, María Soledad; Quirante, José Joaquín

    2013-01-01

    Se analiza el mecanismo de la reacción de cicloadición, catalizada por Cu(I), de azidas a alquinos (CuAAC), haciendo uso de métodos DFT y de herramientas de análisis de la densidad electrónica basadas en la topología de su laplaciana. Comunicación presentada y aceptada en el CHITEL2013, XXXIX International Conference THEORETICAL CHEMISTS OF LATIN EXPRESSION (XXXIX Congreso Internacional de Químicos de Expresión Latina).

  13. Mono and dinuclear arene ruthenium(II) triazoles by 1,3-dipolar cycloadditions to a coordinated azide in ruthenium(II) compounds

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Svitlyk, V.; Mozharivskyj, Y.

    of coordinated azido compound ((Eta sup(6)-C sub(6)Me sub(6))Ru(L sub(1))N sub(3)) (1) with substituted acetylene, RO sub(2)CC sub(2)CO sub(2)R via unexpected oxidation of the coordinated ligand to oxalate (where; L sub(1)= 5-hydroxy-2-(hydroxymethyl)-4-pyrone; R...

  14. Arene ruthenium(II) azido complexes incorporating N intersection O chelate ligands: Synthesis, spectral studies and 1,3-dipolar-cycloaddition to a coordinated azide in ruthenium(II) compounds

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Kaminsky, W.

    The arene ruthenium(II) azido compounds [{(p-cymene)Ru(N^O)N3}] have been prepared by the reaction of [{(p-cymene)Ru(mewN3)Cl}2] with the corresponding ligands. The ruthenium azido compounds [{(p...

  15. Versatile convergent synthesis of a three peptide loop containing protein mimic of whooping cough pertactin by successive Cu(I)-catalyzed azide alkyne cycloaddition on an orthogonal alkyne functionalized TAC-scaffold

    NARCIS (Netherlands)

    Werkhoven, Paul R; van de Langemheen, Helmus; van der Wal, Steffen; Kruijtzer, John A W; Liskamp, Rob M J

    2014-01-01

    Synthetic mimics of discontinuous epitopes may have a wide range of potential applications, including synthetic vaccines and inhibition of protein-protein interactions. However, synthetic access to these relatively complex peptide molecular constructs is limited. This paper describes a versatile con

  16. 叠氮二乙基铝和镓多聚体结构和性质的密度泛函理论研究%Structure properties of Diethylmetallic Azides Clusters of Aluminum and Gallium by DFT

    Institute of Scientific and Technical Information of China (English)

    夏其英; 马登学; 杨吉民

    2009-01-01

    (Et2MN3)n(n=1 to 3, M=Al, Ga) clusters were studied by DFT/B3LYP method with SDD basis set. The dimer(Et2MN3)2 and trimer(Et2MN3)3(M=Al, Ga) are found to exhibit four membered M2N2 and six membered M3N3 ring structure, respectively.Compared with the monomer, the order of the bond length changes for the dimer(Et2MN3)2 and trimer(Et2MN3)3(M=Al, Ga) is as follows: Nα-M>Nα-Nβ>Nβ-Nγ≈M-C. Binding energies of the dimer (Et2AlN3)2 and trimer(Et2AlN3)3 clusters are 35.44 and 45.61 kJ·mol-1 lower than that of (Et2GaN3)2 and(Et2GaN3)3 clusters, respectively. Thermodynamic properties show that the dimer is the main composition of the(Et2MN3)n(n=1 to 3, M=Al, Ga) clusters at 298.2 K. The dimerization and trimerization are very favorable thermodynamically below 500 K.%采用DFT-B3LYP/SDD方法系统研究了(Et2MN3)n(n=1-3,M=Al, Ga) 体系.二聚体(Et2MN3)2和三聚体(Et2MN3)3(M=Al, Ga)分别拥有四元环M2N2和六元环M3N3结构.与单体相比,二聚体(Et2MN3)2和三聚体(Et2MN3)3(M=Al, Ga)的键长变化次序均为Nα-M>Nα-Nβ>Nβ-Nγ≈M-C.二聚体(Et2AlN3)2的结合能比(Et2GaN3)2低35.44 kJ·mol-1,而三聚体(Et2AlN3)3的结合能比(Et2GaN3)3低45.61 kJ·mol-1.热力学性质表明叠氮二乙基铝和镓体系在298.2 K温度下均以二聚体为主.在低于500 K的温度下,二聚化和三聚化反应在热力学上是有利的.

  17. Regioselective [3+2] cycloaddition of chalcones with a sugar azide: easy access to 1-(5-deoxy-D-xylofuranos-5-yl)-4,5-disubstituted-1H-1,2,3-triazoles.

    Science.gov (United States)

    Singh, Nimisha; Pandey, S K; Tripathi, Rama P

    2010-08-16

    [3+2] Cycloaddition of 5-azido-5-deoxy-1,2-O-isopropylidene-alpha-d-xylofuranose with 1,3-diphenyl-prop-3-enones, followed by oxidation of the intermediate triazolines in a tandem manner, led to the regioselective formation of 4-benzoyl-1-(5-deoxy-1,2-O-isopropylidene-alpha-d-xylofuranos-5-yl)-5-phenyl-1H-1,2,3-triazoles in moderate to good yields. PMID:20579636

  18. Azide polyurethane elastomer (Ⅰ)effect of intermolecular force on mechanical properties%叠氮聚氨酯弹性体(Ⅰ)分子间作用力对力学性能的影响

    Institute of Scientific and Technical Information of China (English)

    邱少君; 蔚红建; 崔燕军; 甘孝贤

    2000-01-01

    研究了加强分子间作用力对提高叠氮聚氨酯弹性体力学性能的影响.以HDI三聚体为固化剂的GAP聚叠氮缩水甘油醚弹性体的拉伸强度/断裂伸长率为0.66 MPa/127.2%.GAP与含强极性基团的叠氮聚醚APP共混,弹性体的拉伸强度随APP用量增加而增加.红外谱图显示,氢键作用越强,弹性体力学性能越好.

  19. Experimental and Computational Studies of Binding of Dinitrogen, Nitriles, Azides, Diazoalkanes, Pyridine and Pyrazines to M(PR3)2(CO)3 (M=Mo, W; R=Me, iPr)

    Energy Technology Data Exchange (ETDEWEB)

    Hoff, C.D.; Muckerman, J.; Achord, P.; Fujita, E.; Scott, B.; Fortman, G.C.; Temprado, M.; Cai, X.; Captain, B.; Isrow, D.; Weir, J.J.; McDonough, J.E.

    2009-08-17

    The enthalpies of binding of a number of N-donor ligands to the complex Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3} in toluene have been determined by solution calorimetry and equilibrium measurements. The measured binding enthalpies span a range of {approx}10 kcal mol{sup -1}: {Delta}H{sub binding} = -8.8 {+-} 1.2 (N{sub 2}-Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}); -10.3 {+-} 0.8 (N{sub 2}); -11.2 {+-} 0.4 (AdN{sub 3} (Ad = 1-adamantyl)); -13.8 {+-} 0.5 (N{sub 2}CHSiMe{sub 3}); -14.9 {+-} 0.9 (pyrazine = pz); -14.8 {+-} 0.6 (2,6-Me{sub 2}pz); -15.5 {+-} 1.8 (Me{sub 2}NCN); -16.6 {+-} 0.4 (CH{sub 3}CN); -17.0 {+-} 0.4 (pyridine); -17.5 {+-} 0.8 ([4-CH{sub 3}pz][PF{sub 6}] (in tetrahydrofuran)); -17.6 {+-} 0.4 (C{sub 6}H{sub 5}CN); -18.6 {+-} 1.8 (N{sub 2}CHC(=O)OEt); and -19.3 {+-} 2.5 kcal mol{sup -1} (pz)Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}). The value for the isonitrile AdNC (-29.0 {+-} 0.3) is 12.3 kcal mol{sup -1} more exothermic than that of the nitrile AdCN (-16.7 {+-} 0.6 kcal mol{sup -1}). The enthalpies of binding of a range of arene nitrile ligands were also studied, and remarkably, most nitrile complexes were clustered within a 1 kcal mol{sup -1} range despite dramatic color changes and variation of v{sub CN}. Computed structural and spectroscopic parameters for the complexes Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L are in good agreement with experimental data. Computed binding enthalpies for Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L exhibit considerable scatter and are generally smaller compared to the experimental values, but relative agreement is reasonable. Computed enthalpies of binding using a larger basis set for Mo(PMe{sub 3}){sub 2}(CO){sub 3}L show a better fit to experimental data than that for Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L using a smaller basis set. Crystal structures of Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdCN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(Me{sub 2}NCN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,6-F{sub 2}C{sub 6}H{sub 3}CN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,4,6-Me{sub 3}C{sub 6}H{sub 2}CN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,6-Me{sub 2}pz), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdCN), Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdNC), and W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdNC) are reported.

  20. Research Advances in Synthesis and Modification of Glycidyl Azide Polymer%聚叠氮缩水甘油醚的合成与改性研究进展

    Institute of Scientific and Technical Information of China (English)

    王旭朋; 罗运军; 郭凯; 吕勇

    2009-01-01

    聚叠氮缩水甘油醚(GAP)是国内外重点研究的含能粘合剂之一.该文综述了GAP的合成研究进展,重点介绍了高相对分子质量GAP、支化GAP和等规GAP的合成.针对GAP反应活性低的特点,介绍了GAP的多种端基改性方法.GAP的无规、嵌段共聚物改善了GAP粘合剂的性能,GAP与其他粘合剂的互穿及共混,为GAP在推进剂中的应用提供了广阔前景.引用文献37篇.

  1. Synthesis of DOTA-conjugated multimeric [Tyr3]octreotide peptides via a combination of Cu(I)-catalyzed "click" cycloaddition and thio acid/sulfonyl azide "sulfo-click" amidation and their in vivo evaluation.

    NARCIS (Netherlands)

    Yim, C.B.; Dijkgraaf, I.; Merkx, R.; Versluis, C.; Eek, A.; Mulder, G.E.; Rijkers, D.T.; Boerman, O.C.; Liskamp, R.M.

    2010-01-01

    Herein, we describe the design, synthesis, and biological evaluation of a series of DOTA-conjugated monomeric, dimeric, and tetrameric [Tyr(3)]octreotide-based analogues as a tool for tumor imaging and/or radionuclide therapy. These compounds were synthesized using a Cu(I)-catalyzed 1,3-dipolar cycl

  2. The crystal structure of Cs5Eu(N3)8

    International Nuclear Information System (INIS)

    The crystal structure of pentacesium octaazidoeuropiate(III), Cs5Eu(N3)8, was determined by single crystal X-ray diffraction: orthorhombic, a = 16,811(4), b = 16,860(5), c = 16,964(3)A, space group Pbca, Z = 8, 2310 observed reflections, R = 0,048. Europium atoms are coordinated to eight azide groups, the coordination polyhedra have no azide groups in common. Four cesium atoms are surrounded by eigth, one by seven azide groups. The azide groups are symmetric with mean N - N-distances of 1,17(1)A. (Authors)

  3. Synthesis of GAP and PAMMO Homopolymers from Mesylate Polymeric Precursors

    Science.gov (United States)

    Mura, Claudio; Fruci, Stefania; Lamia, Pietro; Cappello, Miriam; Filippi, Sara; Polacco, Giovanni

    2016-04-01

    In azidic binders for solid propellants, the N3 functionality is introduced by substitution of a halogen or tosyl group, but recently the mesyl group has been suggested as an alternative. The mesylate group has two advantages, mainly related to its small dimensions and low cost. Poly(glycidyl azide) and poly 3-azidomethyl-3-methyl oxetane were prepared by using both tosylate and mesylate precursors. The azidation kinetics were studied at three different temperatures while keeping all other operating parameters the same. The results confirmed the good potential of the mesylate precursors for the production of azidic binders.

  4. Synthesis and Crystal Structure of an Azide Bridged Binuclear Zinc(Ⅱ) Dimer Containing Taurine Schiff Base [Zn2(C8H9N2O3S)2·(N3)2·(H2O)2]2·2H2O

    Institute of Scientific and Technical Information of China (English)

    JIANG Yi-Min; LI Jia-Ming; XIE Fu-Qing; WANG Yan-Fei

    2006-01-01

    The title complex [Zn2L2(N3)2(H2O)2]·2H2O (L = N-(2-pyridylmethylidene) taurine)has been synthesized in a methanol-water solution. The crystal belongs to monoclinic, space group P21/c with a = 15.8064(10), b = 10.5015(5), c = 17.3193(11) (A), β = 111.314(2)°, V = 2678.2(3) (A)3, C16H26N10O10S2Zn2, Mr = 713.33, Z = 4, Dc = 1.769 g/cm3, μ = 2.017 mm-1 and F(000) =1456. The asymmetric unit consists of two half-molecules of the complex and two water molecules.Four N and two O atoms form the coordination environment of each Zn atom, resulting in a distorted octahedral configuration. The two halves of each independent dimer are related by a crystallographic inversion centre, which lies at the centre of the ring formed by two Zn atoms and the coordinating the ac plane.

  5. Cu (I) catalyzed alkyne-azide 1,3-dipolar cycloaddition (CuAAC): Synthesis of 17α-[1-(substituted phenyl)-1,2,3-triazol-4-yl]-19-nor-testosterone-17β-yl acetates targeting progestational and antipro-liferative activities.

    Science.gov (United States)

    Mohamed, Z H; El-Koussi, Nawal A; Mahfouz, Nadia M; Youssef, Adel F; Abdel Jaleel, Gehad A; Shouman, Samia A

    2015-06-01

    The progestational potency and selectivity of synthetic steroidal agonists can be enhanced by even larger chemical moieties at 17α-position of the steroid backbones. Hereby a series 5a-c and 6a-c of novel 17α-[1-(substituted phenyl)-1,2,3-triazol-4-yl]-19-nortestosterone-17β-yl acetates were designed and synthesized using click chemistry approach searching progestogenic derivatives with potential anticancer activity. Compounds 5a,b and 6a,c have affected to different extents the three histopatho-logical parameters considered for evaluation of their progestational activity. The compounds 5a,b and 6a,c showed modifications in rat uterus at 35.7-34.8 nM levels with privileged endometrial thickening effect and least change of uterine weight relative to NEA at 52.9 nM level. Up to 40 mg/kg dose compounds 5b and 6c were non-toxic. Molecular docking of the ligands in PR showed in the majority of cases a conformational fitting into the active site different from that of the reference steroid NEA. Compound 6b revealed about 46.4% growth inhibition of CNS cancer SNB-75 cell line, 56% growth inhibition of renal cancer A498 cell line and 56.7% growth inhibition of prostate cancer PC-3 cell line which was mediated by cell cycle arrest. Drugability of the screened compounds showed tolerated results after being challenged to diverse physicochemical parameters. PMID:25942354

  6. Adhesion of Photon-Driven Molecular Motors to Surfaces via 1,3-Dipolar Cycloadditions : Effect of Interfacial Interactions on Molecular Motion

    NARCIS (Netherlands)

    Carroll, Gregory T.; London, Gabor; Fernández Landaluce, Tatiana; Rudolf, Petra; Feringa, Ben L.

    2011-01-01

    We report the attachment of altitudinal light-driven molecular motors to surfaces using 1,3-dipolar cycloaddition reactions. Molecular motors were designed containing azide or alkyne groups for attachment to alkyne- or azide-modified surfaces. Surface attachment was characterized by UV-vis, IR, XPS,

  7. Method of preparation of uranium nitride

    Science.gov (United States)

    Kiplinger, Jaqueline Loetsch; Thomson, Robert Kenneth James

    2013-07-09

    Method for producing terminal uranium nitride complexes comprising providing a suitable starting material comprising uranium; oxidizing the starting material with a suitable oxidant to produce one or more uranium(IV)-azide complexes; and, sufficiently irradiating the uranium(IV)-azide complexes to produce the terminal uranium nitride complexes.

  8. Analytical use of zide ion. Chemical equilibrium studies and correlates in U(VI)/N3 and Co(III)/N3 systems

    International Nuclear Information System (INIS)

    A monographic study about the azide ion and its structure, as well as, references about the uranyl ion in aqueous medium, and its possible hydrolysis products are shown. Spectral studies of the U(VI), Fe (III) and Cu(II) systems, in azide medium are analyzed. (M.J.C.)

  9. Utilization of metabolic inhibitors for shifting product formation from xylitol to ethanol in pentose fermentations using Candida tropicalis

    Energy Technology Data Exchange (ETDEWEB)

    Lohmeier-Vogel, E.; Hahn-Haegerdal, B.

    1985-02-01

    Xylose, glucose and xylose/glucose mixtures were fermented with Candida tropicalis ATCC 32113 under aerobic, oxygen limited and anaerobic conditions. Ethanol yields were highest under oxygen limited conditions with xylose and xylose/glucose. Anaerobic conditions were best for glucose fermentations. The effect of four metabolic inhibitors (azide, carbonyl cyanide m-chlorophenyl hydrazone (CCCP), oligomycin A and valinomycin-K/sup +/) were then studied under oxygen limited conditions. Only azide had a significant influence on ethanol production. At 2x10/sup -4/ M concentrations, ethanol yield increased up to two times and xylitol levels were repressed by 90% for xylose and glucose/xylose fermentations. 4.2x10/sup -3/ M azide gave highest ethanol yields in glucose fermentations. At this concentration of azide, however, cell growth was inhibited, which seemed to prevent ethanol production in xylose fermentations. The effect of azide is discussed in terms of 'fine-tuning' the respiratory activity necessary for metabolism.

  10. Ligand Binding to Chlorite Dismutase from Magnetospirillum sp.

    Science.gov (United States)

    De Schutter, Amy; Correia, Hugo D; Freire, Diana M; Rivas, María G; Rizzi, Alberto; Santos-Silva, Teresa; González, Pablo J; Van Doorslaer, Sabine

    2015-10-29

    Chlorite dismutase (Cld) catalyzes the reduction of chlorite to chloride and dioxygen. Here, the ligand binding to Cld of Magnetospirillum sp. (MaCld) is investigated with X-ray crystallography and electron paramagnetic resonance (EPR). EPR reveals a large heterogeneity in the structure of wild-type MaCld, showing a variety of low- and high-spin ferric heme forms. Addition of an axial ligand, such as azide or imidazole, removes this heterogeneity almost entirely. This is in line with the two high resolution crystal structures of MaCld obtained in the presence of azide and thiocyanate that show the coordination of the ligands to the heme iron. The crystal structure of the MaCld-azide complex reveals a single well-defined orientation of the azide molecule in the heme pocket. EPR shows, however, a pH-dependent heme structure, probably due to acid-base transitions of the surrounding amino-acid residues stabilizing azide. For the azide and imidazole complex of MaCld, the hyperfine and nuclear quadrupole interactions with the close-by (14)N and (1)H nuclei are determined using pulsed EPR. These values are compared to the corresponding data for the low-spin forms observed in the ferric wild-type MaCld and to existing EPR data on azide and imidazole complexes of other heme proteins. PMID:26287794

  11. Star-Shaped Polyacrylates: Highly Functionalized Architectures via CuAAC Click Conjugation.

    Science.gov (United States)

    Lammens, Mieke; Fournier, David; Fijten, Martin W M; Hoogenboom, Richard; Prez, Filip Du

    2009-12-01

    Well-defined functional star-shaped polymer structures with up to 29 arms have been successfully synthesized by the combination of atom transfer radical polymerization (ATRP) and click chemistry. First, azide end-functionalized poly(isobornyl acrylate) (PiBA) star-shaped polymers were prepared by successive ATRP and bromine substitution. Subsequently, alkyne end-functionalized molecules and polymers were introduced onto the star-shaped PiBA bearing pendant azide moieties by copper-catalyzed azide-alkyne cycloaddition (CuAAC). The possibilities and limits for the CuAAC on such highly branched polyacrylates are described. PMID:21638494

  12. Synthesis of 5-phenyltetrazole and its N-methyl Derivatives in a Microreactor

    OpenAIRE

    E. A. Popova; Abiev, R. Sh.; Lappalainen, L. A.; Svetlov, S. D.; Andreeva, T. V.; Trifonov, R. E.; Ostrovskii, V. A.

    2014-01-01

    Azidation of benzonitrile with dimethylammonium azide yielding 5-phenyltetrazole dimethylammonium salt was performed under microreactor conditions. The kinetics of azidation of benzonitrile in DMF was investigated at the range 80–95 °С. The reaction rate constants were determined:kII·104(L mol–1 s–1): 0.79, 0.97, 1.19, 1.51, at 80, 85, 90, and 95 °С, respectively. It was found that the reaction rate constants obtained in a microreactor are comparable to ones for a batch-type reactor. The ther...

  13. SYNTHESIS AND MICROBIAL EVALUATION OF NOVEL TETRAZOLO-TRIAZOLE DERIVATIVES SYNTHESIS und mikrobielle Evaluierung neuartiger Tetrazolo-triazol DERIVATE

    Directory of Open Access Journals (Sweden)

    Vijay V Dabholkar, Navnath Shinde, Abhishekh Karekar and Prem Naik

    2013-01-01

    Full Text Available 5-(4'-Bromomethyl-1, 1'-biphenyl-2-yl -1H-tetrazole (1 was converted into its azide derivative using sodium azide (2, which on further treatment with malonitrile, diethyl malonate, ethyl acetoacetate and isopropyl acetoacetate to yielded the respective tetrazole-triazole derivatives. The structures of the synthesized compounds were confirmed by Physico-chemical test and spectral techniques, representative samples were screened for their antimicrobial activity against gram positive and gram negative bacteria. Key words: Tetrazoles, Triazoles, Triphenyl phosphine, azides

  14. catena-Poly[[bis[4-(dimethylaminopyridine-κN1]cobalt(II]-di-μ-azido-κ4N1:N3

    Directory of Open Access Journals (Sweden)

    Hocine Merazig

    2013-03-01

    Full Text Available The title layered polymer, [Co(N32(C7H10N22]n, contains CoII, azide and 4-(dimethylaminopyridine (4-DMAP species with site symmetries m2m, 2 and m, respectively. The Co2+ ion adopts an octahedral coordination geometry in which four N atoms from azide ligands lie in the equatorial plane and two 4-DMAP N atoms occupy the axial positions. The CoII atoms are connected by two bridging azide ligands, resulting in a chain parallel to the c axis.

  15. Pentafluorostyrene: A valuable and flexible material design tool when mastered by ATRP

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    scaffold for phophonates for polymer electrolyte membranes. This design idea was executed by use of CuAAC, where clickable azides were fabricated on the PSU (7 mol%) through lithiation chemistry at low temperature introducing first chloromethyl followed by conventional conversion of chloro groups to azides...... by sodium azide treatment. After clicking the two components together the poly(pentafluorostyrene) grafts were phosphonated. Graft copolymer (PSU-g-PhPFS) membranes could be cast that showed high thermal stability and proton conductivity. Soft silicone elastomers are materials in demand for actuators...

  16. Molecular and Crystal Structures of Three Berberine Derivatives

    Directory of Open Access Journals (Sweden)

    Jiří Dostál

    2001-04-01

    Full Text Available Berberine azide, berberine thiocyanate, and 8-cyano-8H-berberine were prepared from berberine chloride, a quaternary protoberberine alkaloid. The molecular and crystal structures of all compounds are reported and discussed.

  17. Microwave-Promoted Rapid Synthesis of 1-Aryl-1, 2, 3-Triazoles

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Aryl azides and a-keto phosphorus ylides were reacted within 4~10 minutes with silica gel support, under microwave irridiation to afford corresponding l-aryl-l, 2, 3-triazoles in moderate to good yields.

  18. Molecular and Crystal Structures of Three Berberine Derivatives

    OpenAIRE

    Jiří Dostál; Zdirad Žák; Marek NeÄÂas; Milan PotáÄÂek; Stanislav Man

    2001-01-01

    Berberine azide, berberine thiocyanate, and 8-cyano-8H-berberine were prepared from berberine chloride, a quaternary protoberberine alkaloid. The molecular and crystal structures of all compounds are reported and discussed.

  19. 76 FR 64974 - Commerce in Explosives; List of Explosive Materials (2011R-18T)

    Science.gov (United States)

    2011-10-19

    ... inorganic salts. * ANFO . Aromatic nitro-compound explosive mixtures. Azide explosives. B Baranol. Baratol...). Explosive nitro compounds of aromatic hydrocarbons. Explosive organic nitrate mixtures. Explosive powders. F... explosive. Nitrated polyhydric alcohol explosives. Nitric acid and a nitro aromatic compound...

  20. 78 FR 64246 - Commerce in Explosives; List of Explosives Materials

    Science.gov (United States)

    2013-10-28

    ... isomorphously substituted inorganic salts. *ANFO . Aromatic nitro-compound explosive mixtures. Azide explosives.... Explosive mixtures containing tetranitromethane (nitroform). Explosive nitro compounds of aromatic... polyhydric alcohol explosives. Nitric acid and a nitro aromatic compound explosive. Nitric acid...

  1. 75 FR 1085 - Commerce in Explosives; List of Explosive Materials (2009R-18T)

    Science.gov (United States)

    2010-01-08

    .... *ANFO . Aromatic nitro-compound explosive mixtures. Azide explosives. B Baranol. Baratol. BEAF . Black...). Explosive nitro compounds of aromatic hydrocarbons. Explosive organic nitrate mixtures. Explosive powders. F... explosive. Nitrated polyhydric alcohol explosives. Nitric acid and a nitro aromatic compound...

  2. Spatially Selective Functionalization of Conducting Polymers by "Electroclick" Chemistry

    DEFF Research Database (Denmark)

    Hansen, Thomas Steen; Daugaard, Anders Egede; Hvilsted, Søren;

    2009-01-01

    Conducting polymer microelectrodes can electrochemically generate the catalyst required for their own functionalization by "click chemistry" with high spatial resolution. Interdigitated microelectrodes prepared from an azide-containing conducting polymer are selectively functionalized in sequence...

  3. A versatile toolbox for posttranscriptional chemical labeling and imaging of RNA

    Science.gov (United States)

    Sawant, Anupam A.; Tanpure, Arun A.; Mukherjee, Progya P.; Athavale, Soumitra; Kelkar, Ashwin; Galande, Sanjeev; Srivatsan, Seergazhi G.

    2016-01-01

    Cellular RNA labeling strategies based on bioorthogonal chemical reactions are much less developed in comparison to glycan, protein and DNA due to its inherent instability and lack of effective methods to introduce bioorthogonal reactive functionalities (e.g. azide) into RNA. Here we report the development of a simple and modular posttranscriptional chemical labeling and imaging technique for RNA by using a novel toolbox comprised of azide-modified UTP analogs. These analogs facilitate the enzymatic incorporation of azide groups into RNA, which can be posttranscriptionally labeled with a variety of probes by click and Staudinger reactions. Importantly, we show for the first time the specific incorporation of azide groups into cellular RNA by endogenous RNA polymerases, which enabled the imaging of newly transcribing RNA in fixed and in live cells by click reactions. This labeling method is practical and provides a new platform to study RNA in vitro and in cells. PMID:26384420

  4. A ratiometric fluorescent probe for gasotransmitter hydrogen sulfide based on a coumarin-benzopyrylium platform.

    Science.gov (United States)

    Duan, Yu-Wei; Yang, Xiao-Feng; Zhong, Yaogang; Guo, Yuan; Li, Zheng; Li, Hua

    2015-02-15

    A ratiometric fluorescent probe for H2S was developed based on a coumarin- benzopyrylium platform. The ratiometric sensing is realized by a selective conversion of acyl azide to the corresponding amide, which subsequently undergoes an intramolecular spirocyclization to alter the large π-conjugated system of CB fluorophore. Compared with the traditional azide-based H2S probes, the proposed probe utilizes the acyl azide as the recognition moiety and exhibits a rapid response (∼1min) towards H2S, which is superior to most of the azide-based H2S probes. Preliminary fluorescence imaging experiments show that probe 1 has potential to track H2S in living cells.

  5. “Electro-Click” on Conducting Polymer Films

    DEFF Research Database (Denmark)

    Hansen, Thomas Steen; Lind, Johan Ulrik; Daugaard, Anders Egede;

    An azide substituted 3,4-ethylenedioxythiophene monomer is polymerised to yield a PEDOT like polymer with available azide groups (Figure 1). The azide groups enable post polymerization functionalization of the conducting polymer using a 1,3 dipolar cycloaddition reaction – also denoted “click...... chemistry”. This facilitates the addition of compounds that can otherwise not withstand the polymerization conditions. Several biological active molecules have been attached and tested on the films. Furthermore conducting polymer microelectrodes can electrochemically generate the catalyst required...... for their own functionalization with high spatial resolution. Interdigitated microelectrodes prepared from the azide-containing conducting polymer were selectively functionalized in sequence by two alkyne-modified fluorophores by control of the applied potentials. “Electro-click” on conducting polymer films...

  6. Synthesis of double-clickable functionalised graphene oxide for biological applications.

    Science.gov (United States)

    Mei, Kuo-Ching; Rubio, Noelia; Costa, Pedro M; Kafa, Houmam; Abbate, Vincenzo; Festy, Frederic; Bansal, Sukhvinder S; Hider, Robert C; Al-Jamal, Khuloud T

    2015-10-18

    Azide- and alkyne-double functionalised graphene oxide (Click(2) GO) was synthesised and characterised with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA) and Raman spectroscopy. Fourteen-percentage increase in azide content was found, after pre-treatment of GO with meta-chloroperoxybenzoic acid (mCPBA), determined with elemental analysis. No effect on A549 cell viability was found, up to 100 μg mL(-1) and 72 h of incubation, determined with the modified lactate dehydrogenase (mLDH) assay. Two sequential copper(i) catalysed azide-alkyne cycloaddition (CuAAC) reactions were performed to conjugate the propargyl-modified blood-brain barrier targeting peptide Angiopep-2, and a bis-azide polyethylene glycol (MW = 3500), to the Click(2) GO. The final conjugate was characterised with ATR-FTIR and TGA. PMID:26295072

  7. Syntheses and Crystal Structures of Two Manganese(H) Coordination Polymers Having 3,4-Diimidazol-Thiophene Ligand Coordinated by Azide and Thiocyanate Counterions%两个含有叠氮根和硫氰根配位单元的3,4-双咪唑噻吩锰(Ⅱ)配位聚合物的合成与晶体结构

    Institute of Scientific and Technical Information of China (English)

    金超; 王银歌; 钱惠芬; 黄伟

    2014-01-01

    制备了2个含有叠氮根和硫氰根配位单元的3,4-双咪唑噻吩(L)的锰(Ⅱ)配位聚合物[Mn(L)(N3)2(H2O)]n(1)和[Mn(L)2(SCN3)2]n(2)并报道了它们的晶体结构.化合物1和2是通过3,4-双咪唑噻吩与四水醋酸锰反应,同时分别引入过量的线性三原子阴离子(N3-和SCN-)以取代醋酸根作为抗衡离子制备而得.单晶结构分析表明1和2具有相同的无限二维链状空间结构,但是由不同的44元的[Mn6(L)4(2N3)2]和36元的[Mn4]大环单元结构组成.此外,配位聚合物1中的叠氮根分别采用端基单齿和桥联双齿的配位方式,而配位聚合物2中的硫氰根仅以端基氮原子与Mn(Ⅱ)离子配位.

  8. Functionalization of olefins by alkoximidoylnitrenes

    Energy Technology Data Exchange (ETDEWEB)

    Subbaraj, A.; Rao, O.S.; Lwowski, W. (New Mexico State Univ., Las Cruces (USA))

    1989-08-04

    (N-Cyano- and N-(methylsulfonyl)alkoxycarbimidoyl)nitrenes, generated in situ from the corresponding azides by 300-nm UV light, convert a variety of olefins cleanly and stereospecifically to the corresponding aziridines. These can readily be hydrolyzed to N-unsubstituted aziridines or ring-opened to allylic isoureas. The nitrenes can also be generated by thermolysis at 80{degree}C. The azides add to norbornene to give triazolines, which lose nitrogen to give the exo-aziridines.

  9. PECH和GAP的玻璃化转变温度研究%Glass-transition Temperature of PECH and GAP

    Institute of Scientific and Technical Information of China (English)

    宋晓庆; 周集义; 王文浩; 王建伟; 白森虎

    2008-01-01

    @@ Glycidyl azide polymer (GAP) is one of the most recognized and prominent azide polymer. Because of its superior properties,GAP is used extensively as a high energetic binder or plasticizer in propellants to increase burning and specific impulse. It is very important to research on the glass-transition temperature (Tg) of GAP and its precursor PECH (poly-epichlorohydrin) due to the Tg of binders is the key factor which can influence low temperature properties of solid propellants.

  10. Synthesis of oxazole, oxazoline and isoxazoline derived marine natural products: A review

    Digital Repository Service at National Institute of Oceanography (India)

    Tilvi, S.; Singh, K.S.

    by oxidative cleavage of the double bond to produce carboxylic acid 2 which was condensed (via its acid chloride) with oxazolidine 3 to give 4. Asymmetric azidation using the Evans procedure gave azide 5 in diastereomerically pure form. Conversion... pseudopterosins [24]. Total synthesis of pseudopterosin A was reported by Broka [25], while pseudopterosin E have been reported by Corey [26]. Recently, David et. al. described the total synthesis of (+)-ileabethoxazole via Iron-midiated Pauson- Khand [2...

  11. Banding and electronic structures of metal azides——Sensitivity and conductivity

    Institute of Scientific and Technical Information of China (English)

    肖鹤鸣; 李永富

    1995-01-01

    By using both DV-Xα and EH-CO methods, the calculation studies of the structure-property relationships of a series of metal azides, of their clusters’ electronic structures in ground and excited states, of their systems with cation vacancy and the doped Pb(N3)2, as well as their crystal band structures have been conducted. The results show that the sensitivity of ionic-type metal azides varies with the degree of difficulty of electronic transition of the losing charge on N3. A metal azide with cation vacancies has a greater sensitivity than the perfect one. When doped with monovalent metal ions, lead azide’s sensitivity increased; when with trivalent ones, its sensitivity decreased; when with divalent ones, little of it changed. Compared with heavy metal azides. an alkali metal azide has a larger band gap, a smaller band width and a greater transition energy of frontier electron with a smaller amount of losing charge on N3, and thus has lower sensitivity and conductivity than heavy metal azides.

  12. Flow-amperometric biosensor for respiratory toxins using myoglobin-adsorbed carbon-felt, based on an inhibitory effect on bioelectrocatalytic reduction of oxygen

    International Nuclear Information System (INIS)

    Novel, simple and highly sensitive reagentless amperometric flow-biosensor for respiratory toxins (i.e. azide and cyanide) has been developed by using myoglobin (Mb)-adsorbed carbon-felt (CF), based on the inhibitory event of azide and cyanide on the Mb-catalyzed O2 reduction. The Mb-adsorbed CF (Mb–CF) showed a sufficient bioelectrocatalytic activity for O2 reduction in the potential region from 0 to −0.4 V vs. Ag/AgCl at pH 5.0, due to the direct electron transfer (DET) between Mb-heme and the CF electrode. The heterogeneous electron transfer rate constant (ks) of the electrochemical redox reaction of Mb-heme–Fe(II)/(III) was estimated to be 15.5 s−1. This Mb–CF-catalyzed O2 reduction was reversibly inhibited by azide and cyanide, which bind to sixth coordination position of heme-iron center of Mb. When air-saturated 0.1 M phosphate/citrate buffer (pH 5.0) was used as a carrier under the applied potential of −0.2 V vs. Ag/AgCl, the steady-state current due to the Mb-catalyzed O2 reduction was reversibly inhibited by the injection (200 μl) of azide and cyanide, resulting in peak-shape current responses. The magnitude of the inhibition peak currents linearly increased with increasing concentrations of azide (up to 3 μM) and cyanide (up to 5 μM), and the detection limit of azide and cyanide were found to be 0.12 and 0.23 μM, respectively (S/N = 2). The apparent inhibition constant, K′i, of azide and cyanide were estimated to be 5.71 and 8.95 μM, respectively.

  13. Solvent-resistant organic transistors and thermally stable organic photovoltaics based on cross-linkable conjugated polymers

    KAUST Repository

    Kim, Hyeongjun

    2012-01-10

    Conjugated polymers, in general, are unstable when exposed to air, solvent, or thermal treatment, and these challenges limit their practical applications. Therefore, it is of great importance to develop new materials or methodologies that can enable organic electronics with air stability, solvent resistance, and thermal stability. Herein, we have developed a simple but powerful approach to achieve solvent-resistant and thermally stable organic electronic devices with a remarkably improved air stability, by introducing an azide cross-linkable group into a conjugated polymer. To demonstrate this concept, we have synthesized polythiophene with azide groups attached to end of the alkyl chain (P3HT-azide). Photo-cross-linking of P3HT-azide copolymers dramatically improves the solvent resistance of the active layer without disrupting the molecular ordering and charge transport. This is the first demonstration of solvent-resistant organic transistors. Furthermore, the bulk-heterojunction organic photovoltaics (BHJ OPVs) containing P3HT-azide copolymers show an average efficiency higher than 3.3% after 40 h annealing at an elevated temperature of 150 °C, which represents one of the most thermally stable OPV devices reported to date. This enhanced stability is due to an in situ compatibilizer that forms at the P3HT/PCBM interface and suppresses macrophase separation. Our approach paves a way toward organic electronics with robust and stable operations. © 2011 American Chemical Society.

  14. Synthesis, crystal structures and spectral properties of cobalt(Ⅱ) complexes: [ CoL(N3) ] ·ClO4 and CoL(N3)2 [ L = tris ( (3,5- dimethylpyrazol-l-yl) methyl) amine

    Institute of Scientific and Technical Information of China (English)

    张智慧; 杨海龙; 马志宏; 戚爱棣

    2000-01-01

    Twomonomeric cob a lt(Ⅱ)complexes, [CoL(N3)]·ClO4 (1) and CoL(N3)2 (2), where L is tris((3,5-di methyl)amineyl) methyl)amine, were synthesized and their crystal structures were determined by X-ray diffraction technique. Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen ato ms of the tris((3,5-dimethylpyrazol-l-yl)-methyl) amine ligand, and the metal center is in distorted trigonal bipyramidal environmnt. Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-l-y l)-methyl)amine ligand. The solution behaviors of the title complexes have been further investigated by UV-Vis, and 1H NMR analvsis. It is found that the formation of1 and2 de - pends on the molar ratio of the azide ion to metal salt and ligand. Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups, and the reasons were well discussed.

  15. Efficient enzymatic synthesis and dual-colour fluorescent labelling of DNA probes using long chain azido-dUTP and BCN dyes.

    Science.gov (United States)

    Ren, Xiaomei; El-Sagheer, Afaf H; Brown, Tom

    2016-05-01

    A sterically undemanding azide analogue of dTTP (AHP dUTP) with an alkyl chain and ethynyl attachment to the nucleobase was designed and incorporated into DNA by primer extension, reverse transcription and polymerase chain reaction (PCR). An azide-modified 523 bp PCR amplicon with all 335 thymidines replaced by AHP dU was shown to be a perfect copy of the template from which it was amplified. Replacement of thymidine with AHP dU increases duplex stability, accounting in part for the high incorporation efficiency of the azide-modified triphosphate. Single-stranded azide-labelled DNA was conveniently prepared from PCR products by λ-exonuclease digestion and streptavidin magnetic bead isolation. Efficient fluorescent labelling of single and double-stranded DNA was carried out using dyes functionalized with bicyclo[6.1.0]non-4-yne (BCN) via the strain-promoted alkyne-azide cycloaddition (SPAAC) reaction. This revealed that the degree of labelling must be carefully controlled to achieve optimum fluorescence and avoid fluorescence quenching. Dual-coloured probes were obtained in a single tube fluorescent labelling reaction; and varying the ratios of the two dyes provides a simple method to prepare DNA probes with unique fluorescent signatures. AHP dUTP is a versatile clickable nucleotide with potentially wide applications in biology and nanotechnology including single molecule studies and synthesis of modified aptamer libraries via SELEX. PMID:26819406

  16. Modular synthesis of a block copolymer with a cleavable linkage via “click” chemistry

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A diblock copolymer poly(ethylene glycol)-block-polystyrene or PEG-b-PS with an olefinic double bond at the PEG and PS junction has been prepared by modular synthesis via"click"chemistry.This involved the synthesis of PS by atom transfer radical polymerization and the nucleophilic substitution of the terminal bromide group with azide to yield azide-terminated PS. PEG with an alkynyl terminal group was prepared from reacting carboxyl-end-functionalized PEG with 4-hydroxybut-2-enyl prop-2-ynyl succinate,which contained an alkynyl group as well as an olefin group.The PS and PEG polymers were linked via the 1,3-dipolar cycloaddition of the end azide and alkyne groups.The obtained copolymer was characterized by 1H NMR spectroscopy and size exclusion chromatography(SEC).SEC analysis indicated that the diblock copolymer produced could be readily cleaved by ozonolysis to regenerate the constituent homopolymers.

  17. Carbocation lifetimes and entropy of water addition to carbocations dependent on their stability

    Indian Academy of Sciences (India)

    V Jagannadham

    2003-02-01

    Iminodiazonium ions (-azidobenzyl carbocations) were produced in aqueous solution by chemical initiation (solvolysis) of benzyl-gem-diazides. Solvolysis reactions of benzyl-gem-diazides in water proceed by a stepwise mechanism through -azidobenzyl carbocation intermediates, which are captured by water to give the corresponding carbonyl compounds as the sole detectable products. Rate constant ratio / (M-1) for partitioning of the carbocation between reaction with azide ion and reaction with water was determined by analysis of azide common ion inhibition of the solvolysis reaction. Rate constants (s-1) for the reaction of the cation with solvent water were determined from the experimental values of / and solv, for the solvolysis of the benzyl-gem-diazides, using = 5 × 109 M-1 s-1 for diffusion-limited reactions of azide ion with -azidobenzyl carbocations. Values of 1/ were thus the lifetimes of the -azidobenzyl carbocations. From the study of effect of temperature on solv and the activation parameters are determined and discussed.

  18. Synthesis & Characterisation of Hydroxy Terminated Polyepichlorohydrin & Polyglycidylazide.

    Directory of Open Access Journals (Sweden)

    S. P. Panda

    1996-12-01

    Full Text Available Polyglycidylazides with molecular weight more than 2000 and 100.000 have been synthesized by reacting polyepichlorohydrin (PECH diol with sodium azide in dimethyl sulphoxide. The conversion of the chloropolymers to azide polymers was above 90 per cent as estimated by fast neutron activation analysis. PECH of Mn around 2000 was synthesized by activated monomer polymerization of epichlorohydrin using boron trifluoride-ethylene glycol complex as catalyst while aluminium triethylethylene glycol complex was employed as catalyst to get PECHof Mn more than 100.000. The polymers were characterized by various spectral analyses. fast neutron activation analysis and molecular weight measurement. The PECHdiols and their corresponding azides of Mn greater than 2000 and 100.000cured readily with toluene diisocyanate using triethylamine and dibutyl tin dilaurate as catalysts.

  19. The Pasteur effect and catabolite repression in an oxidative yeast, Kluyveromyces lactis.

    Science.gov (United States)

    Royt, P W; MacQuillan, A M

    1979-01-01

    The presence of the Pasteur effect in Kluyveromyces lactis grown in glucose was shown by azide-stimulated glucose fermentation. Extracts from these cells contained ATP-sensitive phosphofructokinase activity. Cells grown on succinate oxidized glucose slowly at first without azide-stimulated rates of fermentation. Phosphofructokinase in these cells was ATP-insensitive. The activity of NAD+-isocitrate dehydrogenase in cell extracts did not require AMP activation. These results suggested the presence of a Pasteur effect in glucose-grown but not in succinate-grown K. lactis, mediated by (a) ATP inhibition of phosphofructokinase (b) possibly via feedback control of glucose transport, but not by AMP activation of isocitrate dehydrogenase. Azide inhibition of the Pasteur effect during growth of the cells did not lead to catabolite repression of respiratory activity. The results therefore suggest that the Pasteur effect does not inhibit the development of a Crabtree effect in oxidative yeasts.

  20. Effects of chemical fuel composition on energy generation from thermopower waves

    International Nuclear Information System (INIS)

    Thermopower waves, which occur during combustion within hybrid structures formed from nanomaterials and chemical fuels, result in a self-propagating thermal reaction and concomitantly generate electrical energy from the acceleration of charge carriers along the nanostructures. The hybrid structures for thermopower waves are composed of two primary components: the core thermoelectric material and the combustible fuel. So far, most studies have focused on investigating various nanomaterials for improving energy generation. Herein, we report that the composition of the chemical fuel used has a significant effect on the power generated by thermopower waves. Hybrid nanostructures consisting of mixtures of picric acid and picramide with sodium azide were synthesized and used to generate thermopower waves. A maximum voltage of ∼2 V and an average peak specific power as high as 15 kW kg−1 were obtained using the picric acid/sodium azide/multiwalled carbon nanotubes (MWCNTs) array composite. The average reaction velocity and the output voltage in the case of the picric acid/sodium azide were 25 cm s−1 and 157 mV, while they were 2 cm s−1 and 3 mV, in the case of the picramide/sodium azide. These marked differences are attributable to the chemical and structural differences of the mixtures. Mixing picric acid and sodium azide in deionized water resulted in the formation of 2,4,6-trinitro sodium phenoxide and hydrogen azide (H-N3), owing to the exchange of H+ and Na+ ions, as well as the formation of fiber-like structures, because of benzene π stacking. The negative enthalpy of formation of the new compounds and the fiber-like structures accelerate the reaction and increase the output voltage. Elucidating the effects of the composition of the chemical fuel used in the hybrid nanostructures will allow for the control of the combustion process and help optimize the energy generated from thermopower waves, furthering the development of thermopower waves as an energy

  1. Selective posttranslational modification of phage-displayed polypeptides

    Energy Technology Data Exchange (ETDEWEB)

    Tsao, Meng-Lin; Tian, Feng; Schultz, Peter

    2013-11-19

    The invention relates to posttranslational modification of phage-displayed polypeptides. These displayed polypeptides comprise at least one unnatural amino acid, e.g., an aryl-azide amino acid such as p-azido-L-phenylalanine, or an alkynyl-amino acid such as para-propargyloxyphenylalanine, which are incorporated into the phage-displayed fusion polypeptide at a selected position by using an in vivo orthogonal translation system comprising a suitable orthogonal aminoacyl-tRNA synthetase and a suitable orthogonal tRNA species. These unnatural amino acids advantageously provide targets for posttranslational modifications such as azide-alkyne [3+2] cycloaddition reactions and Staudinger modifications.

  2. Selective posttranslational modification of phage-displayed polypeptides

    Energy Technology Data Exchange (ETDEWEB)

    Tsao, Meng-Lin; Tian, Feng; Schultz, Peter

    2013-02-05

    The invention relates to posttranslational modification of phage-displayed polypeptides. These displayed polypeptides comprise at least one unnatural amino acid, e.g., an aryl-azide amino acid such as p-azido-L-phenylalanine, or an alkynyl-amino acid such as para-propargyloxyphenylalanine, which are incorporated into the phage-displayed fusion polypeptide at a selected position by using an in vivo orthogonal translation system comprising a suitable orthogonal aminoacyl-tRNA synthetase and a suitable orthogonal tRNA species. These unnatural amino acids advantageously provide targets for posttranslational modifications such as azide-alkyne [3+2]cycloaddition reactions and Staudinger modifications.

  3. Complex Surface Concentration Gradients by Stenciled "Electro Click Chemistry"

    DEFF Research Database (Denmark)

    Hansen, Thomas Steen; Lind, Johan Ulrik; Daugaard, Anders Egede;

    2010-01-01

    Complex one- or two-dimensional concentration gradients of alkynated molecules are produced on azidized conducting polymer substrates by stenciled "electro click chemistry". The latter describes the local electrochemical generation of catalytically active Cu(I) required to complete a "click...... reaction" between alkynes and azides at room temperature. A stencil on the counter electrode defines the shape and multiplicity of the gradient(s) on the conducting polymer substrate, while the specific reaction conditions control gradient steepness and the maximum concentration deposited. Biologically...

  4. Functionalization of Mechanochemically Passivated Germanium Nanoparticles via "Click" Chemistry

    Science.gov (United States)

    Purkait, Tapas Kumar

    Germanium nanoparticles (Ge NPs) may be fascinating for their electronic and optoelectronic properties, as the band gap of Ge NPs can be tuned from the infrared into the visible range of solar spectru. Further functionalization of those nanoparticles may potentially lead to numerous applications ranging from surface attachment, bioimaging, drug delivery and nanoparticles based devices. Blue luminescent germanium nanoparticles were synthesized from a novel top-down mechanochemical process using high energy ball milling (HEBM) of bulk germanium. Various reactive organic molecules (such as, alkynes, nitriles, azides) were used in this process to react with fresh surface and passivate the surface through Ge-C or Ge-N bond. Various purification process, such as gel permeation chromatography (GPC), Soxhlet dailysis etc. were introduced to purify nanoparticles from molecular impurities. A size separation technique was developed using GPC. The size separated Ge NPs were characterize by TEM, small angle X-ray scattering (SAXS), UV-vis absorption and photoluminescence (PL) emission spectroscopy to investigate their size selective properties. Germanium nanoparticles with alkyne termini group were prepared by HEBM of germanium with a mixture of n-alkynes and alpha, o-diynes. Additional functionalization of those nanoparticles was achieved by copper(I) catalyzed azide-alkyne "click" reaction. A variety of organic and organometallic azides including biologically important glucals have been reacted in this manner resulting in nanopartilces adorned with ferrocenyl, trimethylsilyl, and glucal groups. Additional functionalization of those nanoparticles was achieved by reactions with various azides via a Cu(I) catalyzed azide-alkyne "click" reaction. Various azides, including PEG derivatives and cylcodextrin moiety, were grafted to the initially formed surface. Globular nanoparticle arrays were formed through interparticle linking via "click" chemistry or "host-guest" chemistry

  5. Diazido{(S-1-phenyl-N,N-bis[(2-pyridylmethyl]ethanamine}copper(II

    Directory of Open Access Journals (Sweden)

    Sankara Rao Rowthu

    2011-07-01

    Full Text Available In the title compound, [Cu(N32(C20H21N3], the CuII ion is coordinated by the three N atoms of the (S-1-phenyl-N,N-bis[(2-pyridylmethyl]ethanamine ligand and two N atoms from two azide anions, resulting in a distorted square-pyramidal environment. A weak intermolecular C—H...N hydrogen-bonding interaction between one pyridine group of the ligand and an azide N atom of an adjacent complex unit gives a one-dimensional chain structure parallel to the c axis.

  6. Effect of ring size on the direction of rearrangement in bicyclic 1-tosyl-5-ethoxy-1,2,3-triazolines

    International Nuclear Information System (INIS)

    The authors determine that the title trazoline, formed in the reaction of tosyl azide with 1-epoxycyclohexene, is converted into ethyl N-tosylcyclopentencarbimidate, which is then converted into cyclopentanecarbohydrazide. The triazoline formed in the reaction of tosyl azide with 1-epoxycyclopentene is converted into N-(2-ethoxy-1-cyclopentenyl)toluenesulfonamide, the production of which indicates the intermediate formation of 2,3-trimethylene-1-tosyl-2-ethoxyaziridine. Consequently, the triazoline does not rearrange to ethyl N-tosylcyclobutanecarbimidate, in spite of the fact that it is substituted at the C-4 atom. Data on spin-spin coupling constants and chemical shift derived from the NMR spectra are analyzed

  7. Improvement of Barley and Chenopodium species in the Andean region by induced mutations

    International Nuclear Information System (INIS)

    Experiments on the genetic improvement of barley (H. vulgare), quinoa (Chenopodium quinoa), and canahua (C. pallidicaule) were conducted in the field and greenhouse at the Centro de Investigaciones Nucleares at Viacha, using different concentrations and treatment durations of sodium azide (NaN3) to induce beneficial mutations. Greenhouse tests were conducted to establish the concentration and treatment duration for sodium azide. The treatments were applied and field evaluations were carried out in different generations to improve the germplasm available in the country, particularly in respect to environmental stresses such as frost, hail, and drought, which severely restrict yields. (author). 3 tabs

  8. Low-Fouling Antibacterial Reverse Osmosis Membranes via Surface Grafting of Graphene Oxide.

    Science.gov (United States)

    Huang, Xinwei; Marsh, Kristofer L; McVerry, Brian T; Hoek, Eric M V; Kaner, Richard B

    2016-06-15

    Azide-functionalized graphene oxide (AGO) was covalently anchored onto commercial reverse osmosis (RO) membrane surfaces via azide photochemistry. Surface modification was carried out by coating the RO membrane with an aqueous dispersion of AGO followed by UV exposure under ambient conditions. This simple process produces a hydrophilic, smooth, antibacterial membrane with limited reduction in water permeability or salt selectivity. The GO-RO membrane exhibited a 17-fold reduction in biofouling after 24 h of Escherichia coli contact and almost 2 times reduced BSA fouling after a 1 week cross-flow test compared to its unmodified counterpart.

  9. Synthesis of 1,2-dihydro-2-oxo-4-quinolinyl phosphates from 2-acyl-benzoic acids

    Science.gov (United States)

    He, Xinhua; Aglio, Tharcilla; Deschamps, Jeffrey R.; Rai, Rachita; Xue, Fengtian

    2015-01-01

    We report a facile synthesis of 1,2-dihydro-2-oxo-4-quinolinyl phosphates (1a-l) starting from 2-acyl-benzoic acids (2a-l) in the presence of phosphoryl azides via a one-pot cascade reaction involving a Curtius rearrangement, an intramolecular nucleophilic addition of the enol carbon to the isocyanate intermediate, and an addition-elimination of the enol oxygen to the phosphoryl azide. During the reaction three new bonds are formed under mild conditions to yield 1,2-dihydro-2-oxo-4-quinolinyl phosphates in modest yields. PMID:25937677

  10. Synthesis of enantiopure sugar-decorated six-armed triptycene derivatives

    Directory of Open Access Journals (Sweden)

    Paola Bonaccorsi

    2013-11-01

    Full Text Available A new class of molecules with a triptycene rigid core surrounded by six monosaccharide residues was synthesized. Hexakis(bromomethyl substituted triptycene was converted into a six-armed triptycene azide (2,3,6,7,14,15-hexakis(azidomethyl-9,10-dihydro-9,10-[1’,2’]benzenoanthracene. The key step of the synthesis was the cycloaddition of the azide to 2-propyn-1-yl β-D-gluco- or galactopyranosides. All products were isolated in good yields and were fully characterized.

  11. Enzymatic production of atranorin: a component of the oak moss absolute by immobilized lichen cells.

    Science.gov (United States)

    Vicente, C; Fontaniella, B; Millanes, A M; Sebastián, B; Legaz, M E

    2003-04-01

    Cells of the lichen, Evernia prunastri, immobilized in calcium alginate were able to produce the depside atranorin from acetate. The synthesis of the depside was enhanced by molecular oxygen and NADH. This enhancement suggested the participation of an oxidase and an alcohol dehydrogenase to produce an aldehyde-substituted phenolic acid, hematommic acid, as the most probable precursor of atranorin. The participation of both enzymes was confirmed by loading immobilized cells with sodium azide, an inhibitor of several metallo-oxidases, and pyrazole, an inhibitor of alcohol dehydrogenase, which impeded atranorin production and accumulated beta-methyl orsellinate (after azide loading) or its alcohol derivative (after pirazole treatment). PMID:18494879

  12. Covalent deposition of zwitterionic polymer and citric acid by click chemistry-enabled layer-by-layer assembly for improving the blood compatibility of polysulfone membrane.

    Science.gov (United States)

    Xiang, Tao; Wang, Rui; Zhao, Wei-Feng; Sun, Shu-Dong; Zhao, Chang-Sheng

    2014-05-13

    Development of blood compatible membranes is critical for biomedical applications. Zwitterionic polymers have been proved to be resistant to nonspecific protein adsorption and platelet adhesion. In this work, two kinds of zwitterionic copolymers bearing alkynyl and azide groups are synthesized by atom transfer radical polymerization (ATRP) and subsequent reactions, namely alkynyl-poly(sulfobetaine methacrylate) (alkynyl-PSBMA) and azide-poly(sulfobetaine methacrylate) (azide-PSBMA). The copolymers are directly used to modify azido-functionalized polysulfone (PSf-N3) membrane via click chemistry-enabled layer-by-layer (LBL) assembly. Alkynyl-citric acid is then clicked onto the membrane when the outermost layer was azide-PSBMA. The chemical compositions, surface morphologies, and hydrophilicity of the zwitterionic polymer and citric acid multilayer modified membranes are characterized. The composite multilayer is resistant to protein adsorption and platelet adhesion and also prolongs clotting times, indicating that the blood compatibility is improved. Moreover, after clicking the small molecule anticoagulant alkynyl-citric acid onto the outermost of the zwitterionic multilayer, the membrane shows further improved anticoagulant property. The deposition of zwitterionic polymer and citric acid via click chemistry-enabled LBL assembly can improve the blood compatibility of the PSf membrane.

  13. Pressure induced tetragonal to monoclinic transition in RbN{sub 3} studied from first principles theory

    Energy Technology Data Exchange (ETDEWEB)

    Vaitheeswaran, G., E-mail: gvsp@uohyd.ernet.in; Babu, K. Ramesh, E-mail: gvsp@uohyd.ernet.in [Advanced Centre of Research in High Energy Materials (ACRHEM), University of Hyderabad, Prof. C. R. Rao Road, Gachibowli, Hyderabad-500046 (India)

    2014-04-24

    Alkali metal azides are well known for their application as explosives and gas generators. They are used as precursors in synthesis of polymeric nitrogen, an ultimate green high energy density material. Among the alkali metal azides, rubidium azide RbN{sub 3} crystallizes in tetragonal structure with linear azide ions arranged in layers and binds through weak dispersive interactions. In this present work, we have studied the structural stability, electronic structure and optical properties of solid RbN{sub 3} by using van der Waals corrected density functional theory. We find that the ambient tetragonal structure undergoes a structural transition to monoclinic structure at 0.72 GPa, which is in good agreement with the experimental transition pressure of less than 1 GPa. The phonon frequencies at the gamma point are calculated and found that the lattice mode Eg softens under pressure which may supports the structural phase transition. The electronic band structure and optical properties are calculated by using Tran Blaha-modified Becke Johnson (TB-mBJ) functional and found that solid RbN{sub 3} is an insulator with a gap of 5.976 eV and the optical absorption starts with the UV light of wave length 207.5 nm.

  14. Bioorthogonal fluorescent labeling of functional G-protein-coupled receptors

    DEFF Research Database (Denmark)

    Tian, He; Naganathan, Saranga; Kazmi, Manija A;

    2014-01-01

    contrast, the strain-promoted [3+2] azide-alkyne cycloaddition (SpAAC) with dibenzocyclooctyne (DIBO) reagents yielded stoichiometric conjugates with azF-rhodopsin while undergoing negligible background reactions. As one application of this technique, we used Alexa488-rhodopsin to measure the kinetics of...

  15. Halomethyl-cobalt(bis-acetylacetonate) for the controlled synthesis of functional polymers.

    Science.gov (United States)

    Demarteau, Jérémy; Kermagoret, Anthony; German, Ian; Cordella, Daniela; Robeyns, Koen; De Winter, Julien; Gerbaux, Pascal; Jérôme, Christine; Debuigne, Antoine; Detrembleur, Christophe

    2015-10-01

    Novel organocobalt complexes featuring weak C-CoL2 bonds (L = acetylacetonate) are prepared and used as sources of halomethyl radicals. They permit the precision synthesis of α-halide functionalized and telechelic polymers in organic media or in water. Substitution of halide by azide allows derivatization of polymers using the CuAAC click reaction. PMID:26273709

  16. Comparison of media for enumeration of Clostridium perfringens from foods

    NARCIS (Netherlands)

    Jong, A.E.I. de; Eijhusen, G.P.; Brouwer-Post, E.J.F.; Grand, M.; Johansson, T.; Kärkkäinen, T.; Marugg, J.; Veld, P.H. in 't; Warmerdam, F.H.M.; Wörner, G.; Zicavo, A.; Rombouts, F.M.; Beumer, R.R.

    2003-01-01

    Many media have been developed to enumerate Clostridium perfringens from foods. In this study, six media [iron sulfite (IS) agar, tryptose sulfite cycloserine (TSC) agar, Shahidi Ferguson perfringens (SFP) agar, sulfite cycloserine azide (SCA), differential clostridial agar (DCA), and oleandomycin p

  17. Comparative studies of photochemical cross-linking methods for stabilizing the bulk hetero-junction morphology in polymer solar cells

    DEFF Research Database (Denmark)

    Carlé, Jon Eggert; Andreasen, Birgitta; Tromholt, Thomas;

    2012-01-01

    We are here presenting a comparative study between four different types of functionalities for cross-linking. With relatively simple means bromine, azide, vinyl and oxetane could be incorporated into the side chains of the low band-gap polymer TQ1. Cross-linking of the polymers was achieved by UV...

  18. Intramolecular redox-active ligand-to-substrate single-electron transfer : Radical reactivity with a palladium(II) complex

    NARCIS (Netherlands)

    Broere, Daniël L J; De Bruin, Bas; Reek, Joost N H; Lutz, Martin; Dechert, Sebastian; Van Der Vlugt, Jarl Ivar

    2014-01-01

    Coordination of the redox-active tridentate NNO ligand LH2 to PdII yields the paramagnetic iminobenzosemiquinonato complex 3. Single-electron reduction of 3 yields diamagnetic amidophenolato complex 4, capable of activating aliphatic azide 5. Experimental and computational studies suggest a redox-no

  19. Antimutagenic potential of curcumin on chromosomal aberrations in Allium cepa

    Institute of Scientific and Technical Information of China (English)

    RAGUNATHAN Irulappan; PANNEERSELVAM Natarajan

    2007-01-01

    Turmeric has long been used as a spice and food colouring agent in Asia. In the present investigation, the antimutagenic potential of curcumin was evaluated in Allium cepa root meristem cells. So far there is no report on the biological properties of curcumin in plant test systems. The root tip cells were treated with sodium azide at 200 and 300 μg/ml for 3 h and curcumin was given at 5, 10 and 20 μg/ml for 16 h, prior to sodium azide treatment. The tips were squashed after colchicine treatment and the cells were analyzed for chromosome aberration and mitotic index. Curcumin induces chromosomal aberration in Allium cepa root tip cells in an insignificant manner, when compared with untreated control. Sodium azide alone induces chromosomal aberrations significantly with increasing concentrations. The total number of aberrations was significantly reduced in root tip cells pretreated with curcumin. The study reveals that curcumin has antimutagenic potential against sodium azide induced chromosomal aberrations in Allium cepa root meristem cells. In addition, it showed mild cytotoxicity by reducing the percentage of mitotic index in all curcumin treated groups, but the mechanism of action remains unknown. The antimutagenic potential of curcumin is effective at 5 μg/ml in Allium cepa root meristem cells.

  20. Enhanced reactivity of dinuclear Copper(I) acetylides in dipolar cycloadditions

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Fokin, V.V.

    2007-01-01

    Dinuclear alkynyl copper(I) complexes exhibit superior reactivity toward organic azides compared to their monomeric analogues. DFT studies indicate that the second copper center facilitates the formation of the cupracycle in the rate-determining step and stabilizes the metallacycle intermediate i...

  1. Versatile Route to Synthesize Heterobifunctional Poly(ethylene glycol of Variable Functionality for Subsequent Pegylation

    Directory of Open Access Journals (Sweden)

    Redouan Mahou

    2012-02-01

    Full Text Available Pegylation using heterotelechelic poly(ethylene glycol (PEG offers many possibilities to create high-performance molecules and materials. A versatile route is proposed to synthesize heterobifunctional PEG containing diverse combinations of azide, amine, thioacetate, thiol, pyridyl disulfide, as well as activated hydroxyl end groups. Asymmetric activation of one hydroxyl end group enables the heterobifunctionalization while applying selective monotosylation of linear, symmetrical PEG as a key step. The azide function is introduced by reacting monotosyl PEG with sodium azide. A thiol end group is obtained by reaction with sodium hydrosulfide. The activation of the hydroxyl end group and subsequent reaction with potassium carbonate/thioacetic acid yields a thioacetate end group. The hydrolysis of the thioester end group by ammonia in presence of 2,2′-dipyridyl disulfide provides PEG pyridyl disulfide. Amine terminated PEG is prepared either by reduction of the azide or by nucleophilic substitution of mesylate terminated PEG using ammonia. In all cases, >95% functionalization of the PEG end groups is achieved. The PEG derivatives particularly support the development of materials for biomedical applications. For example, grafting up to 13% of the Na-alg monomer units with α-amine-ω-thiol PEG maintains the gelling capacity in presence of calcium ions but simultaneous, spontaneous disulfide bond formation reinforces the initial physical hydrogel.

  2. Heterogeneous Catalysis through Microcontact Printing

    NARCIS (Netherlands)

    Spruell, Jason M.; Sheriff, Bonnie A.; Rozkiewicz, Dorota I.; Dichtel, William R.; Rohde, Rosemary D.; Reinhoudt, David N.; Stoddart, Fraser; Heath, James R.

    2008-01-01

    Minting a Stamp: The preparation of copper metal-coated elastomeric stamps and their use in catalyzing the Cu-catalyzed azide-alkyne cycloaddition reaction heterogeneously through microcontact printing is described. This StampCat process is compared to other conventional surface-functionalization te

  3. Azido-Iodo-N-Benzyl Derivatives of threo-Methylphenidate (Ritalin, Concerta): Rational Design, Synthesis, Pharmacological Evaluation, and Dopamine Transporter Photoaffinity Labeling

    OpenAIRE

    Lapinsky, David J.; Velagaleti, Ranganadh; Yarravarapu, Nageswari; Liu, Yi; Huang, Yurong; Surratt, Christopher K.; Lever, John R.; Foster, James D.; Acharya, Rejwi; Vaughan, Roxanne A.; Deutsch, Howard M.

    2010-01-01

    In contrast to tropane-based compounds such as benztropine and cocaine, non-tropane-based photoaffinity ligands for the dopamine transporter (DAT) are relatively unexplored. Towards addressing this knowledge gap, ligands were synthesized in which the piperidine nitrogen of 3- and 4-iodomethylphenidate was substituted with a benzyl group bearing a photoreactive azide. Analog (...

  4. Glycerol mediated synthesis of 5-substituted 1H-tetrazole under catalyst free conditions

    Institute of Scientific and Technical Information of China (English)

    Kamalakar P.Nandre; Jagdish K.Salunke; Jitendra P.Nandre; Vijay S.Patil; Amul U.Borse; Sidhanath V.Bhosale

    2012-01-01

    We have developed simple,cost effective and environmentally benign protocol for the synthesis of 5-substituted 1H-tetrazoles via [2,3] cycloaddition reaction from organic nitriles and sodium azide in glycerol under catalyst free condition.The corresponding 5-substituted 1H-tetrazoles were obtained with good to excellent yields (68-95%).

  5. Zinc chloride catalyzed synthesis of 5-substituted 1H-tetrazoles under solvent free condition

    Institute of Scientific and Technical Information of China (English)

    Shahnaz Rostamizadeh; Hamid Ghaieni; Reza Aryan; Ali Amani

    2009-01-01

    Zinc chloride is an efficient and safe catalyst in the [3 + 2] cycloaddition reaction of organic nitriles with sodium azide in solventless condition. The corresponding 5-substituted IH tetrazoles were obtained under mild conditions. This method can overcome disadvantages such as: the use of toxic metals and expensive reagents, drastic reaction conditions, water sensitivity and the presence of dangerous hydrazoic acid.

  6. Drug: D07697 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available AZIDES C03BX Other low-ceiling diuretics C03BX03 Cicletanine D07697 Cicletanine h...ATC) classification [BR:br08303] C CARDIOVASCULAR SYSTEM C03 DIURETICS C03B LOW-CEILING DIURETICS, EXCL. THI

  7. A fluorescent, photochromic and thermochromic trifunctional material based on a layered metal-viologen complex.

    Science.gov (United States)

    Wan, Fang; Qiu, Li-Xia; Zhou, Liang-Liang; Sun, Yan-Qiong; You, Yi

    2015-11-14

    The azide anion as an energy acceptor and an electron donor has been introduced into a metal-viologen compound to form a 2D layered viologen-based trifunctional material, which exhibits the rare discolored function of reversible photochromism and thermochromism. Interestingly, its fluorescence can be switched by visible light irradiation and heating in air. PMID:26445888

  8. Selective Bifunctional Modification of a Non-catenated Metal-Organic Framework Material via 'Click' Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Gadzikwa, Tendai; Farha, Omar K.; Malliakas, Christos D.; Kanatzidis, Mercouri G.; Hupp, Joseph T.; Nguyen, SonBinh T.; NWU

    2009-12-01

    A noncatenated, Zn-based metal-organic framework (MOF) material bearing silyl-protected acetylenes was constructed and postsynthetically modified using 'click' chemistry. Using a solvent-based, selective deprotection strategy, two different organic azides were 'clicked' onto the MOF crystals, resulting in a porous material whose internal and external surfaces are differently functionalized.

  9. Nano indium oxide as a recyclable catalyst for the synthesis of arylaminotetrazoles

    Indian Academy of Sciences (India)

    Siavash Bahari; Mehdi Ahmadi Sabegh

    2013-01-01

    Nano indium oxide is an effective heterogeneous catalyst for the reaction between aryl cyanamides and sodium azide to synthesize the arylaminotetrazoles in good yields. This method has advantages of high yields, simple methodology, short reaction times and easy work-up. The catalyst can be recovered and reused in good yields.

  10. Multicomponent click synthesis of potentially biologically active triazoles catalysed by copper nanoparticles on activated carbon in water

    OpenAIRE

    Alonso Valdés, Francisco; Moglie, Yanina; Radivoy, Gabriel; Yus Astiz, Miguel

    2011-01-01

    A variety of potentially biologically active 1,2,3-triazoles, derived from (–)-menthol, lactic acid, D-glucose, oestrone, cholesterol, and phenacetin, have been synthesised through the multicomponent alkyne-azide 1,3-dipolar cycloaddition catalysed by copper nanoparticles on activated carbon in neat water.

  11. Synthesis of pentafluorosulfanylpyrazole and pentafluorosulfanyl-1,2,3-triazole and their derivatives as energetic materials by click chemistry.

    Science.gov (United States)

    Ye, Chengfeng; Gard, Gary L; Winter, Rolf W; Syvret, Robert G; Twamley, Brendan; Shreeve, Jean'ne M

    2007-09-13

    1-Pentafluorosulfanyl acetylene and its derivatives react with azide or diazomethane giving rise to an SF5-substituted 1,2,3-triazole or pyrazole. The SF5 group increases density remarkably and as a result enhances the detonation performance of the energetic materials relative to the CF3 group.

  12. One-pot peptide and protein conjugation: a combination of enzymatic transamidation and click chemistry.

    Science.gov (United States)

    Rachel, N M; Pelletier, J N

    2016-02-11

    Enzymatic transamidation and copper-catalyzed azide-alkyne cycloaddition (CuAAC) were combined to yield covalently conjugated peptides and proteins. The addition of glutathione preserved enzymatic activity in the presence of copper. Tuning the reaction kinetics was key to success, providing up to 95% conversion. This one-pot reaction allowed for targeted fluorescent protein labeling. PMID:26741126

  13. Efficient and highly enantioselective formation of the all-carbon quaternary stereocentre of lyngbyatoxin A

    DEFF Research Database (Denmark)

    Vital, Paulo J.V.; Tanner, David

    2006-01-01

    Indole 25, an advanced intermediate in a projected enantioselective total synthesis of lyngbyatoxin A 1, was prepared from allylic alcohol 11 in 9 steps and >95% ee, key transformations being the enantiospecific rearrangement of vinyl epoxide 14 and the Hemetsberger-Knittel reaction of azide 24....

  14. Super-resolution optical DNA Mapping via DNA methyltransferase-directed click chemistry

    DEFF Research Database (Denmark)

    Vranken, Charlotte; Deen, Jochem; Dirix, Lieve;

    2014-01-01

    We demonstrate an approach to optical DNA mapping, which enables near single-molecule characterization of whole bacteriophage genomes. Our approach uses a DNA methyltransferase enzyme to target labelling to specific sites and copper-catalysed azide-alkyne cycloaddition to couple a fluorophore to ...

  15. Application of cyclic ketones in MCR: Ugi/amide coupling based synthesis of fused tetrazolo[1,5-a][1,4]benzodiazepines

    NARCIS (Netherlands)

    Yerande, Swapnil; Newase, Kiran; Singh, Bhawani; Boltjes, André; Dömling, Alex

    2014-01-01

    Azido-Ugi reaction involving cyclic ketone, primary amine, isonitrile, and azide afforded substituted tetrazole derivatives 5. These intermediates were hydrolyzed to corresponding acid derivatives. EDAC/HOBt mediated amide bond formation of 5 gave fused tetrazolo[1,5-a][1,4]benzodiazepine 6 in high

  16. Drug: D10275 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D10275 Mixture, Drug Bisoprolol fumarate - hydrochlorothiazide mixt; Ziac (TN) Biso...prolol fumarate [DR:D00634], Hydrochlorothiazide [DR:D00340] Antihypertensive ATC code: C07BB07 Anatomical T...azides C07BB07 Bisoprolol and thiazides D10275 Bisoprolol fumarate - hydrochlorothiazide mixt PubChem: 163312306 ...

  17. Microwave assisted click chemistry on a conductive polymer film

    DEFF Research Database (Denmark)

    Daugaard, Anders Egede; Hansen, Thomas S.; Larsen, Niels Bent;

    2011-01-01

    Microwave (MW) irradiation has been used to accelerate the functionalization of an azide functional poly(3,4-ethylenedioxythiophene) film by click chemistry. The absorption of MW energy by the conductive polymer has been exploited for localized activation of the reaction on the polymer surface...

  18. One-pot Microwave-Assisted Synthesis of 1H-Phenanthro[9,10- d][1,2,3]triazole

    Directory of Open Access Journals (Sweden)

    Mehrak Faraji

    2008-09-01

    Full Text Available In this study, a fast and good yield one-pot microwave-assisted synthesis (45 seconds of 1H-phenanthro[9,10-d][1,2,3]triazole by a 1,3-dipolar cycloaddition reaction of sodium azide and 9-bromophenanthrene in the presence of potassium tert-butoxide in DMSO as solvent is reported.

  19. Synthesis and Characterization of [60]Fullerene Ferrocenylmethyl Derivatives

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Two new [60]fullerene ferrocenylmethyl derivatives have been prepared via different approaches and characterized by UV-Vis、 FT-IR、 NMR、 FAB-MS spectra and VPO. The second approach , i.e reacting fullerene with ferrocenylmethyl azide directly, was never reported as yet.

  20. Surface enhanced Raman optical activity as an ultra sensitive tool for ligand binding analysis

    DEFF Research Database (Denmark)

    Johannessen, Christian; Abdali, Salim

    2007-01-01

    upon azide complexation. Application of this method allows for rapid analysis of ligand binding in metalloproteins in dilute aqueous solution and could in the future, when combined with theoretical studies, increase the obtainable structural resolution of proteins beyond that of X-ray analysis....

  1. A DOTA-peptide conjugate by copper-free click chemistry

    OpenAIRE

    Martin, Molly E.; Parameswarappa, Sharavathi G.; O’Dorisio, M. Sue; Pigge, F. Christopher; Schultz, Michael K.

    2010-01-01

    Attachment of DOTA to a novel monofluoro-cyclooctyne facilitates bioconjugation to an azide-modified peptide via Cu-free click chemistry. The resulting conjugate was radiolabeled with 111In to afford a potential targeted molecular imaging agent with high specific activity and in excellent radiochemical purity.

  2. Azidoethoxyphenylalanine as a Vibrational Reporter and Click Chemistry Partner in Proteins.

    Science.gov (United States)

    Tookmanian, Elise M; Phillips-Piro, Christine M; Fenlon, Edward E; Brewer, Scott H

    2015-12-21

    An unnatural amino acid, 4-(2-azidoethoxy)-L-phenylalanine (AePhe, 1), was designed and synthesized in three steps from known compounds in 54% overall yield. The sensitivity of the IR absorption of the azide of AePhe was established by comparison of the frequency of the azide asymmetric stretch vibration in water and dimethyl sulfoxide. AePhe was successfully incorporated into superfolder green fluorescent protein (sfGFP) at the 133 and 149 sites by using the amber codon suppression method. The IR spectra of these sfGFP constructs indicated that the azide group at the 149 site was not fully solvated despite the location in sfGFP and the three-atom linker between the azido group and the aromatic ring of AePhe. An X-ray crystal structure of sfGFP-149-AePhe was solved at 1.45 Å resolution and provides an explanation for the IR data as the flexible linker adopts a conformation which partially buries the azide on the protein surface. Both sfGFP-AePhe constructs efficiently undergo a bioorthogonal strain-promoted click cycloaddition with a dibenzocyclooctyne derivative.

  3. Involvement of sulfide:quinone oxidoreductase in sulfur oxidation of an acidophilic iron-oxidizing bacterium, Acidithiobacillus ferrooxidans NASF-1.

    Science.gov (United States)

    Wakai, Satoshi; Kikumoto, Mei; Kanao, Tadayoshi; Kamimura, Kazuo

    2004-12-01

    The effects of cyanide, azide, and 2-n-Heptyl-4-hydroxy-quinoline-N-oxide (HQNO) on the oxidation of ferrous ion or elemental sulfur with Acidithiobacillus ferrooxidans NASF-1 cells grown in iron- or sulfur-medium were examined. The iron oxidation of both iron- and sulfur-grown cells was strongly inhibited by cyanide and azide, but not by HQNO. Sulfur oxidation was relatively resistant to cyanide and azide, and inhibited by HQNO. Higher sulfide oxidation, ubiquinol dehydrogenase activity, and sulfide:quinone oxidoreductase (SQR) activity were observed in sulfur-grown cells more than in iron-grown cells. Sulfide oxidation in the presence of ubiquinone with the membrane fraction was inhibited by HQNO, but not by cyanide, azide, antimycin A, and myxothiazol. The transcription of three genes, encoding an aa(3)-type cytochrome c oxidase (coxB), a bd-type ubiquinol oxidase (cydA), and an sqr, were measured by real-time reverse transcription polymerase chain reaction. The transcriptional levels of coxB and cydA genes were similar in sulfur- and iron-grown cells, but that of sqr was 3-fold higher in sulfur-grown cells than in iron-grown cells. A model is proposed for the oxidation of reduced inorganic sulfur compounds in A. ferrooxidans NASF-1 cells. PMID:15618623

  4. The Formation of Large-Area Conducting Graphene-Like Platelets

    NARCIS (Netherlands)

    Salvio, Riccardo; Krabbenborg, Sven; Naber, Wouter J.M.; Velders, Aldrik H.; Reinhoudt, David N.; Wiel, van der Wilfred G.

    2009-01-01

    The treatment of a suspension of graphite oxide (GO) with sodium azide leads to a material that, after reduction, features amino groups at the top and bottom of the sheets. These groups react through microcontact printing with an isothiocyanate monolayer on a silicon oxide substrate to form covalent

  5. Comparison of methods for specific depletion of ATP in Salmonella typhimurium.

    OpenAIRE

    Johnson, M. S.; Taylor, B L

    1993-01-01

    Three methods of ATP depletion in Salmonella typhimurium were compared. ATP concentrations were lowest after arsenate treatment. Arsenate or alpha-methylglucoside-plus-azide treatment nonspecifically lowered all nucleotide triphosphate levels. Histidine starvation in a hisF mutant was relatively specific for ATP depletion and therefore has potential in distinguishing ATP-dependent processes from processes dependent on other nucleotides.

  6. Sulfonamide bearing oligonucleotides: Simple synthesis and efficient RNA recognition

    DEFF Research Database (Denmark)

    Kumar, P.; Chandak, N.; Nielsen, P.;

    2012-01-01

    Four pyrimidine nucleosides wherein a benzensulfonamide group is linked to the C-5 position of the uracil nucleobase through a triazolyl or an alkynyl linker were prepared by Cu(I)-assisted azide-alkyne cycloadditions (CuAAC) or Sonogashira reactions, respectively, and incorporated into oligonucl...

  7. Bimetallic nickel complexes for selective CO2 carbon capture and sequestration.

    Science.gov (United States)

    Möller, F; Merz, K; Herrmann, C; Apfel, U-P

    2016-01-21

    Herein we report a dinickel azacryptand complex that enables fast, selective, and tight CO2 binding from air. Exploiting the affinity of the cavitand towards azides, CO2 release was observed. Despite the stability of the azido complex, UV irradiation under atmospheric conditions proved to be a suitable pathway for N3(-) replacement by CO2. PMID:26666316

  8. Cytochrome oxidase as an indicator of ice storage and frozen storage

    DEFF Research Database (Denmark)

    Godiksen, Helene; Jessen, Flemming

    2001-01-01

    of 30 degreesC. Maximal activation by Triton X-100 was obtained in a range of 0.62-1.25 mM Triton X-100. The specificity of the assay was high, as cytochrome oxidase was inhibited 98% by 33 muM of the specific inhibitor sodium azide. The coefficient of variation of cytochrome oxidase activity...

  9. Conductive Polymer Functionalization by Click Chemistry

    DEFF Research Database (Denmark)

    Daugaard, Anders Egede; Hvilsted, Søren; Hansen, Thomas Steen;

    2008-01-01

    Click chemistry is used to obtain new conductive polymer films based on poly(3,4-ethylenedioxythiophene) (PEDOT) from a new azide functional monomer. Postpolymerization, 1,3-dipolar cycloadditions in DMF, using a catalyst system of CUS04 and sodium ascorbate, and different alkynes are performed...

  10. Ultramild protein-mediated click chemistry creates efficient oligonucleotide probes for targeting and detecting nucleic acids

    DEFF Research Database (Denmark)

    Nåbo, Lina J.; Madsen, Charlotte Stahl; Jensen, Knud Jørgen;

    2015-01-01

    conditions with fluorophore, peptide, and carbohydrate azide derivatives. In thermal denaturation studies, the modified probes showed specific binding to complementary DNA and RNA targets. Finally, we demonstrated the pH sensitivity of the new rhodamine-based fluorescent probes in vitro and rationalize our...

  11. Mildew-resistant mutants induced in North American two- and six-rowed malting barley cultivars

    DEFF Research Database (Denmark)

    Molina-Cano, J.L.; Simiand, J.P.; Sopena, A.;

    2003-01-01

    Mildew-resistant mutants were induced with sodium azide in three North American malting barley cultivars, two in the six-rowed Ursula (URS1 and URS2), one in the six-rowed Gertrud (GER1), and one in the two-rowed Prudentia (PRU1). Two of the mutants, URS1 and PRU1, showed complete resistance and...

  12. Lectin release by soybean seeds

    Energy Technology Data Exchange (ETDEWEB)

    Fountain, D.W.; Foard, D.E.; Replogle, W.D.; Yang, W.K.

    1977-09-16

    Lectin is released from soybean seeds during water uptake. Hemagglutination activity data show that the lectin is a preferential release product within the first 8 hours of hydration. A qualitative filter-paper assay for detection of lectin released by single seeds is used to show that the release phenomenon is independent of seed viability and insensitive to azide.

  13. Toxic effects exerted on methanogenic, nitrifying and denitrifying bacteria by chemicals used in a milk analysis laboratory

    NARCIS (Netherlands)

    Lopez-Fiuza, J.; Buys, B.; Mosquera-Corral, A.; Omil, F.; Mendez, R.

    2002-01-01

    The toxic effects caused by the chemicals contained in wastewaters generated by laboratories involved in raw milk analyses were assessed using batch assays. These assays were carried out separately with methanogenic, ammonium-oxidizing, nitrite-oxidizing and denitrifying bacteria. Since sodium azide

  14. Functional Group Analysis.

    Science.gov (United States)

    Smith, Walter T., Jr.; Patterson, John M.

    1984-01-01

    Literature on analytical methods related to the functional groups of 17 chemical compounds is reviewed. These compounds include acids, acid azides, alcohols, aldehydes, ketones, amino acids, aromatic hydrocarbons, carbodiimides, carbohydrates, ethers, nitro compounds, nitrosamines, organometallic compounds, peroxides, phenols, silicon compounds,…

  15. Towards copper-free nanocapsules obtained by orthogonal interfacial "click" polymerization in miniemulsion.

    Science.gov (United States)

    Siebert, Joerg Max; Baier, Grit; Musyanovych, Anna; Landfester, Katharina

    2012-06-01

    A facile method to produce nanocapsules by copper-free interfacial "click"-polymerization as orthogonal reaction for the encapsulation of functional molecules is successfully performed using stable miniemulsion droplets. Difunctional azides and alkynes have been used for polymerization around the miniemulsion droplets, leading to the formation of nanocapsules. The results were compared with copper-catalyzed systems.

  16. Conjugating folate on superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles using click chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Xiaofang, E-mail: xfshen@jiangnan.edu.cn; Ge, Zhaoqiang; Pang, Yuehong

    2015-02-15

    Gold-coated magnetic core@shell nanoparticles, which exhibit magneto-optical properties, not only enhance the chemical stability of core and biocompatibility of surface, but also provide a combination of multimodal imaging and therapeutics. The conjugation of these tiny nanoparticles with specific biomolecules allows researchers to target the desired location. In this paper, superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles were synthesized and functionalized with the azide group on the surface by formation of self-assembled monolayers. Folate (FA) molecules, non-immunogenic target ligands for cancer cells, are conjugated with alkyne and then immobilized on the azide-terminated Fe{sub 3}O{sub 4}@Au nanoparticles through copper(I)-catalyzed azide-alkyne cycloaddition (click reaction). Myelogenous leukemia K562 cells were used as a folate receptor (FR) model, which can be targeted and extracted by magnetic field after interaction with the Fe{sub 3}O{sub 4}@Au–FA nanoparticles. - Graphical abstract: Self-assembled azide-terminated group on superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles followed by click reaction with alkyne-functionalized folate, allowing the nanoparticles target folate receptor of cancer cells. - Highlights: • Azidoundecanethiol was coated on the superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles by forming self-assembled monolayers. • Alkyne-terminated folate was synthesized from a reaction between the amine and the carboxylic acid. • Conjugation of Fe{sub 3}O{sub 4}@Au nanoparticles with folate was made by copper-catalyzed azide-alkyne cycloaddition click chemistry.

  17. High-yield clicking and dissociation of doxorubicin nanoclusters exhibiting differential cellular uptakes and imaging.

    Science.gov (United States)

    Kim, Hye Sung; Yoon, Sujin; Son, Young Ju; Park, Yeonju; Jung, Young Mee; Yoo, Hyuk Sang

    2015-11-10

    Gold nanoparticles (AuNPs) and quantum dots (Qdots) were clicked into doxorubicin nanoclusters that showed enzyme-dependent dissociation behaviors for differential cellular uptakes and imaging. The AuNPs were co-functionalized with doxorubicin (DOX) and azide-terminated polymer (DOX/azide@AuNP), while an enzyme-cleavable peptide and alkyne-terminated polymer were sequentially conjugated on Qdot surface (Alkyne-MMP@Qdot). Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and fluorescence imaging detected the azide and alkyne groups on DOX/azide@AuNP and Alkyne-MMP@Qdot, respectively, and the click-reactivity was also confirmed. In the presence of the catalyst, two nanoparticles were clicked to doxorubicin nanoclusters, which increased the volume of the particles ca. 343-fold within 30min. Upon matrix metalloproteinase-2 (MMP-2) digestion, the nanoclusters were clearly dissociated into smaller particles, and the fluorescence of the quenched Qdot was also recovered, which suggests that the nanoclusters respond to MMP-2 concentrations and can thus be employed for cancer imaging. Confocal microscopy and an elemental analysis of the cancer cells revealed that the cellular uptakes of doxorubicin nanoclusters significantly increased at higher MMP-2 concentrations, and doxorubicin could also be cleaved for anti-cancer effects. In vivo and in vitro cytotoxicity assay accordingly showed that the cytotoxicity of doxorubicin nanoclusters against cancer cells increased in MMP-2-rich environments such as tumor site. Thus, these nanoclusters containing DOX/azide@AuNP and Alkyne-MMP@Qdot are expected to be multifunctional carriers for targeted anti-cancer treatments and imaging. PMID:26315815

  18. Comparative study of chemical and physical methods for distinguishing between passive and metabolically active mechanisms of water contaminant removal by biofilms.

    Science.gov (United States)

    Adapa, L M; Azimi, Y; Singh, S; Porcelli, D; Thompson, I P

    2016-09-15

    In this study, physical and chemical approaches were employed to distinguish between passive and active mechanisms in biofilms removing contaminants in waste waters and their relative merits were assessed. Respiration, post-exposure recovery and scanning electron microscopic analysis demonstrated that both ultraviolet (UV) treatment (300 mJ/cm(2)) and sodium azide (10 mM) completely inhibited metabolic activity at 5 and 24 h exposure, respectively, whilst not damaging the integrity of the biofilms. Amongst the commonly used chemical inhibitors, only sodium azide showed complete inhibition after 24 h incubation with only about 10% (±4%) of biofilm carbon released into the bulk solution, compared to 33-41% (±8%) when exposed to 5 mM and 10 mM 2,4-dinitrophenol (DNP) and 69-80% (±5%) when exposed to 2% and 5% w/v formalin, respectively. Biofilm inhibition with UV and sodium azide was found to be equally effective at inhibiting biofilms for treatment of triethanolamine (TEA) and benzotriazole (BTA): the results confirming that the dominant removal mechanism was biodegradation. However, the rates of glucose removal by sodium azide-inhibited biofilms were similar to controls, suggesting that chemical inhibitors were not effective for distinguishing the removal mechanisms of simple sugars. Statistically similar amounts of metal were removed by biofilms treated with UV and sodium azide in zinc, copper and cadmium single-systems: the results indicated that the removal mechanism is predominantly a passive biosorption process. PMID:27314554

  19. The photochemistry of [Fe(III)N3(cyclam-ac)]PF6 at 266 nm.

    Science.gov (United States)

    Torres-Alacan, Joel; Krahe, Oliver; Filippou, Alexander C; Neese, Frank; Schwarzer, Dirk; Vöhringer, Peter

    2012-03-01

    The photochemistry of iron azido complexes is quite challenging and poorly understood. For example, the photochemical decomposition of [Fe(III)N(3)(cyclam-ac)]PF(6) ([1]PF(6)), where cyclam-ac represents the 1,4,8,11-tetraazacyclotetradecane-1-acetate ligand, has been shown to be wavelength-dependent, leading either to the rare high-valent iron(V) nitrido complex [Fe(V)N(cyclam-ac)]PF(6) ([3]PF(6)) after cleavage of the azide N(α)-N(β) bond, or to a photoreduced Fe(II) species after Fe-N(azide) bond homolysis. The mechanistic details of this intriguing reactivity have never been studied in detail. Here, the photochemistry of 1 in acetonitrile solution at room temperature has been investigated using step-scan and rapid-scan time-resolved Fourier transform infrared (FTIR) spectroscopy following a 266 nm, 10 ns pulsed laser excitation. Using carbon monoxide as a quencher for the primary iron-containing photochemical product, it is shown that 266 nm excitation of 1 results exclusively in the cleavage of the Fe-N(azide) bond, as was suspected from earlier steady-state irradiation studies. In argon-purged solutions of [1]PF(6), the solvent-stabilized complex cation [Fe(II)(CH(3)CN)(cyclam-ac)](+) (2red) together with the azide radical (N(3)(.)) is formed with a relative yield of 80%, as evidenced by the appearance of their characteristic vibrational resonances. Strikingly, step-scan experiments with a higher time resolution reveal the formation of azide anions (N(3)(-)) during the first 500 ns after photolysis, with a yield of 20%. These azide ions can subsequently react thermally with 2red to form [Fe(II)N(3)(cyclam-ac)] (1red) as a secondary product of the photochemical decomposition of 1. Molecular oxygen was further used to quench 1red and 2red to form what seems to be the elusive complex [Fe(O(2))(cyclam-ac)](+) (6).

  20. Effects of chemical fuel composition on energy generation from thermopower waves.

    Science.gov (United States)

    Yeo, Taehan; Hwang, Hayoung; Jeong, Dong-Cheol; Lee, Kang Yeol; Hong, Jongsup; Song, Changsik; Choi, Wonjoon

    2014-11-01

    Thermopower waves, which occur during combustion within hybrid structures formed from nanomaterials and chemical fuels, result in a self-propagating thermal reaction and concomitantly generate electrical energy from the acceleration of charge carriers along the nanostructures. The hybrid structures for thermopower waves are composed of two primary components: the core thermoelectric material and the combustible fuel. So far, most studies have focused on investigating various nanomaterials for improving energy generation. Herein, we report that the composition of the chemical fuel used has a significant effect on the power generated by thermopower waves. Hybrid nanostructures consisting of mixtures of picric acid and picramide with sodium azide were synthesized and used to generate thermopower waves. A maximum voltage of ∼2 V and an average peak specific power as high as 15 kW kg(-1) were obtained using the picric acid/sodium azide/multiwalled carbon nanotubes (MWCNTs) array composite. The average reaction velocity and the output voltage in the case of the picric acid/sodium azide were 25 cm s(-1) and 157 mV, while they were 2 cm s(-1) and 3 mV, in the case of the picramide/sodium azide. These marked differences are attributable to the chemical and structural differences of the mixtures. Mixing picric acid and sodium azide in deionized water resulted in the formation of 2,4,6-trinitro sodium phenoxide and hydrogen azide (H-N3), owing to the exchange of H(+) and Na(+) ions, as well as the formation of fiber-like structures, because of benzene π stacking. The negative enthalpy of formation of the new compounds and the fiber-like structures accelerate the reaction and increase the output voltage. Elucidating the effects of the composition of the chemical fuel used in the hybrid nanostructures will allow for the control of the combustion process and help optimize the energy generated from thermopower waves, furthering the development of thermopower waves as an energy

  1. Using click chemistry to modify block copolymers and their morphologies

    Science.gov (United States)

    Wollbold, Johannes

    Microphase separated block copolymers (BCPs) are emerging as promising templates and scaffolds for the fabrication of nanostructured materials. To achieve the desired nanostructures, it is necessary to establish convenient approaches to control the morphology of BCPs. It remains challenging to induce morphological transitions of BCPs via external fields. Click chemistry, especially alkyne/azide click chemistry, has been widely used to synthesize novel functionalized materials. Here, we demonstrate that alkyne/azide click chemistry can be used as an efficient approach to chemically modify BCPs and therefore induce morphological transitions. Alkyne-functionalized diblock copolymers (di-BCPs) poly(ethylene oxide)- block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) have been successfully synthesized. When the di-BCP is blended with an azide additive Rhodamine B azide and annealed at elevated temperatures, click reaction occurs between the two components. With the Rhodamine B structure attached to the polymer backbone, the di-BCP shows dramatic change in the interactions between the two blocks and the volume fraction of each block. As a result, morphological transitions, such as disorder-to-order transitions (DOTs) and order-to-order transitions (OOTs), are observed. The reaction kinetics and morphology evolution during the click chemistry induced DOTs have been investigated by in-situ and ex-situ characterizations, and fast kinetics properties are observed. Microphase separated morphologies after the DOTs or OOTs are dictated by the composition of neat di-BCPs and the mole ratio between the alkyne and azide groups. The DOTs of PEO-b-P(nBMA-r-PgMA) di-BCPs induced by alkyne/azide click chemistry have also been achieved in thin film geometries, with comparable kinetics to bulk samples. The orientation of the microdomains is dependent on the grafting density of Rhodamine B structure as well as film thickness. At higher grafting densities

  2. Staudinger ligation as a method for bioconjugation.

    Science.gov (United States)

    van Berkel, Sander S; van Eldijk, Mark B; van Hest, Jan C M

    2011-09-12

    In 1919 the German chemist Hermann Staudinger was the first to describe the reaction between an azide and a phosphine. It was not until recently, however, that Bertozzi and co-workers recognized the potential of this reaction as a method for bioconjugation and transformed it into the so-called Staudinger ligation. The bio-orthogonal character of both the azide and the phosphine functions has resulted in the Staudinger ligation finding numerous applications in various complex biological systems. For example, the Staudinger ligation has been utilized to label glycans, lipids, DNA, and proteins. Moreover, the Staudinger ligation has been used as a synthetic method to construct glycopeptides, microarrays, and functional biopolymers. In the emerging field of bio-orthogonal ligation strategies, the Staudinger ligation has set a high standard to which most of the new techniques are often compared. This Review summarizes recent developments and new applications of the Staudinger ligation. PMID:21887733

  3. Synthesis and characterization of polymeric azido Zn(II) and Ni(II) complexes based on 3-hydroxypyridine

    Science.gov (United States)

    Mautner, Franz A.; Berger, Christian; Domian, Elisabeth; Fischer, Roland C.; Massoud, Salah S.

    2016-10-01

    The synthesis and structural characterization of two new complexes catena-[Ni(3-O-py)(3-HO-py)2(μ1,3-N3)(H2O)] (1) and catena-[Zn(μ-3-O-py)(μ1,1-N3)] (2), where 3-HO-py = 3-hydroxypyridine, are reported. The complexes were characterized by the elemental microanalyses, IR, and X-ray crystallography and by UV-Vis spectroscopy for complex 1. Single crystal X-ray crystallography revealed the polymeric nature of the complexes: 1 as 1D with a single EE azide bridging, and 2 as 2D with μ(O,O‧,N) bridging of the deprotonated 3-O-py anions and di-EO azide groups, respectively. In 1 the neutral and deprotonated 3-hydroxypyridine molecules act only as N-terminal ligands. The emission spectral properties of the Zn(II) complex were investigated.

  4. A Platform for Functional Conductive Polymers

    DEFF Research Database (Denmark)

    Daugaard, Anders Egede; Hoffmann, Christian; Lind, Johan Ulrik;

    Conductive polymers have been studied extensively during recent years. In order to broaden the application field of conductive polymers different methods have been tested and recently an azide functional poly(3,4-ethylenedioxythiophene) (PEDOT-N3) was developed(1, 2). The azide functional...... conductive polymer can be postpolymerization functionalized to introduce a large number of functionalities through click chemistry(3). Through selection of reaction conditions it is possible control the depth of the reaction into the polymer film to the upper surface or the entire film(4). Thus a conductive...... polymer can be prepared with a subsurface layer of highly conductive polymer where only the upper surface has been grafted with functional groups to ensure selectivity of the surface layer for e.g. interaction with specific biospecies. The conductive polymer can be patterned using selective etching, which...

  5. Metal-Free Route for the Synthesis of 4-Acyl-1,2,3-Triazoles from Readily Available Building Blocks.

    Science.gov (United States)

    Thomas, Joice; Goyvaerts, Vince; Liekens, Sandra; Dehaen, Wim

    2016-07-11

    Functionalized 1,2,3-triazole heterocycles have been known for a long time and hold an extraordinary potential in diverse research areas ranging from medicinal chemistry to material science. However, the scope of therapeutically important 1-substituted 4-acyl-1H-1,2,3-triazoles is much less explored, probably due to the lack of synthetic methodologies of good scope and practicality. Here, we describe a practical and efficient one-pot multicomponent reaction for the synthesis of α-ketotriazoles from readily available building blocks such as methyl ketones, N,N-dimethylformamide dimethyl acetal, and organic azides with 100 % regioselectivity. This reaction is enabled by the in situ formation of an enaminone intermediate followed by its 1,3-dipolar cycloaddition reaction with an organic azide. We effectively utilized the developed strategy for the derivatization of various heterocycles and natural products, a protocol which is difficult or impossible to realize by other means. PMID:27172985

  6. Light effect on Click reaction: Role of photonic quantum dot catalyst.

    Science.gov (United States)

    Nandi, Debkumar; Taher, Abu; Islam, Rafique Ul; Choudhary, Meenakshi; Siwal, Samarjeet; Mallick, Kaushik

    2016-01-01

    Due to the light excitation, the valence band electron of the copper (I) sulfide quantum dot transfer to the conduction band and act as a scavenger of the terminal proton of the alkyne in the presence of organic azide with the formation of 1,4-disubstituted 1,2,3-triazoles, where the copper(I) species of Cu2S act as a catalyst for the reaction. The above cycloaddition reaction between alkyne and azide is commonly known as the Click reaction. In this study, experiments were carried out under the exposure of ultra-violate and daylight and also dark environment. According to the original recommendation for the Click reaction, the role of the base was also considered for this experiment. We found that the effect of conduction band electron is more efficient than the recommended conventional base mediated reaction procedure. PMID:27621031

  7. Light effect on Click reaction: Role of photonic quantum dot catalyst

    Science.gov (United States)

    Nandi, Debkumar; Taher, Abu; Islam, Rafique Ul; Choudhary, Meenakshi; Siwal, Samarjeet; Mallick, Kaushik

    2016-09-01

    Due to the light excitation, the valence band electron of the copper (I) sulfide quantum dot transfer to the conduction band and act as a scavenger of the terminal proton of the alkyne in the presence of organic azide with the formation of 1,4-disubstituted 1,2,3-triazoles, where the copper(I) species of Cu2S act as a catalyst for the reaction. The above cycloaddition reaction between alkyne and azide is commonly known as the Click reaction. In this study, experiments were carried out under the exposure of ultra-violate and daylight and also dark environment. According to the original recommendation for the Click reaction, the role of the base was also considered for this experiment. We found that the effect of conduction band electron is more efficient than the recommended conventional base mediated reaction procedure.

  8. Investigation of concept of efficient short wavelength laser. Interim progress report, 1 April 1977-30 April 1978

    Energy Technology Data Exchange (ETDEWEB)

    Piper, L.G.; Krech, R.H.; Taylor, R.L.

    1978-05-01

    Under this program PSI is investigating the photolytic decomposition of a class of endoergic molecules - azides. Because these compounds contain substantial chemical energy, they offer a potentially more efficient approach for the production of electronically excited fragments. The goal of the present program was to acquire sufficient data and understanding of certain fundamental processes to permit the critical evaluation of this approach for laser development. An apparatus was built to study the wavelength-selected photolysis of gaseous, covalent azides. The photolysis source is a frequency doubled, tuneable dye laser. Detection of fragment species is accomplished by observation of primary fluorescence, or by laser-induced fluorescence (LIF) using a second tuneable dye laser. The design of the apparatus is discussed in detail.

  9. A versatile pathway to end-functionalized cellulose ethers for click chemistry applications.

    Science.gov (United States)

    Kamitakahara, Hiroshi; Suhara, Ryo; Yamagami, Mao; Kawano, Haruko; Okanishi, Ryoko; Asahi, Tomoyuki; Takano, Toshiyuki

    2016-10-20

    This paper describes a versatile pathway to heterobifunctional/telechelic cellulose ethers, such as tri-O-methyl cellulosyl azide and propargyl tri-O-methyl celluloside, having one free C-4 hydroxyl group attached to the glucosyl residue at the non-reducing end for the use in Huisgen 1,3-dipolar cycloaddition and copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The one-step end-functionalization of cellulose ethers for molecular rod synthesis involves the introduction of two reactive groups at both ends of the cellulose molecule, and can afford linear triblock copolymers via CuAAC and further reactions. We were able to tailor the degree of polymerization of end-functionalized cellulose ethers with controlled amounts of a Lewis acid, namely SnCl4. Chemical structures of the above cellulose ethers and the reaction conditions for controlling molecular length are discussed.

  10. Di-μ-azido-κ(4)N:N-bis-({2-[(3-amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1κ(3)N,N',O(1)}copper(II)).

    Science.gov (United States)

    Ghaemi, Akbar; Rayati, Saeed; Fayyazi, Kazem; Ng, Seik Weng; Tiekink, Edward R T

    2012-07-01

    The complete mol-ecule of the title complex, [Cu(2)(C(13)H(19)N(2)O(2))(2)(N(3))(2)], is generated by the application of a centre of inversion. The central Cu(2)N(2) core is a rhombus as the μ(2)-azide ligands bridge in an asymmetric fashion. Each Cu(II) atom is also coordinated by a monoanionic tridentate Schiff base ligand via the anti-cipated oxide O, imine N and amine N atoms. The resulting N(4)O coordination geometry is based on a square pyramid. No specific inter-molecular inter-actions are noted in the crystal packing, but the amine H atoms form intra-molecular N-H⋯O(oxide)/N(azide) hydrogen bonds. PMID:22807806

  11. Di-μ-azido-κ4N:N-bis({2-[(3-amino-2,2-dimethylpropyliminomethyl]-6-methoxyphenolato-1κ3N,N′,O1}copper(II

    Directory of Open Access Journals (Sweden)

    Akbar Ghaemi

    2012-07-01

    Full Text Available The complete molecule of the title complex, [Cu2(C13H19N2O22(N32], is generated by the application of a centre of inversion. The central Cu2N2 core is a rhombus as the μ2-azide ligands bridge in an asymmetric fashion. Each CuII atom is also coordinated by a monoanionic tridentate Schiff base ligand via the anticipated oxide O, imine N and amine N atoms. The resulting N4O coordination geometry is based on a square pyramid. No specific intermolecular interactions are noted in the crystal packing, but the amine H atoms form intramolecular N—H...O(oxide/N(azide hydrogen bonds.

  12. Patterned porous silicon photonic crystals with modular surface chemistry for spatial control of neural stem cell differentiation

    Science.gov (United States)

    Huang, Tiffany H.; Pei, Yi; Zhang, Douglas; Li, Yanfen; Kilian, Kristopher A.

    2016-05-01

    We present a strategy to spatially define regions of gold and nanostructured silicon photonics, each with materials-specific surface chemistry, for azide-alkyne cycloaddition of different bioactive peptides. Neural stem cells are spatially directed to undergo neurogenesis and astrogenesis as a function of both surface properties and peptide identity.We present a strategy to spatially define regions of gold and nanostructured silicon photonics, each with materials-specific surface chemistry, for azide-alkyne cycloaddition of different bioactive peptides. Neural stem cells are spatially directed to undergo neurogenesis and astrogenesis as a function of both surface properties and peptide identity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08327c

  13. Expanding the chemical scope of RNA:methyltransferases to site-specific alkynylation of RNA for click labeling

    Science.gov (United States)

    Motorin, Yuri; Burhenne, Jürgen; Teimer, Roman; Koynov, Kaloian; Willnow, Sophie; Weinhold, Elmar; Helm, Mark

    2011-01-01

    This work identifies the combination of enzymatic transfer and click labeling as an efficient method for the site-specific tagging of RNA molecules for biophysical studies. A double-activated analog of the ubiquitous co-substrate S-adenosyl-l-methionine was employed to enzymatically transfer a five carbon chain containing a terminal alkynyl moiety onto RNA. The tRNA:methyltransferase Trm1 transferred the extended alkynyl moiety to its natural target, the N2 of guanosine 26 in tRNAPhe. LC/MS and LC/MS/MS techniques were used to detect and characterize the modified nucleoside as well as its cycloaddition product with a fluorescent azide. The latter resulted from a labeling reaction via Cu(I)-catalyzed azide-alkyne 1,3-cycloaddition click chemistry, producing site-specifically labeled RNA whose suitability for single molecule fluorescence experiments was verified in fluorescence correlation spectroscopy experiments. PMID:21037259

  14. Oligonucleotide Tagging for Copper-Free Click Conjugation

    Directory of Open Access Journals (Sweden)

    Alan Rowan

    2013-06-01

    Full Text Available Copper-free click chemistry between cyclooctynes and azide is a mild, fast and selective technology for conjugation of oligonucleotides. However, technology for site-specific introduction of the requisite probes by automated protocols is scarce, while the reported cyclooctynes are large and hydrophobic. In this work, it is demonstrated that the introduction of bicyclo[6.1.0]nonyne (BCN into synthetic oligonucleotides is feasible by standard solid-phase phosphoramidite chemistry. A range of phosphoramidite building blocks is presented for incoporation of BCN or azide, either on-support or in solution. The usefulness of the approach is demonstrated by the straightforward and high-yielding conjugation of the resulting oligonucleotides, including biotinylation, fluorescent labeling, dimerization and attachment to polymer.

  15. Sequestering survivin to functionalized nanoparticles: a strategy to enhance apoptosis in cancer cells.

    Science.gov (United States)

    Jenkins, Ragini; Bandera, Yuriy P; Daniele, Michael A; Ledford, LeAnna L; Tietje, Ashlee; Kelso, Andrew A; Sehorn, Michael G; Wei, Yanzhang; Chakrabarti, Mrinmay; Ray, Swapan K; Foulger, Stephen H

    2016-04-01

    Survivin belongs to the family of inhibitor of apoptosis proteins (IAP) and is present in most cancers while being below detection limits in most terminally differentiated adult tissues, making it an attractive protein to target for diagnostic and, potentially, therapeutic roles. Sub-100 nm poly(propargyl acrylate) (PA) particles were surface modified through the copper-catalyzed azide/alkyne cycloaddition of an azide-terminated survivin ligand derivative (azTM) originally proposed by Abbott Laboratories and speculated to bind directly to survivin (protein) at its dimer interface. Using affinity pull-down studies, it was determined that the PA/azTM nanoparticles selectively bind survivin and the particles can enhance apoptotic cell death in glioblastoma cell lines and other survivin over-expressing cell lines such as A549 and MCF7 relative to cells incubated with the original Abbott-derived small molecule inhibitor. PMID:26845086

  16. Cage-like bifunctional chelators, copper-64 radiopharmaceuticals and PET imaging using the same

    Energy Technology Data Exchange (ETDEWEB)

    Conti, Peter S.; Cai, Hancheng; Li, Zibo; Liu, Shuanglong

    2016-08-02

    Disclosed is a class of versatile Sarcophagine based bifunctional chelators (BFCs) containing a hexa-aza cage for labeling with metals having either imaging, therapeutic or contrast applications radiolabeling and one or more linkers (A) and (B). The compounds have the general formula ##STR00001## where A is a functional group selected from group consisting of an amine, a carboxylic acid, an ester, a carbonyl, a thiol, an azide and an alkene, and B is a functional group selected from the group consisting of hydrogen, an amine, a carboxylic acid, and ester, a carbonyl, a thiol, an azide and an alkene. Also disclosed are conjugate of the BFC and a targeting moiety, which may be a peptide or antibody. Also disclosed are metal complexes of the BFC/targeting moiety conjugates that are useful as radiopharmaceuticals, imaging agents or contrast agents.

  17. General method for labeling siRNA by click chemistry with fluorine-18 for the purpose of PET imaging.

    Science.gov (United States)

    Mercier, Frédéric; Paris, Jérôme; Kaisin, Geoffroy; Thonon, David; Flagothier, Jessica; Teller, Nathalie; Lemaire, Christian; Luxen, André

    2011-01-19

    The alkyne-azide Cu(I)-catalyzed Huisgen cycloaddition, a click-type reaction, was used to label a double-stranded oligonucleotide (siRNA) with fluorine-18. An alkyne solid support CPG for the preparation of monostranded oligonucleotides functionalized with alkyne has been developed. Two complementary azide labeling agents (1-(azidomethyl)-4-[(18)F]fluorobenzene) and 1-azido-4-(3-[(18)F]fluoropropoxy)benzene have been produced with 41% and 35% radiochemical yields (decay-corrected), respectively. After annealing with the complementary strand, the siRNA was directly labeled by click chemistry with [(18)F]fluoroazide to produce the [(18)F]-radiolabeled siRNA with excellent radiochemical yield and purity.

  18. Gadolinium(III-DOTA Complex Functionalized with BODIPY as a Potential Bimodal Contrast Agent for MRI and Optical Imaging

    Directory of Open Access Journals (Sweden)

    Matthias Ceulemans

    2015-11-01

    Full Text Available The synthesis and characterization of a novel gadolinium(III DOTA complex functionalized with a boron-dipyrromethene derivative (BODIPY is described. The assembly of the complex relies on azide diazotransfer chemistry in a copper tube flow reactor. The azide thus formed is coupled directly with an alkyne via click chemistry, resulting into a paramagnetic and luminescent gadolinium(III complex. Luminescent data and relaxometric properties of the complex have been evaluated, suggesting the potential applicability of the complexes as a bimodal contrast agent for magnetic resonance and optical imaging. The complex displays a bright emission at 523 nm with an absorption maximum of 507 nm and high quantum yields of up to 83% in water. The proton relaxivity of the complex measured at 310 K and at frequencies of 20 and 60 MHz had the values of 3.9 and 3.6 s−1·mM−1, respectively.

  19. Selective Functionalization of Independently Addressed Microelectrodes by Electrochemical Activation and Deactivation of a Coupling Catalyst

    OpenAIRE

    Devaraj, Neal. K.; Dinolfo, Peter H.; Chidsey, Christopher E. D.; Collman, James P.

    2006-01-01

    We demonstrate selective functionalization of independently addressed microelectrodes by electrochemical activation and deactivation of a coupling catalyst. 1,2,3-Triazole formation between terminal acetylenes and organic azides is efficiently catalyzed by copper(I) complexes (a Sharpless “click” reaction) while the oxidized copper (II) complexes are inactive. By electrochemically activating or deactivating the catalyst by switching its redox state, we demonstrate control over triazole format...

  20. Adhesion of Colletotrichum lindemuthianum Spores to Phaseolus vulgaris Hypocotyls and to Polystyrene

    OpenAIRE

    Young, David H.; Kauss, Heinrich

    1984-01-01

    Adhesion of Colletotrichum lindemuthianum spores to Phaseolus vulgaris hypocotyls and to polystyrene was inhibited by the respiratory inhibitors sodium azide and antimycin A, indicating a requirement for metabolic activity in adhesion. Various commercial proteins and Tween 80 also reduced adhesion to both surfaces. Binding was enhanced by the presence of salts: sodium, potassium, calcium, and magnesium chlorides were equally effective. The removal of surface wax from hypocotyls by chloroform ...

  1. Facile synthesis of N-6 adenosine modified analogue toward S-adenosyl methionine derived probe for protein arginine methyltransferases

    Institute of Scientific and Technical Information of China (English)

    Wei Hong; James Dowden

    2011-01-01

    Chemically modified cellular co-factors that provide function, such as immobilization or incorporation of fluorescent dyes, are valuable probes of biological activity. A convenient route to obtain S-adenosyl methionine (AdoMet) analogues modified at N-6 adenosine to feature a linker terminating in azide functionality is described herein. Subsequent decoration of such AdoMet analogues with guanidinium terminated linkers leads to novel potential bisubstrate inhibitors for protein arginine methyltransferases, PRMTs.

  2. A simple method for enhancing the bioorthogonality of cyclooctyne reagent.

    Science.gov (United States)

    Tian, He; Sakmar, Thomas P; Huber, Thomas

    2016-04-01

    The cross-reactivity between some cyclooctynes and thiols limits the bioorthogonality of the strain-promoted azide-alkyne cycloaddition reaction. We show that a low concentration of β-mercaptoethanol significantly reduces the undesirable side reaction between bicyclononyne (BCN) and cysteine and while preserving free cysteines. We site-specifically label a genetically-encoded azido group in the visual photoreceptor rhodopsin to demonstrate the utility of the strategy. PMID:27009873

  3. Design and Investigation of Novel Porphyrin(oid) Conjugate Systems

    OpenAIRE

    Biedermann, Miriam

    2013-01-01

    Within the first part of this thesis novel water-soluble donor-acceptor arrays built up by porphyrins and pyrene or perylene derivatives were designed via a copper(I)-catalysed 1,3-dipolar azide-alkyne cycloaddition reaction. For this purpose, suitable precursors, which were available by well-established synthetic literature procedures, were combined with newly developed complementary “click” counterparts. Thus, also the substance library of ortho-benzylic functionalised tetraarylporphyrins w...

  4. Maleimide-functionalized closo-dodecaborate albumin conjugates (MID-AC): Unique ligation at cysteine and lysine residues enables efficient boron delivery to tumor for neutron capture therapy.

    Science.gov (United States)

    Kikuchi, Shunsuke; Kanoh, Daisuke; Sato, Shinichi; Sakurai, Yoshinori; Suzuki, Minoru; Nakamura, Hiroyuki

    2016-09-10

    Maleimide-conjugating closo-dodecaborate sodium form 5c (MID) synthesized by the nucleophilic ring-opening reaction of closo-dodecaborate-1,4-dioxane complex 2 with tetrabutylammonium (TBA) azide was found to conjugate to free SH of cysteine and lysine residues in BSA under physiological conditions, forming highly boronated BSA that showed high and selective accumulation in tumor and significant tumor growth inhibition in colon 26 tumor-bearing mice subjected to thermal neutron irradiation. PMID:27422608

  5. Low-cost Adsorbents for the Removal of Mercury (11) from Aqueous Solution-A Comparative Study

    OpenAIRE

    Ajay Kumar Meena,; Mishra, G. K.; Satish Kumar; Chitra Rajagopal; P.N. Nagar

    2004-01-01

    The establishments of the Ministry of Defence, specifically ordnance factories and public sector undertakings (like Bharat Electronics Ltd), carry out operations like electroplating, metal1surface finishing, solid-state wafer processing, and initiatory manufacturing (lead azide, mercury fulminate), which generate waste water contaminated with hazardous heavy metals. Mercuryand its compounds are known to be highly toxic, both for the living organisms and theenvironment. To protect public healt...

  6. Copper Granule-Catalyzed Microwave-Assisted Click Synthesis of Polyphenol Dendrimers

    OpenAIRE

    Lee, Choon Young; Held, Rich; Sharma, Ajit; Baral, Rom; Nanah, Cyprien; Dumas, Dan; Jenkins, Shannon; Upadhaya, Samik; Du, Wenjun

    2013-01-01

    Syringaldehyde and vanillin-based antioxidant dendrimers were synthesized via microwave-assisted alkyne-azide 1,3-dipolar cycloaddition using copper granules as a catalyst. The use of Cu(I) as a catalyst resulted in copper contaminated dendrimers. In order to produce copper-free antioxidant dendrimers for biological applications, Cu(I) was substituted with copper granules. Copper granules were ineffective at both room temperature and under reflux conditions (< 5% yield). However, it was an ex...

  7. Synthesis of N-substituted phthalimidoalkyl 1H-1,2,3-triazoles: a molecular diversity combining click chemistry and ultrasound irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Moara T. da; Oliveira, Ronaldo N. de; Valenca, Wagner O.; Barbosa, Fernanda C.G.; Silva, Mauro G. da; Camara, Celso A., E-mail: ronaldonoliveira@dcm.ufrpe.br [Universidade Federal Rural de Pernambuco (UFRPE), Recife, PE (Brazil). Dept. de Ciencias Moleculares

    2012-10-15

    A series of 1,2,3-triazole derivatives was synthesized from N-phthalimidoalkyl-azides (A{sub 1}-A{sub 4}) and alkynes (a-e) under ultrasound irradiation in the presence of CuI, Et{sub 3}N and DMF as solvent. The present protocol afforded 18 new 1,2,3-triazoles (1-4) in good-to-excellent yields (67-98%). (author)

  8. Application of 1,2,3-triazolylidenes as versatile NHC-type ligands: synthesis, properties, and application in catalysis and beyond

    OpenAIRE

    Donnelly, Kate F.; Petronilho, Ana; Albrecht, Martin

    2013-01-01

    Triazolylidenes have rapidly emerged as a powerful subclass of N-heterocyclic carbene ligands for transition metals. They are readily available through regioselective [2 + 3] cycloaddition of alkynes and azides and subsequent metallation according to procedures established for related carbenes. Due to their mesoionic character, triazolylidenes are stronger donors than Arduengo-type imidazol-2-ylidenes. Spurred by these attractive attributes and despite their only recent emergence, triazolylid...

  9. Biodegradation of Trichloroethylene in Continuous-Recycle Expanded-Bed Bioreactors

    OpenAIRE

    Phelps, T. J.; Niedzielski, J. J.; Schram, R M; Herbes, S. E.; White, D. C.

    1990-01-01

    Experimental bioreactors operated as recirculated closed systems were inoculated with bacterial cultures that utilized methane, propane, and tryptone-yeast extract as aerobic carbon and energy sources and degraded trichloroethylene (TCE). Up to 95% removal of TCE was observed after 5 days of incubation. Uninoculated bioreactors inhibited with 0.5% Formalin and 0.2% sodium azide retained greater than 95% of their TCE after 20 days. Each bioreactor consisted of an expanded-bed column through wh...

  10. Biochemical and ultrastructural processing of [125I]epidermal growth factor in rat epidermis and hair follicles: accumulation of nuclear label

    DEFF Research Database (Denmark)

    Green, M R; Mycock, C; Smith, C G;

    1987-01-01

    . Sodium azide inhibited internalization of label, whereas a series of lysosomal inhibitors (chloroquine, monensin, and iodoacetamide) caused a slight increase in silver grains associated with lysosomal vesicles and a decrease in nuclear label. Biochemical analysis indicated that greater than 35......-linked with low efficiency to a protein having the molecular weight of the EGF receptor. These data are discussed in the light of the effects of EGF on epithelial cell proliferation in skin....

  11. PHOSPHORUS PENTOXIDE-METHANESULFONIC ACID CATALYZED EFFICIENT SYNTHESIS OF 5-SUBSTITUTED 1H-TETRAZOLE DERIVATIVES Phosphorpentoxid-Methansulfonsäure KATALYSIERTEN EFFICIENT Synthese von 5-substituierten 1H-Tetrazolderivate

    Directory of Open Access Journals (Sweden)

    Amulrao U. Borse,Mahesh N. Patil, Nilesh L. Patil, and Sandesh R. Tetgure

    2012-07-01

    Full Text Available The mixture of phosphorus pentoxide-methanesulfonic acid (Eaton’s reagent is prove to be an efficient protocol for the [3+2] cycloaddition reaction between sodium azide and organic nitriles to give the corresponding 5-substituted 1H-tetrazole derivatives in good to excellent yields. The in situ formation of hydrazoic acid helps for the [3+2] cycloaddition reaction providing 5- substituted 1H-tetrazole with short reaction time.

  12. Stealth Polymeric Vesicles via Metal-free Click Coupling

    OpenAIRE

    Isaacman, Michael J.; Corigliano, Eleonora M.; Theogarajan, Luke S.

    2013-01-01

    The strain-promoted azide-alkyne cycloaddition represents an optimal metal-free method for the modular coupling of amphiphilic polymer blocks. Hydrophilic poly(oxazoline) (PMOXA) or poly(ethyleneglycol) (PEG) A-blocks were coupled with a hydrophobic poly(siloxane) B-block to provide triblock copolymers capable of self-assembling into vesicular nanostructures. Stealth properties investigated via a complement activation assay revealed the superior in vitro stealth attributes of polymeric vesicl...

  13. One pot Click chemistry: A three component reaction for the synthesis of 2-mercaptobenzimidazole linked coumarinyl triazoles as anti-tubercular agents.

    Science.gov (United States)

    Anand, Ashish; Kulkarni, Manohar V; Joshi, Shrinivas D; Dixit, Sheshagiri R

    2016-10-01

    2-Propargylthiobenzimidazole 1, 4-bromomethyl coumarins/1-aza-coumarins 2/3 and sodium azide have been reacted in one pot under Click chemistry conditions to give exclusively 1,4-disubstituted triazoles 5a-n. Anti-tubercular assays against M. tuberculosis (H37Rv) coupled with in silico molecular docking studies indicated that dimethyl substituents 5c and 5d showed promising activity with higher C-score values.

  14. Ultrasound-assisted synthesis of 1-N-{beta}-D-glucopyranosyl-1H-1,2,3-triazole benzoheterocycles and their anti-inflammatory activities

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Gilson B. da; Guimaraes, Bruna M.; Oliveira, Ronaldo N. de, E-mail: ronaldonoliveira@dcm.ufrpe.br [Universidade Federal Rural de Pernambuco (UFRPE), Recife, PE (Brazil). Departamento de Ciencias Moleculares; Assis, Shalom P.O.; Lima, Vera L.M. [Universidade Federal Rural de Pernambuco (UFRPE), Recife, PE (Brazil). Departamento de Bioquimica. Laboratorio de Quimica e Metabolismo de Lipideos e Lipoproteinas

    2013-06-15

    In this work, the preparation of various glucosyl triazoles from a reaction between 2,3,4,6-tetra-O-acetyl-{beta}-D-glucopyranosyl azide and terminal alkynes was developed in moderate to excellent yields (63-99%). Ultrasound energy was applied at each step of the reaction to increase chemical reactivity. In addition, the compounds conjugated with benzoheterocycles moieties revealed potent anti-inflammatory activity. (author)

  15. Fabrication and Anti-Fouling Properties of Photochemically and Thermally Immobilized Poly(Ethylene Oxide) and Low Molecular Weight Poly(Ethylene Glycol) Thin Films

    OpenAIRE

    Wang, Hui; Ren, Jin; Hlaing, Aye; Yan, Mingdi

    2010-01-01

    Poly(ethylene oxide) (PEO) and low molecular weight poly(ethylene glycol) (PEG) were covalently immobilized on silicon wafers and gold films by way of the CH insertion reaction of perfluorophenyl azides (PFPAs) by either photolysis or thermolysis. The immobilization does not require chemical derivatization of PEO or PEG, and polymers of different molecular weights were successfully attached to the substrate to give uniform films. Microarrays were also generated by printing polymer solutions o...

  16. Early events in herpes simplex virus type 1 infection: photosensitivity of fluorescein isothiocyanate-treated virions.

    OpenAIRE

    DeLuca, N; Bzik, D; Person, S; Snipes, W

    1981-01-01

    Herpes simplex virus type 1 is photosensitized by treatment with fluorescein isothiocyante (FITC). The inactivation of FITC-treated virions upon subsequent exposure to light is inhibited by the presence of sodium azide, suggesting the involvement of singlet oxygen in the process. Sodium dodecyl sulfate/polyacrylamide gel electrophoresis revealed that treatment with FITC plus light induces crosslinks in viral envelope glycoproteins. Treatment of virions with high concentrations of FITC (50 mic...

  17. 無および低カタラーゼ血症マウスのカタラーゼ分子の性質に関する研究 第1編 マウス肝カタラーゼ活性に対する変性剤の影響

    OpenAIRE

    佐藤,征紀

    1985-01-01

    Homogenates of mouse liver with isotonic sucrose solution were separated by the cell fractionation with repeating centrifugation. The supernatants were used for the inhibition test with the reagents such as 3,5 diiodosalicylic acid lithium salt (LIS), guanidine and azide, heat, acid and alkali. After various treatments, the remaining catalase activities were measured and showed as a relative enzyme activity. Stability of catalase in liver supernatants was compared normal (C3H/C(as)C(as)) and ...

  18. Thermally induced structural transformation of polytriazoleimide to polyindoleimide

    Institute of Scientific and Technical Information of China (English)

    Yan Peng E; Li Qiang Wan; Yu Jing Li; Fa Rong Huang; Lei Du

    2012-01-01

    A new kind of polytriazoleimide containing bisphenyl-1,2,3-triazole (BPT) was synthesized by copper-catalyzed 1,3-dipolar cycloaddition of azides and alkynes (CuAAC) and polycondensation.The thermal stability and degradation mechanism of the polytriazoleimide were investigated.The results show that the structure of BPT in polytriazoleimide transforms to phenylindole after thermal treatment,accompanying the release of N2.

  19. An economical and safe procedure to synthesize 2-hydroxy-4-pentynoic acid: A precursor towards ‘clickable’ biodegradable polylactide

    OpenAIRE

    Quanxuan Zhang; Hong Ren; Baker, Gregory L.

    2014-01-01

    2-Hydroxy-4-pentynoic acid (1) is a key intermediate towards ‘clickable’ polylactide which allows for efficient introduction of a broad range of pendant functional groups onto polymers from a single monomer via convenient ‘click’ chemistry with organic azides. The incorporation of various pendant functional groups could effectively tailor the physicochemical properties of polylactide. The reported synthesis of 1 started from propargyl bromide and ethyl glyoxylate. However, both of starting ma...

  20. Advances in the use of mutation induction for genetic improvement of barley and native grains in Peru

    International Nuclear Information System (INIS)

    Barley seeds of two varieties were treated with several doses of gamma rays and sodium azide. Seeds of a quinoa (Chenopodium) variety were treated with three doses of gamma rays. Yield trials were conducted also for doubled haploid lines of barley derived from earlier mutagenic treatments. Some promising new barley mutant lines were identified in the yield trials. The results from the Chenopodium trials facilitate the determination of the optimum dose of gamma rays for the PRQ-22 variety. (author)

  1. Synthesis studies on the Melodinus alkaloid meloscine

    OpenAIRE

    Feldman, Ken S.; Antoline, Joshua F.

    2013-01-01

    The pentacyclic Melodinus alkaloid (±)-meloscine was synthesized in 19 chemical steps from 2-bromobenzaldehyde through a route featuring an allenyl azide cyclization cascade to deliver the core azabicyclo[3.3.0]octane substructure. Peripheral functionalization of this core included a Tollens-type aldol condensation to set the quaternary center at C(20) and a diastereoselective ring closing metathesis to forge the tetrahydropyridine ring.

  2. Enhancement of TFO Triplex Formation by Conjugation with Pyrene via Click Chemistry.

    Science.gov (United States)

    Taniguchi, Yosuke; Tomizaki, Akira; Matsueda, Nozomu; Okamura, Hidenori; Sasaki, Shigeki

    2015-01-01

    This paper reports the preparation of 14-mer triplex-forming oligonucleotides (TFOs) containing a 2-O-methyl-1-β-phenyl-α-propargyl-ribose unit, which was conjugated with azide-modified molecules via a click reaction. Modification of these TFOs with pyrene assisted triplex formation, improving the stability of the triplex DNA and the anti-proliferative effects against A549 cells. PMID:26521856

  3. Click Chemistry-Mediated Nanosensors for Biochemical Assays

    OpenAIRE

    Chen, Yiping; Xianyu, Yunlei; Wu, Jing; Yin, Binfeng; Jiang, Xingyu

    2016-01-01

    Click chemistry combined with functional nanoparticles have drawn increasing attention in biochemical assays because they are promising in developing biosensors with effective signal transformation/amplification and straightforward signal readout for clinical diagnostic assays. In this review, we focus on the latest advances of biochemical assays based on Cu (I)-catalyzed 1, 3-dipolar cycloaddition of azides and alkynes (CuAAC)-mediated nanosensors, as well as the functionalization of nanopro...

  4. Functional Virus-Based Polymer-Protein Nanoparticles by Atom Transfer Radical Polymerization

    OpenAIRE

    Pokorski, Jonathan K.; Breitenkamp, Kurt; Finn, M. G.

    2011-01-01

    Viruses and virus-like particles (VLPs) are useful tools in biomedical research. Their defined structural attributes make them attractive platforms for engineered interactions over large molecular surface areas. In this report, we describe the use of VLPs as multivalent macroinitiators for atom transfer radical polymerization (ATRP). The introduction of chemically reactive monomers during polymerization provides a robust platform for post-synthetic modification via the copper-catalyzed azide-...

  5. A Traceless Aryl-Triazene Linker for DNA-Directed Chemistry

    DEFF Research Database (Denmark)

    Hejesen, Christian; Pedersen, Lars Kolster; Gothelf, Kurt Vesterager;

    2013-01-01

    DNA-directed synthesis of encoded combinatorial libraries of small organic compounds most often involves transfer of organic building blocks from one DNA strand to another. This requires cleavable linkers to enable cleavage of the link to the original DNA strand from which the building block is t...... to an azide, which was used in a cycloaddition reaction. The linker is generally stable at pH >7 and could be stored for 15 several months in a freezer without significant degradation....

  6. Drug: D09197 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D09197 Mixture, Drug Valsartan - hydrochlorothiazide mixt; Co-dio (TN) Valsartan [DR:D00400], Hydrochlorothi...s 21 Cardiovascular agents 214 Antihypertensives 2149 Others D09197 Valsartan - hydrochlorothiazide...Angiotensin II antagonists and diuretics C09DA03 Valsartan and diuretics D09197 Valsartan - hydrochlorothiazide mixt PubChem: 96025877 ... ...azide [DR:D00340] Therapeutic category: 2149 ATC code: C09DA03 The target of Valsar

  7. Chemical modification of viscose fibres by adsorption of carboxymethyl cellulose and click chemistry

    OpenAIRE

    Anufrijeva, Olga

    2014-01-01

    Functionalization of cellulosic materials to achieve new and advanced properties is a widely explored research area. This thesis is focused on the novel approach for modification of cellulosic materials by the combination of adsorption of carboxymethyl cellulose (CMC) onto cellulose surface and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) “click” reaction. The literature part gives an overview on the basics of cellulose chemistry, chemical functionalization of cellulose, as wel...

  8. The protective effect of tetramethylpyrazine (TMP) against PC12 cells damages

    Institute of Scientific and Technical Information of China (English)

    Xin-ruiCHENG; LanSUN; LiZHANG; Juan-juanHU; Guan-HuaDU

    2004-01-01

    AIM: To discover the protective effects of tetramethylpyrazine (TMP) against PC12 cells damages and explore its protective mechanisms. METHODS: We established three in vitro models to investigate the protective effects of TMP against the injuries. In both of glutamate and natrium azide-induced PC12 injuries, the action of TMP on the cell viability was measured by MTT assay. The LDH efflux was measured by the assay kit, production

  9. Exploring architectures displaying multimeric presentations of a trihydroxypiperidine iminosugar

    Directory of Open Access Journals (Sweden)

    Camilla Matassini

    2015-12-01

    Full Text Available The synthesis of new multivalent architectures based on a trihydroxypiperidine α-fucosidase inhibitor is reported herein. Tetravalent and nonavalent dendrimers were obtained by means of the click chemistry approach involving the copper azide-alkyne-catalyzed cycloaddition (CuAAC between suitable scaffolds bearing terminal alkyne moieties and an azido-functionalized piperidine as the bioactive moiety. A preliminary biological investigation is also reported towards commercially available and human glycosidases.

  10. A versatile and an efficient synthesis of 5-substituted-1-tetrazoles

    Indian Academy of Sciences (India)

    Madhusudana Reddy Muthukur Bhoje Gowd; Mohamed Afzal Pasha

    2011-01-01

    A simple, efficient and a versatile method for the synthesis of 5-substituted-1-tetrazoles by a [3+2]-cycloaddition reaction of arylnitriles with sodium azide in DMF using ZrOCl2·8 H2O as catalyst has been developed. The reactions work well at 100°C and give the desired products in excellent yield. The examples studied include arylnitriles having electron donating as well as electron releasing groups on the arene nucleus.

  11. Non-Specific Inhibition of Ischemia- and Acidosis-Induced Intracellular Calcium Elevations and Membrane Currents by α-Phenyl-N-tert-butylnitrone, Butylated Hydroxytoluene and Trolox

    OpenAIRE

    Christopher Katnik; Javier Cuevas

    2014-01-01

    Ischemia, and subsequent acidosis, induces neuronal death following brain injury. Oxidative stress is believed to be a key component of this neuronal degeneration. Acute chemical ischemia (azide in the absence of external glucose) and acidosis (external media buffered to pH 6.0) produce increases in intracellular calcium concentration ([Ca2+] i ) and inward membrane currents in cultured rat cortical neurons. Two α-tocopherol analogues, trolox and butylated hydroxytoluene (BHT), and the spin t...

  12. Preparation and Biological Evaluation of [18F]Ta-Gluc-TOCA

    Institute of Scientific and Technical Information of China (English)

    WEN; Kai; CHEN; Bao-jun; GUO; Fei-hu; LIANG; Ji-xin; CUI; Hai-ping

    2012-01-01

    <正>The purpose of this research was the synthesis of the glycosylated octreotide derivative quickly and easily, development of a method for 18F labeled peptides by the click chemistry, and exploring the feasibility using 18F labeled glycosylated octreotide derivatives as a somatostatin receptor positive tumor probe. Firstly, the 2-18F-azide ethane precursor compound was prepared by nucleophilic substitution, then

  13. Polysaccharides: The “Click” Chemistry Impact

    OpenAIRE

    Romain Lucas; Daniel Montplaisir; Rachida Zerrouki; Pierre-Antoine Faugeras; François Brouillette; Benjamin Boëns; Pierre-Henri Elchinger

    2011-01-01

    Polysaccharides are complex but essential compounds utilized in many areas such as biomaterials, drug delivery, cosmetics, food chemistry or renewable energy. Modifications and functionalizations of such polymers are often necessary to achieve molecular structures of interest. In this area, the emergence of the “click” chemistry concept, and particularly the copper-catalyzed version of the Huisgen 1,3-dipolar cycloaddition reaction between terminal acetylenes and azides, had an impact on the ...

  14. SYNTHESIS OF POLY ( ETHER-URETHANE) CONTAINING PENDANT AMINO GROUP

    Institute of Scientific and Technical Information of China (English)

    WU Jinhuang; SUN Yanhui; FENG Xinde

    1989-01-01

    This paper is concerned with the synthesis of poly (ether-urethane) with pendant amino groups. The copolyether produced by ring opening copolymerization of tetrahydrofuran and epibromohydrin was treated with sodium azide in dimethylformamide to form azido substituted copolyether. The poly (ether-urethane) made from it was subjected to reduction reaction to convert azido group to amino group. The stress-strain behavior and dynamic-mechanical properties of poly (ether-urethane) containing pendant amino groups were studied.

  15. A new fluorescent probe for gasotransmitter H₂S: high sensitivity, excellent selectivity, and a significant fluorescence off-on response.

    Science.gov (United States)

    Zhang, Jingyu; Guo, Wei

    2014-04-25

    A fluorescent off-on probe for H2S was exploited by coupling the azide-based strategy with the excited-state intramolecular proton transfer (ESIPT) sensing mechanism, which exhibits a considerably high fluorescence enhancement (1150-fold), an extremely low detection limit (0.78 nM), and a relatively fast response time (3-10 min) as well as excellent selectivity.

  16. Sensitive voltammetric and amperometric responses of respiratory toxins at hemin-adsorbed carbon-felt

    Institute of Scientific and Technical Information of China (English)

    Yasushi Hasebe; Yue Wang

    2013-01-01

    A hemin [iron-Fe(Ⅲ) protoporphyrin Ⅸ chloride] was adsorbed onto a carbon-felt (CF),which is a microelectrode ensemble of micro carbon fiber (ca.7 μm diameter).The resulting hemin-adsorbed-CF (hemin-CF) showed a well-defined redox wave based on the hemin-Fe(2)/Fe(Ⅱ) redox process with the formal potential of-0.225 Ⅴ vs.Ag/AgCI in deoxygenated phosphate/citrate buffer solution (0.1mol/L,pH 5.0).The apparent heterogenous electron transfer rate constant was estimated to be 8.6 sec-1.In air-saturated electrolyte solution,the hemin-CF exhibited an excellent electrocatalytic activity for the reduction of dioxygen (O2).This activity was reversibly inhibited by respiratory toxins such as cyanide and azide,which bind sixth coordination position of iron active center of hemin.The electrocatalytic O2 reduction current at the hemin-CF was modulated by the toxins in a concentration-depending manner.Based on the relationship between the %inhibition and the toxin concentration,apparent inhibition constants of cyanide and azide were evaluated to be 4.52 and 1.98 μmol/L,respectively.When the hemin-CF was used as a working electrode unit of the CF-based electrochemical flow-through detector with air-saturated carrier,the injection of the azide induced peak-shape current responses,which allowed rapid and continuous flow-amperometric determination of azide with high sensitivity.

  17. Synthesis and Fluorescence Properties of Coumarin Glycosides and Triazoylglycosides

    Institute of Scientific and Technical Information of China (English)

    WU Zheng; FU Xin-ling; YANG Nan; WANG Qiu-an

    2013-01-01

    Four coumarin glycosides(1-4) and four coumarin triazoylglycosides(5-8) were synthesized by phase transfer catalytic glycosylation and copper-catalyzed azide-alkyne cycloaddition(CuAAC) respectively from 4-methyl-7-hydroxyl coumarin(4-methylumbelliferone).The structures were characterized by 1H NMR,MS or IR.The fluorescent properties of the coumarin glycosides and triazoylglycosides were studied in different solvents and compared to those of 4-methyl-7-hydroxyl coumarin.

  18. A one-pot radiosynthesis of [125I]iodoazido photoaffinity labels

    International Nuclear Information System (INIS)

    A useful method for preparing radioiodinated photoaffinity labels from alkyl anilines which offer significant advantages over present methods is described. The one-pot synthesis gives good radiochemical yields (40-64%) of pure, high specific activity (350-1500 mCi/μmol) 124I labelled iodaryl azides while minimising manipulation of radioactive materials. Purification of the [125I]iodoazido photoaffinity labels is achieved by high performance liquid chromatography. (author)

  19. Nitrene Metathesis and Catalytic Nitrene Transfer Promoted by Niobium Bis(imido) Complexes.

    Science.gov (United States)

    Kriegel, Benjamin M; Bergman, Robert G; Arnold, John

    2016-01-13

    We report a metathesis reaction in which a nitrene fragment from an isocyanide ligand is exchanged with a nitrene fragment of an imido ligand in a series of niobium bis(imido) complexes. One of these bis(imido) complexes also promotes nitrene transfer to catalytically generate asymmetric dialkylcarbodiimides from azides and isocyanides in a process involving the Nb(V)/Nb(III) redox couple. PMID:26698833

  20. Phase-vanishing method with acetylene evolution and its utilization in several organic syntheses.

    Science.gov (United States)

    Matake, Ryosuke; Niwa, Yuki; Matsubara, Hiroshi

    2015-05-15

    A novel quadraphasic phase-vanishing system in which acetylene is evolved from calcium carbide and directly applied in situ to the Sonogashira coupling reaction was developed. This method, which provides a safe, convenient, and one-pot means to utilize gaseous reagents without special equipment, was also applied to a Cu-catalyzed azide-alkyne cycloaddition (CuAAC) reaction and a three-component aldehyde-alkyne-amine (A(3)) coupling reaction with excellent results.

  1. SYNTHESIS AND CHARACTERIZATION OF TRIAZOLE CONTAINING LIQUID CRYSTALLINE POLYMERS THROUGH 1,3-DIPOLAR CYCLOADDITION POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Devamani; Srividhya; Sundaram; Manjunathan; Sivashankaran; Nithyanandan; Subramanan; Balamurugan; Sengodan; Senthil

    2009-01-01

    Liquid crystalline polymers containing 1,2,3-triazole units as linking groups have been synthesized from the monomers containing triad ester diazide and flexible dialkyne ester by 1,3-cycloaddition reaction and were characterized. Click reaction of azide and alkyne functionals catalyzed by Cu(I) yielded target polyesters with 1,2,3-triazole groups.The structure of the polymer was confirmed by spectral techniques.GPC analysis reveals that the polymers have moderate molecular weight with narrow distributio...

  2. Bioorthogonal mimetics of palmitoyl-CoA and myristoyl-CoA and their subsequent isolation by click chemistry and characterization by mass spectrometry reveal novel acylated host-proteins modified by HIV-1 infection.

    Science.gov (United States)

    Colquhoun, David R; Lyashkov, Alexey E; Ubaida Mohien, Ceereena; Aquino, Veronica N; Bullock, Brandon T; Dinglasan, Rhoel R; Agnew, Brian J; Graham, David R M

    2015-06-01

    Protein acylation plays a critical role in protein localization and function. Acylation is essential for human immunodeficiency virus 1 (HIV-1) assembly and budding of HIV-1 from the plasma membrane in lipid raft microdomains and is mediated by myristoylation of the Gag polyprotein and the copackaging of the envelope protein is facilitated by colocalization mediated by palmitoylation. Since the viral accessory protein NEF has been shown to alter the substrate specificity of myristoyl transferases, and alter cargo trafficking lipid rafts, we hypothesized that HIV-1 infection may alter protein acylation globally. To test this hypothesis, we labeled HIV-1 infected cells with biomimetics of acyl azides, which are incorporated in a manner analogous to natural acyl-Co-A. A terminal azide group allowed us to use a copper catalyzed click chemistry to conjugate the incorporated modifications to a number of substrates to carry out SDS-PAGE, fluorescence microscopy, and enrichment for LC-MS/MS. Using LC-MS/MS, we identified 103 and 174 proteins from the myristic and palmitic azide enrichments, with 27 and 45 proteins respectively that differentiated HIV-1 infected from uninfected cells. This approach has provided us with important insights into HIV-1 biology and is widely applicable to many virological systems.

  3. Lifetimes of -halo and -azidobenzyl carbocations in aqueous solution

    Indian Academy of Sciences (India)

    R Sanjeev; V Jagannadham

    2002-02-01

    The title cations were produced in aqueous solution by chemical initiation (solvolysis) of benzyl-gem-dihalides and benzyl-gem-diazides. The solvolysis reactions of benzyl-gem-dihalides and benzyl-gem-diazides in water proceed by a stepwise mechanism through -halobenzyl carbocation and -azidobenzyl carbocation intermediates, which are captured by water to give the corresponding carbonyl compounds as the sole detectable products. Rate constant ratio / (M-1) for partitioning of the carbocation between reaction with halide/azide ion and reaction with water is determined by analysis of halide/azide common ion inhibition of the solvolysis reaction. The rate constants (s-1) for the reaction of the cation with solvent water were determined from the experimental values of / and solv, for the solvolysis of the benzyl-gem-dihalides and benzyl-gem-diazides respectively, using = 5 × 109 M-1 s-1 for diffusion-limited reaction of halide/azide ion with -substituted benzyl carbocations. The values of 1/ are thus the lifetimes of the -halobenzyl carbocations and -azidobenzyl carbocations respectively.

  4. Di-μ-azido-bis(μ-1,4,7,10,13,16-hexaoxacyclooctadecanebis(5,10,15,20-tetraphenylporphyrinatodicadmiumdisodium

    Directory of Open Access Journals (Sweden)

    Hamza Toumi

    2012-12-01

    Full Text Available The asymmetric unit of the title compound, [Cd2Na2(N32(C44H28N42(C12H24O62], consists of one half of the dimeric complex; the tetranuclear molecule lies about an inversion centre. The CdII atom is coordinated by the four pyrrole N atoms of the 5,10,15,20-tetraphenylporphyrinate ligand and one N atom of the axial azide ligand in a square-pyramidal geometry. The azide group is also linked to the NaI atom, which is surrounded by one 18-crown-6 molecule and additionally bonded to a second 18-crown-6 molecule trans to the azide group. The porphyrin core exhibits a major doming distortion (∼40% and the crystal structure is stabilized by weak C—H...π interactions. The molecular structure features weak intramolecular hydrogen bonds: two O—H...O interactions within the 18-crown-6 molecule and one C—H(18-crown-6...N(azido contact.

  5. Surface Modification Using Photo-Crosslinkable Random Copolymers

    Science.gov (United States)

    Bae, Joonwon; Bang, Joona; Lowenhielm, Peter; Spiessberger, Christian; Russell, Thomas P.; Hawker, Craig J.

    2006-03-01

    We recently reported that poly(styrene-r-methyl methacrylate) (PS-r-PMMA) random copolymers containing benzocyclobutene (BCB) group can be used to modify the surface effectively by thermal crosslinking. It was demonstrated that this method is simple, rapid, and robust, and can be applied to various surfaces. However, it requires the large amount of heat for processing, and the BCB monomer itself involves a hard chemistry. An alternative way that can replace BCB with easier chemistry and lower cost, if possible, is highly desirable. We introduce the new functional group, azide group, which can be crosslinked simply by UV irradiation, for this purpose. PS-r-PMMA random copolymers, containing various amounts of azide groups, were synthesized via controlled living-radical polymerization. It was demonstrated that even after 1 minute of the UV irradiation can crosslink the materials effectively, so that they can be used as crosslinked random copolymer mat to control the surface energy. However, it was observed that the longer irradiation time causes the damages on the surface due to the other side reactions. Depending on the UV intensity, the UV irradiation time, and the amount of azide group, the effective processing window that leads to the crosslinking without any surface damages was optimized.

  6. Synthesis of novel ethyl 1-ethyl-6-fluoro-7-(fatty amido)-1,4-dihydro-4-oxoquinoline-3-carboxylate derivatives and their biological evaluation.

    Science.gov (United States)

    Venepally, Vijayendar; Prasad, R B N; Poornachandra, Y; Kumar, C Ganesh; Jala, Ram Chandra Reddy

    2016-01-15

    A series of novel ethyl 1-ethyl-6-fluoro-7-(fatty amido)-1,4-dihydro-4-oxoquinoline-3-carboxylate derivatives were prepared through multistep synthesis. The key step in the synthesis was to obtain the C-7 fatty amide derivative. The azide was selectively formed at C-7 position using sodium azide at 60°C. Subsequently, the azide was reduced under mild conditions using zinc and ammonium chloride to form the corresponding amine. The synthesized derivatives were further subjected to biological evaluation studies like cytotoxicity against a panel of cancer cell lines such as DU145, A549, SKOV3, MCF7 and normal lung cells, IMR-90 as well as with antimicrobial and antioxidant activities. It was observed that the carboxylated quinolone derivatives with hexanoic (8a), octanoic (8b), lauric (8d) and myristic (8e) moieties exhibited promising cytotoxicity against all the tested cancer cell lines. The results also suggested that hexanoic acid-based fatty amide carboxylated quinolone derivative (8a) exhibited promising activity against both bacterial and fungal strains and significant antibacterial activity was observed against Staphylococcus aureus MTCC 96 (MIC value of 3.9μg/mL). The compound 8a also showed excellent anti-biofilm activity against Staphylococcus aureus MTCC 96 and Bacillus subtilis MTCC 121 with MIC values of 2.1 and 4.6μg/mL, respectively. PMID:26646219

  7. Mixed silane monolayers for controlling the surface areal density of click-reactive alkyne groups: a method to assess preferential surface adsorption on flat substrates and a method to verify compositional homogeneity on nanoparticles.

    Science.gov (United States)

    Maidenberg, Yanir; Zhang, Shuo; Luo, Kai; Akhavein, Nima; Koberstein, Jeffrey T

    2013-09-24

    SAMs formed from mixtures of alkyne-silanes and alkane-silanes are used to control the areal density of click-reactive alkyne groups on the surface of flat germanium substrates, silicon wafers, and silica nanoparticles. Two new analytical tools are described for characterization of the mixed SAMs: a thermogravimetric analysis (TGA) technique for quantifying the compositional homogeneity of the mixed monolayers formed on nanoparticles, and an infrared spectroscopy (IR) technique to detect preferential surface adsorption. The TGA technique involves measurement of the change in weight when azide-terminated polymers react with surface alkyne groups on silica nanoparticles via a click reaction, while the IR technique is based on the use of attenuated total reflectance infrared spectroscopy (ATR-IR) to monitor click reactions between azide compounds with infrared "labels" and alkyne-functional mixed SAMs deposited on germanium ATR plates. Upon application of the new characterization techniques, we are able to prove that the mixed silane monolayers show neither phase separation nor preferential surface adsorption on any of the three substrates studied. When reacted with azide terminal polymers, the areal density at saturation, σ(sat) is found to scale with molecular weight according to σ(sat) ≈ N(-0.57). We conclude that mixed monolayers of alkyne-silanes and alkane-silanes are an effective means of controlling the surface areal density of click-reactive alkyne groups on both flat and nanoparticle substrates. PMID:23985021

  8. Synthesis, antimicrobial activity, and membrane permeabilizing properties of C-terminally modified nisin conjugates accessed by CuAAC.

    Science.gov (United States)

    Slootweg, Jack C; van der Wal, Steffen; Quarles van Ufford, H C; Breukink, Eefjan; Liskamp, Rob M J; Rijkers, Dirk T S

    2013-12-18

    Functionalization of the lantibiotic nisin with fluorescent reporter molecules is highly important for the understanding of its mode of action as a potent antimicrobial peptide. In addition to this, multimerization of nisin to obtain multivalent peptide constructs and conjugation of nisin to bioactive molecules or grafting it on surfaces can be attractive methods for interference with bacterial growth. Here, we report a convenient method for the synthesis of such nisin conjugates and show that these nisin derivatives retain both their antimicrobial activity and their membrane permeabilizing properties. The synthesis is based on the Cu(I)-catalyzed alkyne-azide cycloaddition reaction (CuAAC) as a bioorthogonal ligation method for large and unprotected peptides in which nisin was C-terminally modified with propargylamine and subsequently efficiently conjugated to a series of functionalized azides. Two fluorescently labeled nisin conjugates together with a dimeric nisin construct were prepared while membrane insertion as well as antimicrobial activity were unaffected by these modifications. This study shows that C-terminal modification of nisin does not deteriorate biological activity in sharp contrast to N-terminal modification and therefore C-terminally modified nisin analogues are valuable tools to study the antibacterial mode of action of nisin. Furthermore, the ability to use stoichiometric amounts of the azide containing molecule opens up possibilities for surface tethering and more complex multivalent structures.

  9. "Click" and Olefin Metathesis Chemistry in Water at Room Temperature Enabled by Biodegradable Micelles.

    Science.gov (United States)

    Lipshutz, Bruce H; Bošković, Zarko; Crowe, Christopher S; Davis, Victoria K; Whittemore, Hannah C; Vosburg, David A; Wenzel, Anna G

    2013-11-12

    The two laboratory reactions focus on teaching several concepts associated with green chemistry. Each uses a commercial, nontoxic, and biodegradable surfactant, TPGS-750-M, to promote organic reactions within the lipophilic cores of nanoscale micelles in water. These experiments are based on work by K. Barry Sharpless (an azide-alkyne "click" reaction) and Robert Grubbs (an olefin cross-metathesis reaction); both are suitable for an undergraduate organic laboratory. The copper-catalyzed azide-alkyne [3+2] cycloaddition of benzyl azide and 4-tolylacetylene is very rapid: the triazole product is readily isolated by filtration and is characterized by thin-layer chromatography and melting point analysis. The ruthenium-catalyzed olefin cross-metathesis reaction of benzyl acrylate with 1-hexene is readily monitored by thin-layer chromatography and gas chromatography. The metathesis experiment comparatively evaluates the efficacy of a TPGS-750-M/water medium relative to a traditional reaction performed in dichloromethane (a common solvent used for olefin metathesis).

  10. Signaling mechanisms underlying the glioprotective effects of resveratrol against mitochondrial dysfunction.

    Science.gov (United States)

    Bellaver, Bruna; Bobermin, Larissa Daniele; Souza, Débora Guerini; Rodrigues, Marília Danielly Nunes; de Assis, Adriano Martimbianco; Wajner, Moacir; Gonçalves, Carlos-Alberto; Souza, Diogo Onofre; Quincozes-Santos, André

    2016-09-01

    Resveratrol, a polyphenol found in grapes and red wine, exhibits antioxidant, anti-inflammatory, anti-aging and, neuroprotective effects. Resveratrol also plays a significant role modulating glial functionality, protecting the health of neuroglial cells against several neuropsychiatric in vivo and in vitro experimental models. Mitochondrial impairment strongly affected astrocyte functions and consequently brain homeostasis. Molecules that promote astrocyte mitochondrial protection are fundamental to maintain brain energy balance and cellular redox state, contributing to brain healthy. Thus, the present study was designed to evaluate some glioprotective mechanisms of resveratrol against mitochondrial damage promoted by azide exposure in hippocampal primary astrocyte cultures. Azide treatment provoked deleterious effects, including the dysfunction of mitochondria, the deterioration of redox homeostasis, the augmentation of pro-inflammatory cytokines and impairment of glutamate uptake activity. However, resveratrol prevented these effects, protecting hippocampal astrocytes against azide-induced cytotoxicity through the heme-oxygenase-1 (HO-1) pathway and inhibiting p38 mitogen-activated protein kinase (p38 MAPK) and nuclear factor kappa B (NFκB) activation. Resveratrol also protected astrocytes via phosphatidylinositide 3-kinase (PI3K)/Akt. These results contribute to the comprehension of the mechanisms by which resveratrol mediates hippocampal astrocyte protection against mitochondrial failure and implicate resveratrol as an important glioprotective molecule. PMID:27373419

  11. Brain catalase mediates potentiation of social recognition memory produced by ethanol in mice.

    Science.gov (United States)

    Manrique, Héctor M; Miquel, Marta; Aragon, Carlos M G

    2005-09-01

    The involvement of catalase in ethanol-induced locomotion has been clearly proven. However, studies addressing the role of this enzyme in the effects that ethanol exerts on memory are lacking. In the present study, the social recognition test (SRT) was used to evaluate ethanol effects on memory. In this test, the reduction in investigation time of a juvenile conspecific, when this social stimulus is presented for the second time, is considered a reliable index of memory. Exploration ratios (ER) were calculated to evaluate the recognition capacity of mice. Ethanol (0.0, 0.5, 1.0 or 1.5g/kg, i.p.) was administered immediately after the first juvenile presentation, and 2h later the juvenile was re-exposed to the adult. Additionally, adult mice received aminotriazole (AT) or sodium azide (two catalase inhibitors) 5h or 30 min before juvenile presentation, respectively. Ethanol (1.0 and 1.5g/kg) was able to reduce ER, indicating an improving effect on memory. This improvement was prevented by either AT or sodium azide pre-treatment. However, neither AT nor sodium azide attenuated the memory-enhancing capacity of NMDA or nicotine, suggesting a specific interaction between catalase inhibitors and ethanol in their effects on memory. The present results suggest that brain catalase activity could mediate the memory-enhancing capacity of ethanol and add further support to the idea that this enzyme mediates some of the psychopharmacological effects produced by ethanol. PMID:16102377

  12. Bioorthogonal Copper Free Click Chemistry for Labeling and Tracking of Chondrocytes In Vivo.

    Science.gov (United States)

    Yoon, Hwa In; Yhee, Ji Young; Na, Jin Hee; Lee, Sangmin; Lee, Hyukjin; Kang, Sun-Woong; Chang, Hyeyoun; Ryu, Ju Hee; Lee, Seulki; Kwon, Ick Chan; Cho, Yong Woo; Kim, Kwangmeyung

    2016-04-20

    Establishment of an appropriate cell labeling and tracking method is essential for the development of cell-based therapeutic strategies. Here, we are introducing a new method for cell labeling and tracking by combining metabolic gylcoengineering and bioorthogonal copper-free Click chemistry. First, chondrocytes were treated with tetraacetylated N-azidoacetyl-D-mannosamine (Ac4ManNAz) to generate unnatural azide groups (-N3) on the surface of the cells. Subsequently, the unnatural azide groups on the cell surface were specifically conjugated with near-infrared fluorescent (NIRF) dye-tagged dibenzyl cyclooctyne (DBCO-650) through bioorthogonal copper-free Click chemistry. Importantly, DBCO-650-labeled chondrocytes presented strong NIRF signals with relatively low cytotoxicity and the amounts of azide groups and DBCO-650 could be easily controlled by feeding different amounts of Ac4ManNAz and DBCO-650 to the cell culture system. For the in vivo cell tracking, DBCO-650-labeled chondrocytes (1 × 10(6) cells) seeded on the 3D scaffold were subcutaneously implanted into mice and the transplanted DBCO-650-labeled chondrocytes could be effectively tracked in the prolonged time period of 4 weeks using NIRF imaging technology. Furthermore, this new cell labeling and tracking technology had minimal effect on cartilage formation in vivo. PMID:26930274

  13. Polarity Sensitive Bioorthogonally Applicable Far-Red Emitting Labels for Postsynthetic Nucleic Acid Labeling by Copper-Catalyzed and Copper-Free Cycloaddition.

    Science.gov (United States)

    Eördögh, Ádám; Steinmeyer, Jeannine; Peewasan, Krisana; Schepers, Ute; Wagenknecht, Hans-Achim; Kele, Péter

    2016-02-17

    Two series of new, water-soluble, membrane-permeable, far-red/NIR emitting benzothiazolium-based fluorescent labels with large Stokes' shifts were synthesized that can be conjugated to alkyne-modified biomolecules through their azide moiety via azide-alkyne cycloaddition. We have used these azide bearing labels to make fluorescent DNA constructs using copper-catalyzed "click" reaction. All dyes showed good or remarkable fluorescence intensity enhancement upon conjugation to DNA. We also investigated the possibility to incorporate the benzocyclooctyne motif through rigid (ethnynyl) or flexible (ethyl) linkers into the DNA, thus enabling copper-free labeling schemes. We observed that there is a marked difference between the two linkers applied in terms of optical properties of the labeled oligonucleotides. We have also tested the in vivo labeling potential of these newly synthesized dyes on HeLa cells previously transfected with cyclooctynylated DNA. Confocal fluorescent images showed that the dyes are all able to cross the membrane and suitable for background-fluorescence free fluorescent tagging of nucleic acids. Moreover, we have observed different accumulation of the two dye series in the endosomal particles, or in the nuclei, respectively. PMID:26786593

  14. The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4](2-) (M=Mo, W).

    Science.gov (United States)

    Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

    2015-08-10

    Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2'-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4](2-) were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. PMID:26178877

  15. Water-soluble PEGylated silicon nanoparticles and their assembly into swellable nanoparticle aggregates

    International Nuclear Information System (INIS)

    Water-soluble silicon nanoparticles were synthesized by grafting PEG polymers onto functionalized silicon nanoparticles with distal alkyne or azide moieties. The surface-functionalized silicon nanoparticles were produced in one step from the reactive high-energy ball milling (RHEBM) of silicon wafers with a mixture of either 5-chloro-1-pentyne in 1-pentyne or 1,7 octadiyne in 1-hexyne to afford air and water-stable chloroalkyl or alkynyl-terminated nanoparticles, respectively. Nanoparticles with the ω-chloroalkyl substituents were easily converted to ω-azidoalkyl groups through the reaction of the Si nanoparticles with sodium azide in DMF. The azido-terminated nanoparticles were then grafted with mono-alkynyl-PEG polymers using a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction to afford core–shell silicon nanoparticles with a covalently attached PEG shell. Covalently linked Si nanoparticle clusters were synthesized via the CuAAC “click” reaction of functional Si NPs with α,ω-functional PEG polymers of various lengths. Dynamic light scattering studies show that the flexible globular nanoparticle aggregates undergo a solvent-dependent change in volume (ethanol > dichloromethane > toluene) similar in behavior to hydrogel nanocomposites

  16. "Click" and Olefin Metathesis Chemistry in Water at Room Temperature Enabled by Biodegradable Micelles.

    Science.gov (United States)

    Lipshutz, Bruce H; Bošković, Zarko; Crowe, Christopher S; Davis, Victoria K; Whittemore, Hannah C; Vosburg, David A; Wenzel, Anna G

    2013-11-12

    The two laboratory reactions focus on teaching several concepts associated with green chemistry. Each uses a commercial, nontoxic, and biodegradable surfactant, TPGS-750-M, to promote organic reactions within the lipophilic cores of nanoscale micelles in water. These experiments are based on work by K. Barry Sharpless (an azide-alkyne "click" reaction) and Robert Grubbs (an olefin cross-metathesis reaction); both are suitable for an undergraduate organic laboratory. The copper-catalyzed azide-alkyne [3+2] cycloaddition of benzyl azide and 4-tolylacetylene is very rapid: the triazole product is readily isolated by filtration and is characterized by thin-layer chromatography and melting point analysis. The ruthenium-catalyzed olefin cross-metathesis reaction of benzyl acrylate with 1-hexene is readily monitored by thin-layer chromatography and gas chromatography. The metathesis experiment comparatively evaluates the efficacy of a TPGS-750-M/water medium relative to a traditional reaction performed in dichloromethane (a common solvent used for olefin metathesis). PMID:24324282

  17. Novel 1,3-dipolar cycloadditions of dinitraminic acid: implications for the chemical stability of ammonium dinitramide.

    Science.gov (United States)

    Rahm, Martin; Brinck, Tore

    2008-03-20

    Density functional theory at the B3LYP/6-31+G(d,p) level and ab initio calculations at the CBS-QB3 level have been used to analyze 1,3 dipolar cycloaddition reactions of dinitraminic acid (HDN) and its proton transfer isomer (HO(O)NNNO2). It is shown that the nitro group of HDN and the -N-N=O functionality of the isomer react readily with carbon-carbon double bonds. Cycloadditions of HDN are compared with the corresponding reactions with azides and nitrile oxides as 1,3 dipoles. It is shown that the reactivities of HDN and its proton transfer isomer decrease with increasing electron withdrawing power of the substituents adjacent to the carbon-carbon double bond. In contrast, for azides and nitrile oxides, the highest reactivity is obtained with dipolarophiles with strongly electron withdrawing substituents. The observed reactivity trends allow for the design of unsaturated compounds that are highly reactive toward azides and chemically inert toward dinitramides. This may be of relevance for the development of binder materials for ammonium dinitramide based propellants. PMID:18278886

  18. Effects of chemical anoxia on NHE1, p38 MAPK, p53, Akt and ERM proteins in NIH3T3 fibroblasts: evidence for a role of NHE1 upstream of p38 MAPK

    DEFF Research Database (Denmark)

    Rentsch, M. L.; Hoffmann, E. K.; Pedersen, Stine Helene Falsig

    2006-01-01

    Activation of the plasma membrane Na+/H+ exchanger NHE1 contributes importantly to ischemic/anoxic cell damage, yet the mechanisms involved are unclear. In NIH3T3 cells, PCR studies confirmed the expression of NHE1 and -8, yet not NHE2, -3, and -4. Chemical anoxia (10 mM azide, 10 min) was associ......Activation of the plasma membrane Na+/H+ exchanger NHE1 contributes importantly to ischemic/anoxic cell damage, yet the mechanisms involved are unclear. In NIH3T3 cells, PCR studies confirmed the expression of NHE1 and -8, yet not NHE2, -3, and -4. Chemical anoxia (10 mM azide, 10 min......) was associated with a decrease in pHi which was exacerbated by the NHE1 inhibitor EIPA (5 µM). Reperfusion (azide washout) elicited a rapid, EIPA-sensitive alkalinization to 7.60 ± 0.057 (n=6), compared to a starting pHi of 7.49 ± 0.032 (n=6). Cell survival was reduced by prolonged chemical anoxia (to 87% at 3 h...... and 41% at 24 h, MTT assay), an effect counteracted by EIPA at early ( 6 h) time points. Chemical anoxia was furthermore associated with: (i) a rapid ( 10 min) and transient phosphorylation of p38 MAPK, which was abolished by NHE1 inhibitors (EIPA, cariporide, 5 µM); (ii) increased phosphorylation...

  19. The niobium oxoazides [NbO(N3)3], [NbO(N3)3·2CH3CN], [(bipy)NbO(N3)3], Cs2[NbO(N3)5] and [PPh4]2[NbO(N3)5].

    Science.gov (United States)

    Haiges, Ralf; Vasiliu, Monica; Dixon, David A; Christe, Karl O

    2016-06-28

    Niobium oxotriazide, [NbO(N3)3], was prepared in a fluoride-azide exchange reaction between [NbOF3] and an excess of Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adduct [NbO(N3)3·2CH3CN]. The subsequent reaction of [NbO(N3)3] with 2,2'-bipyridine (bipy) resulted in the isolation of the bipyridine adduct [(bipy)NbO(N3)3]. The pentaazido anion [NbO(N3)5](2-) was obtained by the reaction of [NbO(N3)3] with two equivalents of ionic azide. The novel niobium oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [(bipy)NbO(N3)3], Cs2[NbO(N3)5], and [PPh4]2[NbO2(N3)5] by their X-ray crystal structures. PMID:27198621

  20. Water-soluble PEGylated silicon nanoparticles and their assembly into swellable nanoparticle aggregates

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Zejing; Li, Yejia; Zhang, Boyu; Purkait, Tapas [Tulane University, Department of Chemistry (United States); Alb, Alina [Tulane University, Department of Physics and Engineering Physics (United States); Mitchell, Brian S. [Tulane University, Department of Chemical and Biomolecular Engineering (United States); Grayson, Scott M.; Fink, Mark J., E-mail: fink@tulane.edu [Tulane University, Department of Chemistry (United States)

    2015-01-15

    Water-soluble silicon nanoparticles were synthesized by grafting PEG polymers onto functionalized silicon nanoparticles with distal alkyne or azide moieties. The surface-functionalized silicon nanoparticles were produced in one step from the reactive high-energy ball milling (RHEBM) of silicon wafers with a mixture of either 5-chloro-1-pentyne in 1-pentyne or 1,7 octadiyne in 1-hexyne to afford air and water-stable chloroalkyl or alkynyl-terminated nanoparticles, respectively. Nanoparticles with the ω-chloroalkyl substituents were easily converted to ω-azidoalkyl groups through the reaction of the Si nanoparticles with sodium azide in DMF. The azido-terminated nanoparticles were then grafted with mono-alkynyl-PEG polymers using a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction to afford core–shell silicon nanoparticles with a covalently attached PEG shell. Covalently linked Si nanoparticle clusters were synthesized via the CuAAC “click” reaction of functional Si NPs with α,ω-functional PEG polymers of various lengths. Dynamic light scattering studies show that the flexible globular nanoparticle aggregates undergo a solvent-dependent change in volume (ethanol > dichloromethane > toluene) similar in behavior to hydrogel nanocomposites.

  1. Biodegradabilite et proprietes energetiques d'elastomeres azotures

    Science.gov (United States)

    Lavoie, Jonathan

    The interest for polymer materials has steadily increased in the last decades and the use of polymer materials has been increasing ever since. These polymers are used in a vast range of applications from civil to military (Colclough et al., 1994; Nair & Laurencin, 2007; Sansone et al., 2012). This demand for polymer materials resulted in the development of various polymers with a wide range of properties depending on the desired application. In the field of propellants, this interest led to the development of glycidyl azide polymer (GAP) and other similar materials. Growing environmental concerns has led to a demand for more environmentally friendly polymers. This demand so far has been increasing and shows no sign of following a different trend for the next years. This demand is in part due to the presence of non-recyclable polymers, for which end of life can be problematic. At the same time, another problematic arose: the soil contamination originating from repeated military training as well as the subsequent contamination of water supplies by rain water seeping into the ground absorbing part of the contaminants (Dontsova, Pennington, Hayes, imunek, & Williford, 2009; M. R. Walsh, Thiboutot, Walsh, & Ampleman, 2012). This phenomenon incurs large decontamination costs and can result in the abandonment of training grounds due to contamination (Michael R. Walsh, Walsh, & Hewitt, 2010). The compounds responsible for the contamination of military training grounds are in part present in elastomers used as binders for propellants. The binders are non-biodegradable as well. In order to make greener propellants, it is not only necessary to replace the contaminants by non-contaminant materials, but also necessary to replace the binder by using new biodegradable materials. Glycidyl azide polymer, a commonly used energetic polymer in binders is non-biodebradable and as such unburned residue will accumulate in the environment. The main objective of this work is to develop new

  2. The fermentation of lignocellulose hydrolysates with xylose isomerases and yeasts

    Energy Technology Data Exchange (ETDEWEB)

    Linden, T.

    1992-01-01

    Untreated spent sulphite liquor (SSL) was fermented with Canida tropicalis, Pichia stipitis, Pachysolen tannophilus, Schizosaccharomyces pombe, Saccharomyces cerevisiae and a co-culture of P. Tannophilus and A. cerevisiae, in the presence of xylose isomerases and 4.6 mM azide. The highest yield of ethanol, 0.41 g/g total sugar was obtained with S. cerevisiae, C. tropicalis, and P. tannophilus produced considerble amounts of polyoles, mainly xylitol. With P. stipitis sugar uptake was rapidly inhibited in untreated SSL. The presence of azide contributed to the yield by about 0.04. The fermentation of hydrogen fluoride-pretreated and acid-hydrolysed wheat straw with S. cerevisiae, xylose isomerase, and azide gave a yield of 0.40 g ethanol/g total sugar. In this substrate the xylose utilisation was 84% compared with 51% in SSL. In the concentration range appropriate for enzymatic xylose isomerization, xylulose was measured in a lignocellulose hydrolysate using HPLC with two hydrogen loaded ion exchange columns in series. SSL was used as a model for lignocellulose hydrolysates. The enzymatic isomerization of xylose to xylulose was followed directly in SSL, providing a method for the direct determination of xylose isomerase activity in lignocellulose hydrolysates. Three different xylose isomerase preparations of L. brevis whole cells were compared with a commercial enzyme preparation Maxazyme GI-immob., with respect to activity and stability. From a continuous SSL fermentation plant, two species of yeasts were isolated, S. cerevisiae and Pichia membranaefaciens. One of the isolates of S. cerevisiae, no. 3 was heavily flocculating. Without acetic acid present, both bakers' yeast and isolate no. 3 showed catabolite repression and fermented glucose and galactose sequentially. Galactose fermentation with bakers' yeast was strongly inhibited by acetic acid at pH values below 6. Isolate no. 3 fermented galactose, glucose and mannose, in the presence of acetic acid

  3. The fermentation of lignocellulose hydrolysates with xylose isomerases and yeasts

    Energy Technology Data Exchange (ETDEWEB)

    Linden, T.

    1992-09-01

    Untreated spent sulphite liquor (SSL) was fermented with Canida tropicalis, Pichia stipitis, Pachysolen tannophilus, Schizosaccharomyces pombe, Saccharomyces cerevisiae and a co-culture of P. Tannophilus and A. cerevisiae, in the presence of xylose isomerases and 4.6 mM azide. The highest yield of ethanol, 0.41 g/g total sugar was obtained with S. cerevisiae, C. tropicalis, and P. tannophilus produced considerble amounts of polyoles, mainly xylitol. With P. stipitis sugar uptake was rapidly inhibited in untreated SSL. The presence of azide contributed to the yield by about 0.04. The fermentation of hydrogen fluoride-pretreated and acid-hydrolysed wheat straw with S. cerevisiae, xylose isomerase, and azide gave a yield of 0.40 g ethanol/g total sugar. In this substrate the xylose utilisation was 84% compared with 51% in SSL. In the concentration range appropriate for enzymatic xylose isomerization, xylulose was measured in a lignocellulose hydrolysate using HPLC with two hydrogen loaded ion exchange columns in series. SSL was used as a model for lignocellulose hydrolysates. The enzymatic isomerization of xylose to xylulose was followed directly in SSL, providing a method for the direct determination of xylose isomerase activity in lignocellulose hydrolysates. Three different xylose isomerase preparations of L. brevis whole cells were compared with a commercial enzyme preparation Maxazyme GI-immob., with respect to activity and stability. From a continuous SSL fermentation plant, two species of yeasts were isolated, S. cerevisiae and Pichia membranaefaciens. One of the isolates of S. cerevisiae, no. 3 was heavily flocculating. Without acetic acid present, both bakers` yeast and isolate no. 3 showed catabolite repression and fermented glucose and galactose sequentially. Galactose fermentation with bakers` yeast was strongly inhibited by acetic acid at pH values below 6. Isolate no. 3 fermented galactose, glucose and mannose, in the presence of acetic acid even at pH.

  4. Layer-by-layer assembly of graphene oxide on polypropylene macroporous membranes via click chemistry to improve antibacterial and antifouling performance

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Clickable membrane prepared by photo bromination and SN2 nucleophilic substitution. • Azide graphene oxide prepared by ring-opening reaction. • Alkyne graphene oxide was prepared via esterification reaction. • Layer-by-layer assembly of graphene oxide on membrane by click chemistry. • Antibacterial and antifouling characteristics were enhanced greatly. - Abstract: Polypropylene is an extensively used membrane material; yet, polypropylene membranes exhibit extremely poor resistance to protein fouling. To ameliorate this issue, graphene oxide (GO) nanosheets were used to modify macroporous polypropylene membrane (MPPM) via layer-by-layer assembly technique through click reaction. First, alkyne-terminated GO was prepared through esterification between carboxyl groups in GO and amide groups in propargylamine; azide-terminated GO was synthesized by the ring-opening reaction of epoxy groups in GO with sodium azide. Second, GO was introduced to the membrane by click chemistry. Characterizations of infrared spectra and X-ray photoelectron spectroscopy confirmed the modification. The sharply decreasing of static water contact angle indicated the improvement of the surface hydrophilicity for GO modified membrane. Introducing GO to the membrane results in a dramatic increase of water flux, improvements in the antifouling characteristics and antibacterial property for the membranes. The pure water flux through the 5-layered GO modified membrane is 1.82 times that through the unmodified one. The water flux restores to 43.0% for the unmodified membrane while to 79.8% for the modified membrane. The relative flux reduction decreases by 32.1% due to GO modification. The antibacterial property was also enhanced by two-thirds. These results demonstrate that the antifouling and antibacterial characteristics can be raised by tethering GO to the membrane surface

  5. Activity-based protein profiling of ammonia monooxygenase in Nitrosomonas europaea.

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, Kristen; Sadler, Natalie C.; Wright, Aaron T.; Yeager, Chris; Hyman, Michael R.

    2016-01-29

    Nitrosomonas europaea is an aerobic nitrifying bacterium that oxidizes ammonia (NH3) to nitrite (NO2-) through the sequential activities of ammonia monooxygenase (AMO) and hydroxylamine oxidoreductase (HAO). Many alkynes are mechanism-based inactivators of AMO and here we describe an activity-based protein profiling method for this enzyme using 1,7-octadiyne (17OD) as a probe. Inactivation of NH4+-dependent O2 uptake by N. europaea by 17OD was time- and concentration-dependent. The effects of 17OD were specific for ammonia-oxidizing activity and de novo protein synthesis was required to reestablish this activity after cells were exposed to 17OD. Cells were reacted with AlexaFluor 647-azide using a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, solubilized and analyzed by SDS-PAGE and IR scanning. A fluorescent 28 kDa polypeptide was observed for cells previously exposed to 17OD, but not for cells treated with either allylthiourea or acetylene prior to exposure to 17OD, or for cells not previously exposed to 17OD. The 28 kDa polypeptide was membrane-associated and aggregated when heated with β-mercaptoethanol and SDS. The fluorescent 28 kDa polypeptide was also detected in cells pretreated with other diynes, but not in cells pretreated with structural homologs containing a single ethynyl functional group. The membrane fraction from 17OD-treated cells was conjugated with biotin-azide and solubilized in SDS. Streptavidin affinity-purified polypeptides were on-bead trypsin-digested and amino acid sequences of the peptide fragments were determined by LC-MS analysis. Peptide fragments from amoA were the predominant peptides detected in 17OD-treated samples. In gel digestion and MALDI-TOF/TOF analysis also confirmed the fluorescent 28 kDa polypeptide was amoA.

  6. Crystal structures of (Z-5-[2-(benzo[b]thiophen-2-yl-1-(3,5-dimethoxyphenylethenyl]-1H-tetrazole and (Z-5-[2-(benzo[b]thiophen-3-yl-1-(3,4,5-trimethoxyphenylethenyl]-1H-tetrazole

    Directory of Open Access Journals (Sweden)

    Narsimha Reddy Penthala

    2016-05-01

    Full Text Available (Z-5-[2-(Benzo[b]thiophen-2-yl-1-(3,5-dimethoxyphenylethenyl]-1H-tetrazole methanol monosolvate, C19H16N4O2S·CH3OH, (I, was prepared by the reaction of (Z-3-(benzo[b]thiophen-2-yl-2-(3,5-dimethoxyphenylacrylonitrile with tributyltin azide via a [3 + 2]cycloaddition azide condensation reaction. The structurally related compound (Z-5-[2-(benzo[b]thiophen-3-yl-1-(3,4,5-trimethoxyphenylethenyl]-1H-tetrazole, C20H18N4O3S, (II, was prepared by the reaction of (Z-3-(benzo[b]thiophen-3-yl-2-(3,4,5-trimethoxyphenylacrylonitrile with tributyltin azide. Crystals of (I have two molecules in the asymmetric unit (Z′ = 2, whereas crystals of (II have Z′ = 1. The benzothiophene rings in (I and (II are almost planar, with r.m.s deviations from the mean plane of 0.0084 and 0.0037 Å in (I and 0.0084 Å in (II. The tetrazole rings of (I and (II make dihedral angles with the mean planes of the benzothiophene rings of 88.81 (13 and 88.92 (13° in (I, and 60.94 (6° in (II. The dimethoxyphenyl and trimethoxyphenyl rings make dihedral angles with the benzothiophene rings of 23.91 (8 and 24.99 (8° in (I and 84.47 (3° in (II. In both structures, molecules are linked into hydrogen-bonded chains. In (I, these chains involve both tetrazole and methanol, and are parallel to the b axis. In (II, molecules are linked into chains parallel to the a axis by N—H...N hydrogen bonds between adjacent tetrazole rings.

  7. Development of Synthesis and Application on Phosphazene Energetic Compounds%磷腈类含能化合物的合成及应用研究进展

    Institute of Scientific and Technical Information of China (English)

    肖啸; 甘孝贤; 蔚红建; 刘庆; 栗磊

    2012-01-01

    分类综述了环磷腈含能化合物和聚磷腈含能粘合剂的合成及应用研究进展.目前,国内外关于环磷腈类含能化合物的研究不多,其中以螺环、叠氮以及螺环-叠氮复合类环磷腈为代表的含能化合物因其优越的性能和特点,成为绿色起爆药研究领域的重要方向.聚磷腈含能粘合剂主要包括叠氮粘合剂和硝酸酯粘合剂两大类,其具有比传统含能粘合剂更高的能量密度和分解焓,低温性能优良,对开发环境友好型含能粘合剂具有重要意义.%The development and application of cyclophosphazene and polyphosphazene compounds in energetic materials in recent years were classifiedly reviewed. Some synthesis and research trends of phosphazene-energetic materials were introduced. Spiro-, azide- and spiro-azide energetic cyclophosphazene compound are the three most important hazard primary explosives which have attracted more and more attention due to their excellent performance and distinctive structure characteristics. Azide- and nitric polyphosphazene will be of important significance to development environment-friendly energetic binders because of higher energy density and decomposition energy compared to conventional ones.

  8. Activity-Based Protein Profiling of Ammonia Monooxygenase in Nitrosomonas europaea.

    Science.gov (United States)

    Bennett, Kristen; Sadler, Natalie C; Wright, Aaron T; Yeager, Chris; Hyman, Michael R

    2016-04-01

    Nitrosomonas europaea is an aerobic nitrifying bacterium that oxidizes ammonia (NH3) to nitrite (NO2 (-)) through the sequential activities of ammonia monooxygenase (AMO) and hydroxylamine dehydrogenase (HAO). Many alkynes are mechanism-based inactivators of AMO, and here we describe an activity-based protein profiling method for this enzyme using 1,7-octadiyne (17OD) as a probe. Inactivation of NH4 (+)-dependent O2 uptake by N. europaea by 17OD was time- and concentration-dependent. The effects of 17OD were specific for ammonia-oxidizing activity, andde novoprotein synthesis was required to reestablish this activity after cells were exposed to 17OD. Cells were reacted with Alexa Fluor 647 azide using a copper-catalyzed azide-alkyne cycloaddition (CuAAC) (click) reaction, solubilized, and analyzed by SDS-PAGE and infrared (IR) scanning. A fluorescent 28-kDa polypeptide was observed for cells previously exposed to 17OD but not for cells treated with either allylthiourea or acetylene prior to exposure to 17OD or for cells not previously exposed to 17OD. The fluorescent polypeptide was membrane associated and aggregated when heated with β-mercaptoethanol and SDS. The fluorescent polypeptide was also detected in cells pretreated with other diynes, but not in cells pretreated with structural homologs containing a single ethynyl functional group. The membrane fraction from 17OD-treated cells was conjugated with biotin-azide and solubilized in SDS. Streptavidin affinity-purified polypeptides were on-bead trypsin-digested, and amino acid sequences of the peptide fragments were determined by liquid chromatography-mass spectrometry (LC-MS) analysis. Peptide fragments from AmoA were the predominant peptides detected in 17OD-treated samples. In-gel digestion and matrix-assisted laser desorption ionization-tandem time of flight (MALDI-TOF/TOF) analyses also confirmed that the fluorescent 28-kDa polypeptide was AmoA. PMID:26826234

  9. Bio-orthogonal Coupling as a Means of Quantifying the Ligand Density on Hydrophilic Quantum Dots.

    Science.gov (United States)

    Zhan, Naiqian; Palui, Goutam; Merkl, Jan-Philip; Mattoussi, Hedi

    2016-03-01

    We describe the synthesis of two metal-coordinating ligands that present one or two lipoic acid (LA) anchors, a hydrophilic polyethylene glycol (PEG) segment and a terminal reactive group made of an azide or an aldehyde, two functionalities with great utility in bio-orthogonal coupling techniques. These ligands were introduced onto the QD surfaces using a combination of photochemical ligation and mixed cap exchange strategy, where control over the fraction of azide and aldehyde groups per nanocrystal can be easily achieved: LA-PEG-CHO, LA-PEG-N3, and bis(LA)-PEG-CHO. We then demonstrate the application of two novel bio-orthogonal coupling strategies directly on luminescent quantum dot (QD) surfaces that use click chemistry and hydrazone ligation under catalyst-free conditions. We applied the highly efficient hydrazone ligation to couple 2-hydrozinopyridine (2-HP) to aldehyde-functionalized QDs, which produces a stable hydrazone chromophore with a well-defined optical signature. This unique optical feature has enabled us to extract a measure for the ligand density on the QDs for a few distinct sizes and for different ligand architectures, namely mono-LA-PEG and bis(LA)-PEG. We found that the foot-print-area per ligand was unaffected by the nanocrystal size but strongly depended on the ligand coordination number. Additionally, we showed that when the two bio-orthogonal functionalities (aldehyde and azide) are combined on the same QD platform, the nanocrystal can be specifically reacted with two distinct targets and with great specificity. This design yields QD platforms with distinct chemoselectivities that are greatly promising for use as carriers for in vivo imaging and delivery. PMID:26854900

  10. ANIONIC SYNTHESIS OF A "CLICKABLE" MIDDLE-CHAIN AZIDEFUNCTIONALIZED POLYSTYRENE AND ITS APPLICATION IN SHAPE AMPHIPHILES

    Institute of Scientific and Technical Information of China (English)

    Kan Yue; Jinlin He; Chang Liu; Mingjun Huang; Xue-Hui Dong; Kai Guo; Peihong Ni

    2013-01-01

    "Click chemistry" is,by definition,a general functionalization methodology (GFM) and its marriage with living anionic polymerization is particularly powerful in precise macromolecular synthesis.This paper reports the synthesis of a "clickable" middle-chain azide-functionalized polystyrene (mPS-N3) by anionic polymerization and its application in the preparation of novel shape amphiphiles based on polyhedral oligomeric silsesquioxane (POSS).The mPS-N3 was synthesized by coupling living poly(styryl)lithium chains (PSLi) with 3-chloropropylmethyldichlorosilane and subsequent nucleophilic substitution of the chloro group in the presence of sodium azide.Excess PSLi was end-capped with ethylene oxide to facilitate its removal by flash chromatography.The mPS-N3 was then derived into a giant lipid-like shape amphiphile in two steps following a sequential "click" strategy.The copper(I)-catalyzed azide-alkyne cycloaddition between mPS-N3 and alkyne-functionalized vinyl-substituted POSS derivative (VPOSS-alkyne) ensured quantitative ligation to give polystyrene with VPOSS tethered at the middle of the chain (mPS-VPOSS).The thiol-ene reaction with 1-thioglycerol transforms the vinyl groups on the POSS periphery to hydroxyls,resulting in an amphiphilic shape amphiphile,mPS-DPOSS.This synthetic approach is highly efficient and modular.It demonstrates the "click" philosophy of facile complex molecule construction from a library of simple building blocks and also suggests that mPS-N3 can be used as a versatile "clickable" motif in polymer science for the precise synthesis of complex macromolecules.

  11. “Flash” Solvent-free Synthesis of Triazoles Using a Supported Catalyst

    Directory of Open Access Journals (Sweden)

    Ibtissem Jlalia

    2009-01-01

    Full Text Available A solvent-free synthesis of 1,4-disubstituted-1,2,3-triazoles using neat azides and alkynes and a copper(I polymer supported catalyst (Amberlyst® A21•CuI is presented herein. As it provides the products in high yields and purities within minutes, this method thus being characterized as a "flash" synthesis, and was exemplified through the synthesis of a 24-compound library on a small scale.

  12. Copper (I iodide nanoparticles on polyaniline as a green, recoverable and reusable catalyst for multicomponent click synthesis of 1,4-disubstituted-1H-1,2,3-triazoles

    Directory of Open Access Journals (Sweden)

    Shervin Saadat

    2015-06-01

    Full Text Available A one-pot procedure for the synthesis of 1,4-disubstituted-1H-1,2,3-triazole derivatives via the three component coupling reaction between terminal alkynes, benzyl halides/α-halo ketones and sodium azide in the presences of CuI nanoparticles supported onto polyaniline (Nano CuI/PANI catalyst in water has been developed. This heterogeneous catalyst showed high catalytic activity and 1,4-regioselectivity for click cyclization in water as a “green” solvent and good to excellent yields were obtained in all cases over repeated five runs

  13. Copper (I) iodide nanoparticles on polyaniline as a green, recoverable and reusable catalyst for multicomponent click synthesis of 1,4-disubstituted-1H-1,2,3-triazoles

    OpenAIRE

    Shervin Saadat; Simin Nazari; Mozhgan Afshari; Maryam Shahabi; Mosadegh Keshavarz

    2015-01-01

    A one-pot procedure for the synthesis of 1,4-disubstituted-1H-1,2,3-triazole derivatives via the three component coupling reaction between terminal alkynes, benzyl halides/α-halo ketones and sodium azide in the presences of CuI nanoparticles supported onto polyaniline (Nano CuI/PANI) catalyst in water has been developed. This heterogeneous catalyst showed high catalytic activity and 1,4-regioselectivity for click cyclization in water as a “green” solvent and good to excellent yields were ob...

  14. Breeding of Hordeum Vulgare L. via chemical and physical Mutagenesis

    International Nuclear Information System (INIS)

    A field experiment was conducted under field conditions to compare for yield, yield components and some agronomic traits, of four selective mutants that have been obtained by using chemical mutagen (Sodium Azide) and physical mutagen ( Gamma ray, 20 KG) and their parent Arivate and Numar. The results show that the selective mutants have a high degree of genetic stability and exceeded their parents in some agronomic parameters. There fore, the two best selective mutants were accepted for registration and release under the name of Barrak and Amel as a new varieties by Nacional Committee for Registration and Release of Agricultural varieties

  15. The Non-Isotypical Nitride Selenides Dy3NSe3 and Ho3NSe3: Chains and Dimers

    OpenAIRE

    Lissner, Falk; Schleid, Thomas

    2009-01-01

    Abstract The non-isotypical lanthanoid(III) nitride selenides M3NSe3 of dysprosium (Dy3NSe3) and holmium (Ho3NSe3) are formed by the reaction of the respective rare-earth metal (M = Dy and Ho) with sodium azide (NaN3), selenium and an excess of iodine at 900 ?C from torch-sealed evacuated silica ampoules within seven days. Dy3NSe3 crystallizes orthorhombically (a = 1245.38(9), b = 393.69(3), c = 1303.74(9) pm) in space group Pnma with Z = 4, whereas monoclinic Ho3NSe3 (a = 1152.93(...

  16. A modular approach for the construction and modification of glyco-SAMs utilizing 1,3-dipolar cycloaddition.

    Science.gov (United States)

    Kleinert, Mike; Winkler, Tobias; Terfort, Andreas; Lindhorst, Thisbe K

    2008-06-21

    We report the synthesis of a broad variety of functionalized molecules for assembly on gold, allowing the formation of biologically relevant SAMs by a modular approach: either utilizing 1,3-dipolar cycloaddition of alkynes and azides in solution or by 'click on SAM'. Extensive studies into the various parameters of SAM formation and stability have been carried out, leading us to deduce reliable conditions under which glyco-decorated self-assembled monolayers can be formed and studied such as in SPR-supported binding assays.

  17. Genetically encoded cleavable protein photo-cross-linker.

    Science.gov (United States)

    Lin, Shixian; He, Dan; Long, Teng; Zhang, Shuai; Meng, Rong; Chen, Peng R

    2014-08-27

    We have developed a genetically encoded, selenium-based cleavable photo-cross-linker that allows for the separation of bait and prey proteins after protein photo-cross-linking. We have further demonstrated the efficient capture of the in situ generated selenenic acid on the cleaved prey proteins. Our strategy involves tagging the selenenic acid with an alkyne-containing dimethoxyaniline molecule and subsequently labeling with an azide-bearing fluorophore or biotin probe. This cleavage-and-capture after protein photo-cross-linking strategy allows for the efficient capture of prey proteins that are readily accessible by two-dimensional gel-based proteomics and mass spectrometry analysis.

  18. Visible Light Driven Photocascade Catalysis: Ru(bpy)3(PF6)2/TBHP-Mediated Synthesis of Fused β-Carbolines in Batch and Flow Microreactors.

    Science.gov (United States)

    Chandrasekhar, D; Borra, Satheesh; Nanubolu, Jagadeesh Babu; Maurya, Ram Awatar

    2016-06-17

    1,2,3,4-Tetrahydro-β-carbolines were coupled with α-keto vinyl azides through an unprecedented visible light-Ru(bpy)3(PF6)2/TBHP mediated photocascade strategy that involves photosensitization, photoredox catalysis and [3 + 2] cycloaddition reaction. The scope and scale-up feasibility of the photocascade strategy was demonstrated by synthesizing 18 different fused β-carbolines in moderate to good yields using batch and continuous flow microreactor. This operationally simple synthetic protocol allows the formation of one C-C and two C-N new bonds in the overall transformation. PMID:27226119

  19. Synthesis, anti-microbial activity and molecular docking studies on triazolylcoumarin derivatives

    Indian Academy of Sciences (India)

    Chinnadurai Satheeshkumar; Mahalingam Ravivarma; Pandian Arjun; Vaithiyanathan Silambarasan; Nanjian Raaman; Devadasan Velmurugan; Changsik Song; Perumal Rajakumar

    2015-03-01

    A series of triazolylcoumarins was synthesized by the cycloaddition of acetylenic derivatives to azide in the presence of Cu(I) catalyst at room temperature. All the synthesized compounds were evaluated for their anti-microbial activity against Gram-positive (B. subtilis and S. aureus), Gram-negative bacteria (K. pneumonia and P. vulgaris) and human pathogenic fungi (C. tropicalis and C. krusei), with tetracycline and fluconazole as standards for anti-microbial and anti-fungal activity. Triazolylcoumarins exhibit anti-microbial activity against all the tested pathogens, which is further supported by molecular docking studies.

  20. Preparation of significant complexes of selected transition elements with appropriate ligands

    International Nuclear Information System (INIS)

    New complexes of copper (II), nickel (II) and cobalt (II) have been prepared using triphenylphosphine and benzofurazan-1-oxide as ligands. Benzofurazan-1-oxide was prepared from the reaction between o-nitrophenyl azide and toluene as a catalyst. These complexes have been identified by means of infra-red spectra and also melting points determination. The coordination bonding was found to be through phosphorus-metal and nitrogen-metal. The melting points and colour confirmed are used as initial confirmation or identification procedure. Stability constants were studied to the new complexes prepared which is in good agreement with reported value for similar complexes. (Author)

  1. Synthesis of bi- and bis-1,2,3-triazoles by copper-catalyzed Huisgen cycloaddition: A family of valuable products by click chemistry

    Directory of Open Access Journals (Sweden)

    Zhan-Jiang Zheng

    2015-12-01

    Full Text Available The Cu(I-catalyzed azide-alkyne cycloaddition reaction, also known as click chemistry, has become a useful tool for the facile formation of 1,2,3-triazoles. Specifically, the utility of this reaction has been demonstrated by the synthesis of structurally diverse bi- and bis-1,2,3-triazoles. The present review focuses on the synthesis of such bi- and bistriazoles and the importance of using copper-promoted click chemistry (CuAAC for such transformations. In addition, the application of bitriazoles and the related CuAAAC reaction in different fields, including medicinal chemistry, coordination chemistry, biochemistry, and supramolecular chemistry, have been highlighted.

  2. Synthesis and evaluation of 1-alkyl-4-phenyl-[1,2,3]-triazole derivatives as antimycobacterial agent

    Energy Technology Data Exchange (ETDEWEB)

    Gallardo, Hugo; Conte, Gilmar; Bryk, Fernando [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Quimica]. E-mail: hugo@qmc.ufsc.br; Lourenco, Maria Cristina S. [Fundacao Oswaldo Cruz (FIOCRUZ), Rio de Janeiro, RJ (Brazil). Instituto de Pesquisa Evandro Chagas; Costa, Marilia S.; Ferreira, Vitor F. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Inst. de Quimica]. E-mail: cegvito@vm.uff.br

    2007-07-01

    Fourteen small molar mass 1-alkyl-4-phenyl-[1,2,3]-triazole derivatives were prepared using a straightforward and efficient method for the regioselective synthesis of [1,2,3]-triazoles and the compounds were screened for antimycobacterial activity against multiple-drug-resistant strains of Mycobacterium tuberculosis H37Rv. The synthetic methodology consisted of a Cu(I)-catalyzed 1,3-dipolar cycloaddition of aryl azides to terminal arylacetylenes (click-reaction). Six [1,2,3]-triazoles were found to be more active against M. tuberculosis than the positive control ethambutol. (author)

  3. Dual Function Additives: A Small Molecule Crosslinker for Enhanced Efficiency and Stability in Organic Solar Cells

    KAUST Repository

    Rumer, Joseph W.

    2015-02-01

    A bis-azide-based small molecule crosslinker is synthesized and evaluated as both a stabilizing and efficiency-boosting additive in bulk heterojunction organic photovoltaic cells. Activated by a noninvasive and scalable solution processing technique, polymer:fullerene blends exhibit improved thermal stability with suppressed polymer skin formation at the cathode and frustrated fullerene aggregation on ageing, with initial efficiency increased from 6% to 7%. © 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Application of Cu(I)-catalyzed azide–alkyne cycloaddition for the design and synthesis of sequence specific probes targeting double-stranded DNA

    Science.gov (United States)

    Filichev, Vyacheslav V; Boutorine, Alexandre S

    2016-01-01

    Summary Efficient protocols based on Cu(I)-catalyzed azide–alkyne cycloaddition were developed for the synthesis of conjugates of pyrrole–imidazole polyamide minor groove binders (MGB) with fluorophores and with triplex-forming oligonucleotides (TFOs). Diverse bifunctional linkers were synthesized and used for the insertion of terminal azides or alkynes into TFOs and MGBs. The formation of stable triple helices by TFO-MGB conjugates was evaluated by gel-shift experiments. The presence of MGB in these conjugates did not affect the binding parameters (affinity and triplex stability) of the parent TFOs. PMID:27559384

  5. One-pot synthesis of Au@SiO2 catalysts: A click chemistry approach

    KAUST Repository

    Solovyeva, Vera A.

    2014-10-13

    Using the copper-catalyzed azide-alkyne cycloaddition "click" reaction, a library of triazole amphiphiles with a variety of functional polar "heads" and hydrophobic or superhydrophobic "tails" was synthesized. The amphiphiles were evaluated for their ability to stabilize small Au nanoparticles, and, at the same time, serve as templates for nanocasting porous SiO2. One of the Au@SiO2 materials thus prepared was found to be a highly active catalyst for the Au nanoparticle-catalyzed regioselective hydroamination of alkynes.

  6. One-step ligand exchange reaction as an efficient way for functionalization of magnetic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Mrowczynski, Radoslaw [Humboldt-University Berlin, Department of Chemistry (Germany); Rednic, Lidia; Turcu, Rodica [National Institute of Research and Development for Isotopic and Molecular Technologies (Romania); Liebscher, Juergen, E-mail: liebscher@chemie.hu-berlin.de [Humboldt-University Berlin, Department of Chemistry (Germany)

    2012-07-15

    Novel magnetic Fe{sub 3}O{sub 4} nanoparticles (NPs) covered by one layer of functionalized fatty acids, bearing entities (Hayashi catalyst, biotin, quinine, proline, and galactose) of high interest for practical application in nanomedicine or organocatalysis, were synthesized. The functionalized fatty acids were obtained by Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) of azido fatty acids with alkynes. All the magnetic NPs show superparamagnetic behavior with high values of magnetization and high colloidal stability in DCM solution.

  7. Update: An efficient synthesis of poly(ethylene glycol)-supported iron(II) porphyrin using a click reaction and its application for the catalytic olefination of aldehydes

    KAUST Repository

    Chinnusamy, Tamilselvi R.

    2012-05-09

    The facile synthesis of polyethylene glycol (PEG)-immobilized iron(II) porphyrin using a copper-catalyzed azide-alkyne [3+2] cycloaddition "click" reaction is reported. The prepared complex 5 (PEG-C 51H 39FeN 7O) was found to be an efficient catalyst for the selective olefination of aldehydes with ethyl diazoacetate in the presence of triphenylphosphine, and afforded excellent olefin yields with high (E) selectivities. The PEG-supported catalyst 5 was readily recovered by precipitation and filtration, and was recycled through ten runs without significant activity loss. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 'Click' functionalised polymer resins: a new approach to the synthesis of surface attached bipyridinium and naphthalene diimide [2]rotaxanes.

    Science.gov (United States)

    Wilson, Hannah; Byrne, Sean; Bampos, Nick; Mullen, Kathleen M

    2013-04-01

    Herein we describe the design and synthesis of a series of solid-tethered [2]rotaxanes utilising crown ether-naphthalene diimide or crown ether-bipyridinium host guest interactions. TentaGel polystyrene resins were initially modified in a two-stage procedure to azide functionalised beads before the target supramolecular architectures were attached using a copper catalysed "click" procedure. The final assembly was examined using IR spectroscopy and gel-phase (1)H High Resolution Magic Angle Spinning (HR MAS) NMR spectroscopy. The HR MAS technique enabled a direct comparison between the solid-tethered architectures and the synthesis and characterisation of analogous solution-based [2]rotaxanes to be made.

  9. Process for producing wurtzitic or cubic boron nitride

    International Nuclear Information System (INIS)

    Disclosed is a process for producing wurtzitic or cubic boron nitride comprising the steps of: [A] preparing an intimate mixture of powdered boron oxide, a powdered metal selected from the group consisting of magnesium or aluminum, and a powdered metal azide; [B] igniting the mixture and bringing it to a temperature at which self-sustaining combustion occurs; [C] shocking the mixture at the end of the combustion thereof with a high pressure wave, thereby forming as a reaction product, wurtzitic or cubic boron nitride and occluded metal oxide; and, optionally [D] removing the occluded metal oxide from the reaction product. Also disclosed are reaction products made by the process described

  10. Synthesis of click-reactive HPMA copolymers using RAFT polymerization for drug delivery applications

    DEFF Research Database (Denmark)

    Ebbesen, Morten F; Schaffert, D.H.; Crowley, Michael L;

    2013-01-01

    This study describes a versatile strategy combining reversible addition fragmentation transfer (RAFT) polymerization and click chemistry to synthesize well-defined, reactive copolymers of N-(2-hydroxypropyl)methacrylamide (HPMA) for drug delivery applications. A novel azide containing monomer N-(3......-alkyne cycloaddition (CuAAC) was demonstrated by efficient conjugation (up to 92%) of phosphocholine, a near infrared dye, and poly(ethylene glycol) (PEG) with different substitution degrees, either alone or in combination. This study introduces a novel and versatile method to synthesize well-defined click-reactive...

  11. Dipolar cross-linkers for PDMS networks with enhanced dielectric permittivity and low dielectric loss

    DEFF Research Database (Denmark)

    Bahrt, Frederikke; Daugaard, Anders Egede; Hvilsted, Søren;

    2013-01-01

    -(4-((4-nitrophenyl)diazenyl)phenoxy)-prop-1-yn-1-ylium, with a synthesized silicone compatible azide-functional cross-linker by click chemistry. The thermal, mechanical and electromechanical properties were investigated for PDMS films with 0 to 3.6 wt% of dipole-cross-linker. The relative dielectric permittivity...... was found to increase by ∼20% at only 0.46 wt% of incorporated dipole without significant changes in the mechanical properties. Furthermore, the dielectric losses were proved to be remarkably low while the electrical breakdown strengths were high....

  12. Design, Synthesis and Anti-HIV Integrase Evaluation of 1,2,3-Triazol-4-yl-substituted 1,4-Dihydro-4-oxo-1,5-napthyridine-3-carboxylic Acids

    Institute of Scientific and Technical Information of China (English)

    ZENG,Jia; L(U),Xiuhua; ZENG,Chengchu; HU,Liming; ZHONG,Rugang

    2009-01-01

    Copper(I)-eatalyzed terminal alkyne-azide 1,3-cycloaddition reaction has emerged as one of the main strategies for the rapid creation and screening of a small molecular library. The present work describes the design and synthe-sis of a series of 1,2,3-triazol-4-yl-substituted 1,4-dihydro-4-oxo-1,5-napthyridine-3-carboxylic acids in which the hydrophobic and hydrophilic domains were efficiently incorporated by a click reaction. The structures of the desired products 8 and 12 were characterized by spectroscopic methods and their HIV integrase inhibitory activities were also screened.

  13. Hypervalent iodine(iii)-promoted N-incorporation into N-aryl vinylogous carbamates to quinoxaline diesters: access to 1,4,5,8-tetraazaphenanthrene.

    Science.gov (United States)

    Sagar, A; Vidaycharan, Shinde; Shinde, Anand H; Sharada, Duddu S

    2016-04-26

    A novel oxidative N-incorporation strategy for synthesis of quinoxaline diesters under metal-free conditions is described for the first time. The mild reaction conditions allow for this transformation via the formation of two C(sp(2))-N bonds utilizing cheaply available NaN3 as the N-atom source. N-Aryl vinylogous carbamates in this study undergo azidation at enamino C(sp(2))-H selectively. The robustness of this strategy is further demonstrated by the synthesis of a valuable 1,4,5,8-tetraazaphenanthrene derivative using a mild and convenient approach.

  14. Efficient one-pot synthesis of amino-benzotriazolodiazocinone scaffolds via catalyst-free tandem Ugi-Huisgen reactions.

    Science.gov (United States)

    Barlow, T M A; Jida, M; Guillemyn, K; Tourwé, D; Caveliers, V; Ballet, S

    2016-05-18

    Herein we describe a catalyst-free, one-pot procedure employing an Ugi-4CR between propargyl glycine, functionalised 2-azidoanilines, different isocyanides and aldehydes, followed by a thermal azide-alkyne Huisgen cycloaddition to generate a 14-member set of amino-benzotriazolodiazocine-bearing dipeptides with multiple points of diversification and high atom economy. These structures were derivatized by means of Suzuki-Miyaura cross-coupling reactions at two positions with good to excellent yields, leading to conformationally constrained tricyclic structures. In silico and NMR conformational analysis studies demonstrated that turn conformations are adopted by these structures. PMID:27117259

  15. Poly[(μ2-azido-κ2N1:N1[μ2-5-(8-quinolyloxymethyltetrazolato-κ4N1,O,N5:N4]zinc(II

    Directory of Open Access Journals (Sweden)

    Hong-ling Cai

    2009-06-01

    Full Text Available In the title compound, [Zn(C11H8N5O(N3]n, the Zn atom is hexacoordinated by five N atoms and one O atom in a distorted octahedral geometry. The chelating 5-(8-quinolyloxymethyltetrazolate ligands are approximately planar, with a dihedral angle of 3.6 (2° between the quinoline and tetrazole planes. Adjacent Zn atoms are linked by two bridging azide ligands across a centre of inversion, and further coordination by one N atom of an adjacent tetrazole unit forms two-dimensional frameworks in (100. C—H...N interactions exist between ligands in neighbouring layers.

  16. A novel approach for the synthesis of 5-substituted-1H-tetrazoles

    Energy Technology Data Exchange (ETDEWEB)

    Akhlaghinia, Batool; Rezazadeh, Soodabeh, E-mail: akhlaghinia@um.ac.ir [Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad (Iran, Islamic Republic of)

    2012-12-15

    A series of 5-substituted-1H-tetrazoles (RCN{sub 4}H) have been synthesized by cycloaddition reaction of different aryl and alkyl nitriles with sodium azide in DMSO using CuSO{sub 4}{center_dot}5H{sub 2}O as catalyst. A wide variety of aryl nitriles underwent [3+2] cycloaddition to afford tetrazoles under mild reaction conditions in good to excellent yields. The catalyst used is readily available and environmentally friendly. Short reaction times, good to excellent yields, safe process and simple workup make this method an attractive and useful contribution to present organic synthesis of 5-substituted-1H-tetrazoles. (author)

  17. Synthesis of bi- and bis-1,2,3-triazoles by copper-catalyzed Huisgen cycloaddition: A family of valuable products by click chemistry

    OpenAIRE

    Zhan-Jiang Zheng; Ding Wang; Zheng Xu; Li-Wen Xu

    2015-01-01

    The Cu(I)-catalyzed azide-alkyne cycloaddition reaction, also known as click chemistry, has become a useful tool for the facile formation of 1,2,3-triazoles. Specifically, the utility of this reaction has been demonstrated by the synthesis of structurally diverse bi- and bis-1,2,3-triazoles. The present review focuses on the synthesis of such bi- and bistriazoles and the importance of using copper-promoted click chemistry (CuAAC) for such transformations. In addition, the application of bitri...

  18. Synthesis of Glycosyl Amides Using Selenocarboxylates as Traceless Reagents for Amide Bond Formation.

    Science.gov (United States)

    Silva, Luana; Affeldt, Ricardo F; Lüdtke, Diogo S

    2016-07-01

    Carbohydrate-derived amides were successfully prepared in good yields from a broad range of substrates, including furanosyl and pyranosyl derivatives. The methodology successfully relied on the in situ generation of lithium selenocarboxylates from Se/LiEt3BH and acyl chlorides or carboxylic acids and their reaction with sugar azides. A key aspect of the present protocol is that we start from elemental selenium; isolation and handling of all reactive and sensitive selenium-containing intermediates is avoided, therefore providing the selenocarboxylate the status of a traceless reagent. PMID:27275515

  19. 64Cu Core-labeled Nanoparticles with High Specific Activity via Metal-Free Click Chemistry

    OpenAIRE

    Zeng, Dexing; Lee, Nam S.; Liu, Yongjian; Zhou, Dong; Dence, Carmen S.; Wooley, Karen L.; Katzenellenbogen, John A.; Welch, Michael J.

    2012-01-01

    A novel strategy based on metal-free click chemistry was developed for the copper-64 radiolabeling of the core in shell-crosslinked nanoparticles (SCK-NPs). Compared with Cu(I)-catalyzed click chemistry, this metal-free strategy provides the following advantages for Cu-64 labeling of the core of SCK-NPs: (1) elimination of copper exchange between non-radioactive Cu in the catalyst and DOTA-chelated Cu-64; (2) elimination of the internal “click” reactions between the azide and acetylene groups...

  20. Triazole-containing N-acyl homoserine lactones targeting the quorum sensing system in Pseudomonas aeruginosa

    DEFF Research Database (Denmark)

    Hansen, Mette Reimert; Jakobsen, Tim H.; Bang, Claus Gunnar;

    2015-01-01

    pathogenesis and antibiotic tolerance of a bacterial biofilm. To identify the structural elements important for antagonistic or agonistic activity against the Pseudomonas aeruginosa LasR protein, we report the synthesis and screening of new triazole-containing mimics of natural N-acyl homoserine lactones. A...... series of azide- and alkyne-containing homoserine lactone building blocks was used to prepare an expanded set of 123 homoserine lactone analogues through a combination of solution- and solid-phase synthesis methods. The resulting compounds were subjected to cell-based quorum sensing screening assays...

  1. Multifunctional Pt(II) Reagents: Covalent Modifications of Pt Complexes Enable Diverse Structural Variation and In-Cell Detection.

    Science.gov (United States)

    White, Jonathan D; Haley, Michael M; DeRose, Victoria J

    2016-01-19

    To enhance the functionality of Pt-based reagents, several strategies have been developed that utilize Pt compounds modified with small, reactive handles. This Account encapsulates work done by us and other groups regarding the use of Pt(II) compounds with reactive handles for subsequent elaboration with fluorophores or other functional moieties. Described strategies include the incorporation of substituents for well-known condensation or nucleophilic displacement-type reactions and their use, for example, to tether spectroscopic handles to Pt reagents for in vivo investigation. Other chief uses of displacement-type reactions have included tethering various small molecules exhibiting pharmacological activity directly to Pt, thus adding synergistic effects. Click chemistry-based ligation techniques have also been applied, primarily with azide- and alkyne-appended Pt complexes. Orthogonally reactive click chemistry reactions have proven invaluable when more traditional nucleophilic displacement reactions induce side-reactivity with the Pt center or when systematic functionalization of a larger number of Pt complexes is desired. Additionally, a diverse assortment of Pt-fluorophore conjugates have been tethered via click chemistry conjugation. In addition to providing a convenient synthetic path for diversifying Pt compounds, the use of click-capable Pt complexes has proved a powerful strategy for postbinding covalent modification and detection with fluorescent probes. This strategy bypasses undesirable influences of the fluorophore camouflaged as reactivity due to Pt that may be present when detecting preattached Pt-fluorophore conjugates. Using postbinding strategies, Pt reagent distributions in HeLa and lung carcinoma (NCI-H460) cell cultures were observed with two different azide-modified Pt compounds, a monofunctional Pt(II)-acridine type and a difunctional Pt(II)-neutral complex. In addition, cellular distribution was observed with an alkyne-appended difunctional

  2. CuAAC: An Efficient Click Chemistry Reaction on Solid Phase.

    Science.gov (United States)

    Castro, Vida; Rodríguez, Hortensia; Albericio, Fernando

    2016-01-11

    Click chemistry is an approach that uses efficient and reliable reactions, such as Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC), to bind two molecular building blocks. CuAAC has broad applications in medicinal chemistry and other fields of chemistry. This review describes the general features and applications of CuAAC in solid-phase synthesis (CuAAC-SP), highlighting the suitability of this kind of reaction for peptides, nucleotides, small molecules, supramolecular structures, and polymers, among others. This versatile reaction is expected to become pivotal for meeting future challenges in solid-phase chemistry.

  3. Immobilization of Antibody on a Cyclic Olefin Copolymer Surface with Functionalizable, Non-Biofouling Poly[Oligo(Ethylene Glycol) Methacrylate].

    Science.gov (United States)

    Jeong, Seung Pyo; Kang, Sung Min; Hong, Daewha; Lee, Hee-Yoon; Choi, Insung S; Ko, Sangwon; Lee, Jungkyu K

    2015-02-01

    We report a perfluoroaryl azide-based photoreaction for synthesizing functionalizable and nonbiofouling poly[oligo(ethylene glycol) methacrylate] (pOEGMA) films on a chemically inert COC substrate, and an estimation of a surface coverage of the antibody immobilized onto the surface with the immuno-gold nanoparticles. The processes were confirmed by water contact angle measurement, FT-IR spectroscopy, and FE-SEM. The strategy demonstrated in this work could be applied to functionalizations of other polymeric materials and determination of the binding capacity of analytes in biosensors and microfluidic devices.

  4. Brønsted acid-promoted azide–olefin [3 + 2] cycloadditions for the preparation of contiguous aminopolyols: The importance of disiloxane ring size to a diastereoselective, bidirectional approach to zwittermicin A

    Directory of Open Access Journals (Sweden)

    Hubert Muchalski

    2010-12-01

    Full Text Available We report the first study of substrate-controlled diastereoselection in a double [3 + 2] dipolar cycloaddition of benzyl azide with α,β-unsaturated imides. Using a strong Brønsted acid (triflic acid to activate the electron deficient imide π-bond, high diastereoselection was observed provided that a 1,1,3,3-tetraisopropoxydisiloxanylidene group (TIPDS is used to restrict the conformation of the central 1,3-anti diol. This development provides a basis for a stereocontrolled approach to the aminopolyol core of (−-zwittermicin A using a bidirectional synthesis strategy.

  5. The azido ligand: a useful tool in designing chain compounds exhibiting alternating ferro- and antiferro-magnetic interactions

    OpenAIRE

    Viau, Guillaume; Lombardi, Maria Grazia; De Munno, Giovanni; Julve Olcina, Miguel; Lloret Pastor, Francisco; Faus, Juan; Caneschi, Andrea; Clemente Juan, Juan Modesto

    1997-01-01

    A one-pot reaction of NiII 1, CoII 2, FeII 3 and MnII 4 with 2,2A-bipyridine (bipy) and azide in water leads to [M(bipy)(N3)2]n chains where the metal ion is alternatively bridged by double end-on (EO) and end-to-end (EE) azido bridges; theoretical analysis of the variable-temperature magnetic susceptibility data of 1 and 4 reveals the occurrence of intrachain alternating ferro- (through EO) and antiferro-magnetic (through EE) interactions. Julve Olcina, Miguel, ; Lloret...

  6. Shock Hugoniot and equations of states of water, castor oil, and aqueous solutions of sodium chloride, sucrose and gelatin

    Science.gov (United States)

    Gojani, A. B.; Ohtani, K.; Takayama, K.; Hosseini, S. H. R.

    2016-01-01

    This paper reports a result of experiments for the determination of reliable shock Hugoniot curves of liquids, in particular, at relatively low pressure region, which are needed to perform precise numerical simulations of shock wave/tissue interaction prior to the development of shock wave related therapeutic devices. Underwater shock waves were generated by explosions of laser ignited 10 mg silver azide pellets, which were temporally and spatially well controlled. Measuring temporal variation of shock velocities and over-pressures in caster oil, aqueous solutions of sodium chloride, sucrose and gelatin with various concentrations, we succeeded to determine shock Hugoniot curves of these liquids and hence parameters describing Tait type equations of state.

  7. Evaluation of 5-ethynyl-2′-deoxyuridine staining as a sensitive and reliable method for studying cell proliferation in the adult nervous system

    OpenAIRE

    Zeng, Chenbo; Pan, Fenghui; Jones, Lynne A.; Lim, Miranda M.; Griffin, Elizabeth A.; Sheline, Yvette I.; Mark A. Mintun; Holtzman, David M.; Mach, Robert H.

    2010-01-01

    Recently, a novel method for detection of DNA synthesis has been developed based on the incorporation of 5–ethynyl–2′–deoxyuridine (EdU), a thymidine analogue, into cellular DNA and the subsequent reaction of EdU with a fluorescent azide in a copper–catalyzed [3+2] cycloaddition (“Click” reaction). In the present study, we evaluated this method for studying cell proliferation in the adult central nervous system in comparison with the “gold standard” method of 5–bromo–2′–deoxyuridine (BrdU) st...

  8. Stereospecific Synthesis of Substituted Aziridines by a Crystal-to-Crystal Photodenitrogenation of Δ(2)-1,2,3-Triazolines.

    Science.gov (United States)

    Chung, Tim S; Lopez, Steven A; Houk, K N; Garcia-Garibay, Miguel A

    2015-09-18

    Crystalline cis- or trans-Δ(2)-1,2,3-triazolines prepared by highly stereospecific and regioselective hydrogen bonding-catalyzed dipolar cycloaddition of activated cis- or trans-alkenes with aryl azides undergo a highly stereospecific photodenitrogenation to form the corresponding cis- or trans- azidirines in high chemical yields. While examples involving disubstituted and trisubstituted triazolines highlight steric challenges encountered in the dipolar cycloaddition reaction, the stereochemical control exerted by the crystalline lattice is enhanced by bulky substituents in the triazoline precursors to generate aziridines photochemically. PMID:26338467

  9. Synthesis and Fluorophilicity of Compounds with Tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl Substituent.

    OpenAIRE

    Strašák, T. (Tomáš); Červenková Šťastná, L. (Lucie); Bílková, V. (Veronika); Skoupá, V. (Veronika); Karban, J.; Cuřínová, P. (Petra); Čermák, Jan K.

    2015-01-01

    A series of new highly fluorous compounds with tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl substituent was synthesized starting from 3-halopropyltris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-silanes. The series can be divided into three subgroups based on the potential use of theses compounds: (i) cyclopentadienyl transition metal complexes and N-ligands, (ii) synthons for azide-alkyne [3+2] cycloaddition, (iii) imidazolium-type ionic liquids. Partition coefficients between f...

  10. Neomycin-phenolic conjugates: polycationic amphiphiles with broad-spectrum antibacterial activity, low hemolytic activity and weak serum protein binding.

    Science.gov (United States)

    Findlay, Brandon; Zhanel, George G; Schweizer, Frank

    2012-02-15

    Here we present a proof-of-concept study, combining two known antimicrobial agents into a hybrid structure in order to develop an emergent cationic detergent-like interaction with the bacterial membrane. Six amphiphilic conjugates were prepared by copper (I)-catalyzed 1,3-dipolar cycloaddition between a neomycin B-derived azide and three alkyne-modified phenolic disinfectants. Three conjugates displayed good activity against a variety of clinically relevant Gram positive and Gram negative bacteria, including MRSA, without the high level of hemolysis or strong binding to serum proteins commonly observed with other cationic antimicrobial peptides and detergents.

  11. Synthesis of an antimetastatic tetrasaccharide β-D-Gal-(1 → 4)-β-D-GlcpNAc-(1 → 6)-α-D-Manp-(1 → 6)-β-D-Manp-Ome

    Institute of Scientific and Technical Information of China (English)

    Kai Jun Liao; Xiao Feng Jin; Xiang Bao Meng; Chen Li; Zhong Jun Li

    2012-01-01

    An antimetastatic tetrasaccharide T1,β-D-Gal-(1 → 4)-β-D-GlcpNAc-(1 → 6)-α-D-Manp-(1 → 6)-β-D-Manp-OMe,was synthesized with two approaches.The first approach was a conventional method employing thioglycoside and Koenigs-Knorr glycosylation reaction in 24% overall yield.The second one was a novel route through the azidoiodo-glycosylation strategy by using 2-iodo-2-deoxylactosyl azide as the donor in 36% overall yield.

  12. On-Surface Synthesis by Click Chemistry Investigated by STM and XPS

    DEFF Research Database (Denmark)

    Vadapoo, Sundar Raja

    2014-01-01

    Molecular synthesis is essential in the bottom-up approach of achieving highly stable nanostructures. On-surface synthesis is highly interesting from the basic science of view to improve the understanding of molecular behavior adsorbed on metal surfaces, and has potential applications...... such as molecular electronics and surface functionalization. In this thesis, a well-defined click chemistry approach is followed, with the study of azide-alkyne cycloaddition on Cu(111) surface in UHV environment. A successful achievement of the click reaction product via on-surface synthesis has been shown, which...... is characterised by STM and XPS....

  13. DNA Three Way Junction Core Decorated with Amino Acids-Like Residues-Synthesis and Characterization.

    Science.gov (United States)

    Addamiano, Claudia; Gerland, Béatrice; Payrastre, Corinne; Escudier, Jean-Marc

    2016-01-01

    Construction and physico-chemical behavior of DNA three way junction (3WJ) functionalized by protein-like residues (imidazole, alcohol and carboxylic acid) at unpaired positions at the core is described. One 5'-C(S)-propargyl-thymidine nucleotide was specifically incorporated on each strand to react through a post synthetic CuACC reaction with either protected imidazolyl-, hydroxyl- or carboxyl-azide. Structural impacts of 5'-C(S)-functionalization were investigated to evaluate how 3WJ flexibility/stability is affected. PMID:27563857

  14. Synthesis of 7-Azidoacetamido-4,6-Dinitro-Benzofuroxan

    Institute of Scientific and Technical Information of China (English)

    WANG Jian-long; OU Yu-xiang; L(U) Lian-ying; CHEN Bo-ren

    2005-01-01

    7-Azidoacetamido-4, 6-dinitro-benzofuroxan has been synthesized from the starting materials of chloroacetyl chloride and m-chloroaniline, and has been characterized by elemental analysis, IR, 1H NMR and MS spectroscopies. The title compound was obtained through the reactions of amidation, nitration, azidation and pyrolysis. Azido group was introduced into benzofuroxan derivative to give the energetic compound of high nitrogen content and high enthalpy of formation. It is hopeful that the title compound can be developed into new energetic material and energetic plastic additives.

  15. Pd(0)-Catalyzed Direct C-H Functionalization of 2-H-4-Benzylidene Imidazolones: Friendly and Large-Scale Access to GFP and Kaede Protein Fluorophores.

    Science.gov (United States)

    Muselli, Mickaël; Baudequin, Christine; Perrio, Cécile; Hoarau, Christophe; Bischoff, Laurent

    2016-04-11

    The first one-pot synthesis of N-substituted 2-H-4-benzylidene imidazolones and their subsequent palladium-catalyzed and copper-assisted direct C2-H arylation and alkenylation with aryl- and alkenylhalides are described. This innovative synthesis is step-economical, azide-free, high yielding, highly flexible in the introduction of a variety of electronically different groups, and can be operated on large-scale. Moreover, the method allows direct access to C2-arylated or alkenylated imidazolone-based green fluorescent protein (GFP) and Kaede protein fluorophores, including ortho-hydroxylated models. PMID:26960963

  16. Multicomponent click synthesis of new 1,2,3-triazole derivatives of pyrimidine nucleobases: promising acidic corrosion inhibitors for steel.

    Science.gov (United States)

    González-Olvera, Rodrigo; Espinoza-Vázquez, Araceli; Negrón-Silva, Guillermo E; Palomar-Pardavé, Manuel E; Romero-Romo, Mario A; Santillan, Rosa

    2013-12-06

    A series of new mono-1,2,3-triazole derivatives of pyrimidine nucleobases were synthesized by one-pot copper(I)-catalyzed 1,3-dipolar cycloaddition reactions between N-1-propargyluracil and thymine, sodium azide and several benzyl halides. The desired heterocyclic compounds were obtained in good yields and characterized by NMR, IR, and high resolution mass spectrometry. These compounds were investigated as corrosion inhibitors for steel in 1 M HCl solution, using electrochemical impedance spectroscopy (EIS) technique. The results indicate that these heterocyclic compounds are promising acidic corrosion inhibitors for steel.

  17. Polystyrene or Magnetic Nanoparticles as Support in Enantioselective Organocatalysis? A Case Study in Friedel-Crafts Chemistry.

    Science.gov (United States)

    Ranjbar, Sara; Riente, Paola; Rodríguez-Escrich, Carles; Yadav, Jagjit; Ramineni, Kishore; Pericàs, Miquel A

    2016-04-01

    Heterogenized versions of the second-generation MacMillan imidazolidin-4-one are described for the first time. This versatile organocatalyst has been supported on 1% DVB Merrifield resin and Fe3O4 magnetic nanoparticles through a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction. The resulting catalytic materials have been successfully applied to the asymmetric Friedel-Crafts alkylation of indoles with α,β-unsaturated aldehydes. While both catalytic systems can be easily recovered and admit repeated recycling, the polystyrene-based catalyst shows higher stability and provides better stereoselectivities. PMID:27010999

  18. Novel peptide-based protease inhibitors

    DEFF Research Database (Denmark)

    Roodbeen, Renée

    This thesis describes the design and synthesis of peptide-based serine protease inhibitors. The targeted protease, urokinase-type plasminogen activator (uPA) activates plasminogen, which plays a major role in cancer metastasis. The peptide upain-2 (S 1 ,S 12-cyclo-AcCSWRGLENHAAC-NH2) is a highly...... increased. Finally, the effect of multivalent display of upain-2 was investigated. Several dimers of upain-2 were made and the attachment of upain-2 via the Copper-catalyzed Azide-Alkyne Cycloaddition (CuAAC) onto an alkyne functionalized carbohydrate scaffold was investigated. Besides the synthesis...

  19. Synthesis of disk-rod-disk liquid crystal trimers by using click chemistry

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A series of disk-rod-disk liquid crystal trimers were synthesized.CuI-NEt3 catalyzed alkyne azide cycloaddition in toluene at room temperature connected two triphenylene discogens to a biphenyl rod-shaped mesogen.The trimers were characterized by using 1H NMR,IR,and high resolution mass spectrometry.The mesomorphic properties were investigated using polarized optical microscopy(POM) ,differential scanning calorimetry(DSC) ,and wide-angle X-ray diffraction.The results showed that the trimers exhibited rectangular columnar mesophase(Colr) .The length of the flexible spacer connecting the three segments has prominent influence on the phase transition temperatures of the trimers.

  20. Monitoring Wnt Protein Acylation Using an In Vitro Cyclo-Addition Reaction

    Science.gov (United States)

    Tuladhar, Rubina; Yarravarapu, Nageswari; Lum, Lawrence

    2016-01-01

    We describe here a technique for visualizing the lipidation status of Wnt proteins using azide-alkyne cycloaddition chemistry (click chemistry) and SDS-PAGE. This protocol incorporates in vivo labeling of a Wnt-IgG Fc fusion protein using an alkynylated palmitate probe but departs from a traditional approach by incorporating a secondary cycloaddition reaction performed on single-step purified Wnt protein immobilized on protein A resin. This approach mitigates experimental noise by decreasing the contribution of labeling from other palmitoylated proteins and by providing a robust method for normalizing labeling efficiency based on protein abundance. PMID:27590147

  1. Azidopropylvinylsulfonamide as a New Bifunctional Click Reagent for Bioorthogonal Conjugations: Application for DNA-Protein Cross-Linking.

    Science.gov (United States)

    Dadová, Jitka; Vrábel, Milan; Adámik, Matej; Brázdová, Marie; Pohl, Radek; Fojta, Miroslav; Hocek, Michal

    2015-11-01

    N-(3-Azidopropyl)vinylsulfonamide was developed as a new bifunctional bioconjugation reagent suitable for the cross-linking of biomolecules through copper(I)-catalyzed azide-alkyne cycloaddition and thiol Michael addition reactions under biorthogonal conditions. The reagent is easily clicked to an acetylene-containing DNA or protein and then reacts with cysteine-containing peptides or proteins to form covalent cross-links. Several examples of bioconjugations of ethynyl- or octadiynyl-modified DNA with peptides, p53 protein, or alkyne-modified human carbonic anhydrase with peptides are given.

  2. Synthèse et étude d'un complexe de cuivre(II) tensioactif, fluorophile et photoréductible : application à la chimie click en millieux biphasiques perfluorocarbure-eau et hydrocarbure-eau

    OpenAIRE

    Jochyms, Quentin

    2015-01-01

    The aim of this thesis was to develop a new metallosurfactant for the catalysis between an alkyne and an azide. The goal of such a system was to keep separated the reactants and the catalyst in two different phases to facilitate the purification of the reaction mixture. The first step was to synthetized the complex [Cu(TF6)(3-benzoylbenzoate)2]. Then it was shown that this complex, insoluble in water and DIPE-water. This complex is also photoreductible to form a copper(I) complex. Finally, it...

  3. DNA Three Way Junction Core Decorated with Amino Acids-Like Residues-Synthesis and Characterization

    Directory of Open Access Journals (Sweden)

    Claudia Addamiano

    2016-08-01

    Full Text Available Construction and physico-chemical behavior of DNA three way junction (3WJ functionalized by protein-like residues (imidazole, alcohol and carboxylic acid at unpaired positions at the core is described. One 5′-C(S-propargyl-thymidine nucleotide was specifically incorporated on each strand to react through a post synthetic CuACC reaction with either protected imidazolyl-, hydroxyl- or carboxyl-azide. Structural impacts of 5′-C(S-functionalization were investigated to evaluate how 3WJ flexibility/stability is affected.

  4. Biochemical requirements for singlet oxygen production by purified human myeloperoxidase.

    OpenAIRE

    Kanofsky, J R; Wright, J; Miles-Richardson, G E; Tauber, A I

    1984-01-01

    The myeloperoxidase (MPO)-hydrogen peroxide (H2O2)-halide systems were found to produce chemiluminescence at 1,268 nm, a characteristic emission band for singlet oxygen (1O2). The emission was enhanced by a factor of 29 +/- 5 in deuterium oxide and was inhibited by the 1O2 quenchers, histidine and azide ion. Inactivation of MPO with heat or with cyanide ion prevented light production. The combined weight of all data strongly supported the production of 1O2 by these enzyme systems. The amount ...

  5. Synthesis of Conformationally Locked Versions of Puromycin Analogues

    Science.gov (United States)

    Saneyoshi, Hisao; Michel, Benoît Y.; Choi, Yongseok; Strazewski, Peter; Marquez, Victor E.

    2009-01-01

    Conformationally locked North and South versions of puromycin analogues built on a bicyclo[3.1.0]hexane pseudosugar template were synthesized. The final assembly of the products was accomplished by the Staudinger-Vilarrasa coupling of the corresponding North (2 and 3) and South (6 and 7) 3′-azidopurine carbanucleosides with the Fmoc-protected 1-hydroxybenzotriazole ester of 4-methoxy-L-tyrosine. North azides 2 and 3 were reported earlier. The 3′-azido intermediates 6 and 7 that are necessary for the synthesis of the South puromycin analogues are described herein for the first time. PMID:18991379

  6. Synthesis of Donor-Acceptor Conjugated Polymers by "CLICK" Polymerization for OPV applications

    DEFF Research Database (Denmark)

    Brandt, Rasmus Guldbæk; Yu, Donghong

    The intent of this study was to utilize the Copper(I)-catalyzed Azide Alkyne Cycloaddition (CuAAC) as a polymerization technique (“Click” Polymerization) for synthesizing novel π-conjugated low band gap polymers for organic photovoltaic applications (OPV). The chosen approach was to synthesize...... an alternating electron donating (donor, D) and electron withdrawing (acceptor, A) co-polymer. The chosen monomers were well known units, and the novelty lies in using the monomer units with the click methodology. An insoluble alternating copolymer consisting of 2,7-diazido-9,9-dioctyl-9Hflourene and 1...

  7. Synthesis and Fluorescence Spectra of Triazolylcoumarin Fluorescent Dyes

    Institute of Scientific and Technical Information of China (English)

    PENG Xian-fu; LI Hong-qi

    2009-01-01

    Much attention is devoted to fluorescent dyes especially those with potential in versatile applications. Reactions under "click" conditions between nonfluorescent 3 - azidocoumarins and terminal alkynes produced 3 -(1, 2, 3- triazol- 1 - yl)cournarins, a novel type of fluorescent dyes with intense fluorescence. The structures of the new coumarins were characterized by 1H NMR, MS, and IR spectra. Fluorescence spectra measurement demonstrated excellent fluorescence performance of the triazolylcoumarins and this click reaction is a promising candidate for bioconjugation and bioimaging applications since both azide and alkynes are quite inert to biological systems.

  8. Benzimidazole-1,2,3-triazole Hybrid Molecules: Synthesis and Evaluation for Antibacterial/Antifungal Activity

    OpenAIRE

    Ouahrouch, Abdelaaziz; Ighachane, Hana; Taourirte, Moha; Joachim W. Engels; Sedra, My Hassan; Lazrek, Hassan B.

    2014-01-01

    A novel series of hybrid molecules 4a–i and 5a–i were prepared by condensation of 4-(trimethylsilylethynyl)benzaldehyde 1 with substituted o-phenylenediamines. These in turn were reacted with 2-(azidomethoxy)ethyl acetate in a Cu alkyne–azide cycloaddition (CuAAC) to generate the 1,2,3-triazole pharmacophore under microwave assistance. The newly synthesized compounds were examined for their in vitro antimicrobial activities against Gram-positive and Gram-negative bacteria and the phytopathoge...

  9. Temperature dependence of turnover in a Sc(OTf)3-catalyzed intramolecular Schmidt reaction

    Science.gov (United States)

    Fehl, Charlie; Hirt, Erin E.; Li, Sze-Wan; Aubé, Jeffrey

    2015-01-01

    The intramolecular Schmidt reaction of ketones and tethered azides is an efficient method for the generation of amides and lactams. This reaction is catalyzed by Lewis acids, which tightly bind the strongly basic amide product and result in product inhibition. We report herein conditions to achieve a catalytic Schmidt reaction using substoichiometric amounts of the heat-stable Lewis acid Sc(OTf)3. This species was shown to effectively release products of the Schmidt reaction in a temperature-dependent fashion. Thus, heat was able to promote catalyst turnover. A brief substrate scope was conducted using these conditions. PMID:26085693

  10. Synthesis, structure and in vitro cytostatic activity of ferrocene-Cinchona hybrids.

    Science.gov (United States)

    Kocsis, László; Szabó, Ildikó; Bősze, Szilvia; Jernei, Tamás; Hudecz, Ferenc; Csámpai, Antal

    2016-02-01

    Exploring copper(I)- and ruthenium(II)-catalyzed azide-alkyne cycloadditions and a Sonogashira protocol, novel cytostatic ferrocene-cinchona hybrids were synthetized displaying significant in vitro activity on HepG-2 and HT-29 cells. Preliminary SAR studies disclosed that compounds incorporating linkers with 1,2,3-triazole and chalchone residues can be considered as promising lead structures. According to the best of our knowledge this is the first letter on the incorporation of ferrocene nucleus in the reputed cinchona family via triazole and chalcone linkers with established pharmaceutical profile. PMID:26739780

  11. A new efficient route for the synthesis of 4,4′,6,6′-tetra(azido) azo- 1,3,5-triazine

    Institute of Scientific and Technical Information of China (English)

    Xiao Tong Li; Sheng Hua Li; Si Ping Pang; Yong Zhong Yu; Yun Jun Luo

    2007-01-01

    A new method for the synthesis of 4,4′,6,6′-tetra(azido)azo- 1,3,5-triazine (TAAT) is described. The key intermediate 4,4′,6,6′-tetra(azido)hydrazo-1,3,5-triazine (THAT) was synthesized by nucleophilic substitution in the case of sodium azide as nucleophile.N-Bromosuccinide (NBS) was used as oxidant to oxidize THAT by a tractable operation under mild reaction condition. The target compound TAAT was obtained with a facile process and high overall yield of 81%. The structures of TAAT and its intermediates were identified by spectroscopic methods.

  12. -Phenoxo--pseudohalide and -pseudohalide dinuclear, tetranuclear and one-dimensional complexes: magneto-structural correlation and interesting type of solid state isomerism

    Indian Academy of Sciences (India)

    Sujit Sasmal; Sasankasekhar Mohanta

    2012-11-01

    Five Schiff base ligands have been utilized to explore metallo-pseudohalide (azide or cyanate) systems. These ligands are the 1:1 condensation products of 3-methoxysalicylaldehyde with ethanolamine (H2L1)/1-(2-aminoethyl)-piperidine (HL2)/ 4-(2-aminoethyl)-morpholine (HL3) or salicylaldehyde with 1-(2-aminoethyl)-piperidine (HL4)/4-(2-aminoethyl)-morpholine (HL5). The derived complexes are as follows: Four heterobridged -phenoxo-1,1-azide/cyanate dinickel(II) compounds of composition [Ni$^{\\text{II}}_{2}$ (HL1)3(1,1-N3)]$\\cdot$3H2O (1), [Ni$^{\\text{II}}_{2}$ (L2)2(1,1-N3)(N3)(H2O)]·CH3CH2OH (2), [Ni$^{\\text{II}}_{2}$ (L3)2-(1,1-N3)(CH3CN)(H2O)](ClO4)·H2O·CH3CN (3) and [Ni$^{\\text{II}}_{2}$ (HL1)3(1,1-NCO)]·2H2O (4); Two 1,3-azide bridged tetranickel(II) compounds [{NiII(L4)(1,3-N3)(H2O)}4] (5) and [{NiII(L5)(1,3-N3)(H2O)}4] (6); Two 1,3-azide/cyanate one-dimensional compounds [CuIIL5(1,3-NCO)]·2H2O (7) and [CuIIL5(1,3-N3)]·2H2O (8). Except compound 5 which shows overall antiferromagnetic coupling, other compounds exhibit overall ferromagnetic interaction. Syntheses, crystal structures, magnetic properties, density functional theoretical (DFT) calculations and experimental/theoretical magneto-structural correlations have been carried out which have revealed some interesting observations on composition/topology, magneto-structural correlations and solid state isomerism. The results have been already published. The present report deals with a review of the salient and interesting features of these works.

  13. Plasma membrane electron transport in frog blood vessels

    Indian Academy of Sciences (India)

    Rashmi P Rao; K Nalini; J Prakasa Rao

    2009-12-01

    In an attempt to see if frog blood vessels possess a plasma membrane electron transport system, the postcaval vein and aorta isolated from Rana tigrina were tested for their ability to reduce ferricyanide, methylene blue, and 2,6-dichloroindophenol. While the dyes remained unchanged, ferricyanide was reduced to ferrocyanide. This reduction was resistant to inhibition by cyanide and azide. Heptane extraction or formalin fixation of the tissues markedly reduced the capability to reduce ferricyanide. Denuded aortas retained only 30% of the activity of intact tissue. Our results indicate that the amphibian postcaval vein and aorta exhibit plasma membrane electron transport

  14. Synthesis of new 1,2,3-triazol-carbohydrates

    Directory of Open Access Journals (Sweden)

    Bruna M. Guimarães

    2012-06-01

    Full Text Available The reaction of a mixture of 1-azide-glycopyranoside (1 and appropriate alkynes (2a-e, in the presence of CuI/Et3N as catalyst system, and acetonitrile as solvent, provided the glycoside triazoles (3a-e in moderate-to-excellent yields (60-93%. We observed that the reactivity of the alcohols decreased due to steric hindrance (prim>sec>terc. Furthermore, the use of ultrasound irradiation was favorable to furnish the desired products with excellent yields and a shorter reaction time, except for the compound (3e.      

  15. Ultrasound-Assisted Synthesis of 1-N-glycosyl-1H-1,2,3-Triazole Derivatives and their Anti-inflammatory Activity

    Directory of Open Access Journals (Sweden)

    Gilson Bezerra Silva

    2012-06-01

    Full Text Available We have been synthesized various glycosyl triazoles from the reaction between glycosyl azide (1 and terminal alkynes (2a-g. The glycopiranosyl 1,2,3-triazoles (3-9 have been obtained in moderate-to-excellent yields (63-99% through the copper (I-catalyst 1,3-dipolar cycloaddition reaction at room temperature using ultrasound irradiation. In addition, preliminary anti-inflammatory tests have been performed in the compounds conjugates with benzoheterocycles (3-7 moieties that shown moderate activity

  16. Anion directed cation templated synthesis of three ternary copper(II) complexes with a monocondensed N2O donor Schiff base and different pseudohalides

    OpenAIRE

    Bhowmik, Prasanta; Bhattacharyya, Anik; Harms, Klaus; Sproules, Stephen; Chattopadhyay, Shouvik

    2015-01-01

    Three copper(II) complexes, [Cu2(L)2(μ1,1-N3)2] (1), [Cu2(L)2(μ1,1-NCO)2] (2) and [Cu(L)(μ1,5-dca)]n (3), where HL is a tridentate mono-condensed Schiff base, 1-(2-aminoethyliminomethyl)naphthalen-2-ol, and dca is dicyanamide, have been prepared and characterized by elemental analysis, IR, UV–Vis and fluorescence spectroscopy and single crystal X-ray diffraction studies. The Schiff base ligand was prepared by a counter anion mediated copper(II) templated synthesis. The azide ligand in complex...

  17. Degradable polymeric nanoparticles by aggregation of thermoresponsive polymers and ``click'' chemistry

    Science.gov (United States)

    Dworak, Andrzej; Lipowska, Daria; Szweda, Dawid; Suwinski, Jerzy; Trzebicka, Barbara; Szweda, Roza

    2015-10-01

    This study describes a novel approach to the preparation of crosslinked polymeric nanoparticles of controlled sizes that can be degraded under basic conditions. For this purpose thermoresponsive copolymers containing azide and alkyne functions were obtained by ATRP of di(ethylene glycol) monomethyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) followed by post polymerization modification. The amino groups of A were reacted with propargyl chloroformate or 2-azido-1,3-dimethylimidazolinium hexafluorophosphate, which led to two types of copolymers. Increasing the temperature of aqueous solutions of the mixed copolymers caused their aggregation into spherical nanoparticles composed of both types of chains. Their dimensions could be controlled by changing the concentration and heating rate of the solutions. Covalent stabilization of aggregated chains was performed by a ``click'' reaction between the azide and alkyne groups. Due to the presence of a carbamate bond the nanoparticles undergo pH dependent degradation under mild basic conditions. The proposed procedure opens a route to new carriers for the controlled release of active species.This study describes a novel approach to the preparation of crosslinked polymeric nanoparticles of controlled sizes that can be degraded under basic conditions. For this purpose thermoresponsive copolymers containing azide and alkyne functions were obtained by ATRP of di(ethylene glycol) monomethyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) followed by post polymerization modification. The amino groups of A were reacted with propargyl chloroformate or 2-azido-1,3-dimethylimidazolinium hexafluorophosphate, which led to two types of copolymers. Increasing the temperature of aqueous solutions of the mixed copolymers caused their aggregation into spherical nanoparticles composed of both types of chains. Their dimensions could be controlled by changing the concentration and heating rate of the solutions. Covalent

  18. 5-Azido-4-dimethylamino-1-methyl-1,2,4-triazolium Hexafluoridophosphate and Derivatives

    Directory of Open Access Journals (Sweden)

    Gerhard Laus

    2016-02-01

    Full Text Available 5-Azido-4-(dimethylamino-1-methyl-1,2,4-triazolium hexafluoridophosphate was synthesized from the corresponding 5-bromo compound with NaN3. Reaction with bicyclo[2.2.1]hept-2-ene yielded a tricyclic aziridine, addition of an N-heterocyclic carbene resulted in a triazatrimethine cyanine, and reduction with triphenylphosphane gave the 5-amino derivative. The crystal structures of three nitrogen-rich salts were determined. Thermoanalysis of the cationic azide and triazene showed exothermal decomposition. The triazene exhibited negative solvatochromism in polar solvents involving the dipolarity π* and hydrogen-bond donor acidity α of the solvent.

  19. Diazidobis[4,4,5,5-tetramethyl-2-(1,3-thiazol-2-yl-2-imidazoline-1-oxyl-3-oxide-κ2O,N]manganese(II

    Directory of Open Access Journals (Sweden)

    Kai Jiang

    2009-02-01

    Full Text Available In the crystal structure of the title compound, [Mn(N32(C10H14N3O2S2], the Mn(II atom exhibits a roughly octahedral coordination geometry. The Mn(II atom lies on an inversion centre, thus the asymmetric unit comprises one half-molecule. The metal center is six-coordinated by two azide anions and by two chelating 4,4,5,5-tetramethyl-2-(1,3-thiazol-2-yl-2-imidazoline-1-oxyl-3-oxide nitronyl nitroxide radical ligands, leading to two six-membered chelate rings.

  20. Bio-Conjugates for Nanoscale Applications

    DEFF Research Database (Denmark)

    Villadsen, Klaus

    Bio-conjugates for Nanoscale Applications is the title of this thesis, which covers three different projects in chemical bio-conjugation research, namely synthesis and applications of: Lipidated fluorescent peptides, carbohydrate oxime-azide linkers and N-aryl O-R2 oxyamine derivatives. Lipidated...... fluorescent peptides were designed and synthesized as part of two collaboration projects utilizing peptide conjugates in nanoscale applications to increase understanding of the role peptides and proteins plays in biological systems. Ras proteins are membrane bound molecular switches involved in many signaling...

  1. Synthesis and In Vitro Antiproliferative Activity of Novel Androst-5-ene Triazolyl and Tetrazolyl Derivatives

    Directory of Open Access Journals (Sweden)

    János Wölfling

    2011-06-01

    Full Text Available A straightforward and reliable method for the regioselective synthesis of steroidal 1,4-disubstituted triazoles and 1,5-disubstituted tetrazoles via copper(I-catalyzed cycloadditions is reported. Heterocycle moieties were efficiently introduced onto the starting azide compound 3β-acetoxy-16β-azidomethylandrost-5-en-17β-ol through use of the “click” chemistry approach. The antiproliferative activities of the newly-synthesized triazoles were determined in vitro on three human gynecological cell lines (HeLa, MCF7 and A2780 using the microculture tetrazolium assay.

  2. Synthesis and in vitro antiproliferative activity of novel androst-5-ene triazolyl and tetrazolyl derivatives.

    Science.gov (United States)

    Kádár, Zalán; Kovács, Dóra; Frank, Éva; Schneider, Gyula; Huber, Judit; Zupkó, István; Bartók, Tibor; Wölfling, János

    2011-01-01

    A straightforward and reliable method for the regioselective synthesis of steroidal 1,4-disubstituted triazoles and 1,5-disubstituted tetrazoles via copper(I)-catalyzed cycloadditions is reported. Heterocycle moieties were efficiently introduced onto the starting azide compound 3β-acetoxy-16β-azidomethylandrost-5-en-17β-ol through use of the "click" chemistry approach. The antiproliferative activities of the newly-synthesized triazoles were determined in vitro on three human gynecological cell lines (HeLa, MCF7 and A2780) using the microculture tetrazolium assay. PMID:21659965

  3. Synthesis of 18F-Arenes from Spirocyclic Iodonium(III) Ylides via Continuous-Flow Microfluidics

    Science.gov (United States)

    Calderwood, Samuel; Collier, Thomas Lee; Gouverneur, Véronique; Liang, Steven H.; Vasdev, Neil

    2016-01-01

    Spirocyclic hypervalent iodine(III) ylides have proven to be synthetically versatile precursors for efficient radiolabelling of a diverse range of non-activated (hetero)arenes, highly functionalised small molecules, building blocks and radiopharmaceuticals from [18F]fluoride ion. Herein, we report the implementation of these reactions onto a continuous-flow microfluidic platform, thereby offering an alterative and automated synthetic procedure of a radiopharmaceutical, 3-[18F]fluoro-5-[(pyridin-3-yl)ethynyl]benzonitrile ([18F]FPEB) and a routinely used building block for click-radiochemistry, 4-[18F]fluorobenzyl azide. This new protocol was applied to the synthesis of [18F]FPEB (radiochemical conversion (RCC) = 68 ± 5%) and 4-[18F]fluorobenzyl azide (RCC=68 ± 5%; isolated radiochemical yield = 24±0%). We anticipate that the high throughput microfluidic platform will accelerate the discovery and applications of 18F-labelled building blocks and labelled compounds prepared by iodonium ylide precursors as well as the production of radiotracers for preclinical imaging studies.

  4. Reversible dissociation of active octamer of cyanase to inactive dimer promoted by alteration of the sulfhydryl group.

    Science.gov (United States)

    Anderson, P M; Johnson, W V; Korte, J J; Xiong, X F; Sung, Y C; Fuchs, J A

    1988-04-25

    Cyanase is an inducible enzyme in Escherichia coli that catalyzes the reaction of cyanate with bicarbonate resulting in the decomposition of cyanate to ammonia and bicarbonate. In this study, the role of the single sulfhydryl group in each of the eight identical subunits of cyanase was investigated. Tetranitromethane, methyl methanethiosulfonate, N-ethylmaleimide, and Hg2+ all reacted with the sulfhydryl group to give derivatives which had reduced activities and which dissociated reversibly to inactive dimer. Association of inactive dimer to active octamer was facilitated by the presence of azide (cyanate analog) and bicarbonate, increased temperature and enzyme concentration, and presence of phosphate. Nitration of tyrosine residues by tetranitromethane occurred only in the absence of azide and bicarbonate, suggesting that at least some of the tyrosine residues become exposed when octamer dissociates to dimer. Site-directed mutagenesis was used to prepare a mutant enzyme in which serine was substituted for cysteine. The mutant enzyme was catalytically active and had properties very similar to native enzyme, except that it was less stable to treatment with urea and to high temperatures. These results establish that in native cyanase the sulfhydryl group per se is not required for catalytic activity, but it may play a role in stabilizing octameric structure, and that octameric structure is required for catalytic activity.

  5. Archaeosomes varying in lipid composition differ in receptor-mediated endocytosis and differentially adjuvant immune responses to entrapped antigen

    Directory of Open Access Journals (Sweden)

    G. Dennis Sprott

    2003-01-01

    Full Text Available Archaeosomes prepared from total polar lipids extracted from six archaeal species with divergent lipid compositions had the capacity to deliver antigen for presentation via both MHC class I and class II pathways. Lipid extracts from Halobacterium halobium and from Halococcus morrhuae strains 14039 and 16008 contained archaetidylglycerol methylphosphate and sulfated glycolipids rich in mannose residues, and lacked archaetidylserine, whereas the opposite was found in Methanobrevibacter smithii, Methanosarcina mazei and Methanococcus jannaschii. Annexin V labeling revealed a surface orientation of phosphoserine head groups in M. smithii, M. mazei and M. jannaschii archaeosomes. Uptake of rhodamine-labeled M. smithii or M. jannaschii archaeosomes by murine peritoneal macrophages was inhibited by unlabeled liposomes containing phosphatidylserine, by the sulfhydryl inhibitor N-ethylmaleimide, and by ATP depletion using azide plus fluoride, but not by H. halobium archaeosomes. In contrast, N-ethylmaleimide failed to inhibit uptake of the four other rhodamine-labeled archaeosome types, and azide plus fluoride did not inhibit uptake of H. halobium or H. morrhuae archaeosomes. These results suggest endocytosis of archaeosomes rich in surface-exposed phosphoserine head groups via a phosphatidylserine receptor, and energy-independent surface adsorption of certain other archaeosome composition classes. Lipid composition affected not only the endocytic mechanism, but also served to differentially modulate the activation of dendritic cells. The induction of IL-12 secretion from dendritic cells exposed to H. morrhuae 14039 archaeosomes was striking compared with cells exposed to archaeosomes from 16008. Thus, archaeosome types uniquely modulate antigen delivery and dendritic cell activation.

  6. New surface-modified zinc oxide nanoparticles with aminotriethylene oxide chains linked by 1,2,3-triazole ring: Preparation, and visible light-emitting and noncytotoxic properties

    Science.gov (United States)

    Sato, Moriyuki; Shimatani, Kanako; Iwasaki, Yuko; Morito, Shigekazu; Tanaka, Hidekazu; Fujita, Yasuhisa; Nakamura, Morihiko

    2011-11-01

    Novel surface-modified, visible light-emitting and noncytotoxic ZnO nanoparticles (NPs) (ZPAZ) having aminotriethylene oxide chains linked by 1,4- and/or 1,5-disubstituted 1,2,3-triazole rings were prepared from ZnO NPs (ZPA) with ethynyl groups on the surfaces and an azide derivative of triethylene oxide chain linking terminal amino group (ATA) via 1,3-dipolar azide/alkyne click reaction by heating without Cu(I) catalyst. FTIR spectroscopy, elemental analysis, XRD analysis and TEM observation suggested that the resulting ZPA and ZPAZ NPs have the particle sizes below 10 nm in diameters, triethylene oxide chains linking the terminal amino groups and wurtzite crystal structure. UV-vis absorption spectrum of the ZPAZ NPs in methanol showed maximum absorption band at 346.5 nm, supporting the TEM observation. PL spectra depicted that the ZPA and ZPAZ NPs display broad light green and lightly greenish yellow visible light emitting bands in methanol. Zeta potentials measured in distilled water suggested that the ZPAZ NPs have a low tendency to aggregate and possess better stability than the ZPA NPs. Cytotoxicity assay revealed that the ZPAZ NPs, having water-dispersion properties, are noncytotoxic at low concentrations and almost all RAW264.7 cells are alive after 24 h of treatment.

  7. Elastin-like recombinamer catalyst-free click gels: characterization of poroelastic and intrinsic viscoelastic properties.

    Science.gov (United States)

    González de Torre, Israel; Santos, Mercedes; Quintanilla, Luis; Testera, Ana; Alonso, Matilde; Rodríguez Cabello, José Carlos

    2014-06-01

    Elastin-like recombinamer catalyst-free click gels (ELR-CFCGs) have been prepared and characterized by modifying both a structural ELR (VKVx24) and a biofunctionalized ELR-bearing RGD cell-adhesion sequence (HRGD6) to bear the reactive groups needed to form hydrogels via a click reaction. Prior to formation of the ELR-CFCGs, azide-bearing and cyclooctyne-modified ELRs were also synthesized. Subsequent covalent crosslinking was based on the reaction between these azide and cyclooctyne groups, which takes place under physiological conditions and without the need for a catalyst. The correlation among SEM micrographs, porosity, swelling ratio, and rheological measurements have been carried out. The storage and loss moduli at 1Hz are in the range 1-10kPa and 100-1000Pa, respectively. The linear dependence of |G∗| on f(½) and the peak value of tan δ were considered to be consistent with a poroelastic mechanism dominating the frequency range 0.3-70Hz. The discrete relaxation spectrum was obtained from stress relaxation measurements (t>5s). The good fit of the relaxation modulus to decrease exponential functions suggests that an intrinsic viscoelastic mechanism dominates the transients. Several recombinamer concentrations and temperatures were tested to obtain gels with fully tuneable properties that could find applications in the biomedical field. PMID:24530853

  8. Photocleavable junctions in complex polymer architectures and photoetchable thermoplastics

    Science.gov (United States)

    Sterner, Elizabeth Surles

    Polymer materials have become important tools in nanomanufacturing due to their facile processing and ready attainment of the necessary feature sizes. The development of cleavable junctions has led to advances in the production of polymer nanotemplates. Photocleavage strategies have come to the forefront of the field because photons, as a cleavage stimulus, do not have the mass-transport limitations of chemical methods, and provide for targeted two- and three-dimensional feature control. This dissertation presents a method for producing photocleavable materials by one-pot copper-catalyzed azide-alkyne "click" chemistry (CuAAC), activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) and activated ester substitution methods that have each block labeled with a fluorescent dye, enabling exploration of the polymer physics of these systems by correlation fluorescence spectroscopy. It also introduces a novel photocleavable linker, the o-nitrobenzyl-1,2,3-triazole, its behavior on photocleavage, and a facile method for the production of the o-nitrobenzyl azides necessary for their synthesis. The synthesis and properties of a bulk photodegradable polytriazole are reported, as are proof of concept experiments demonstrating its potential as a directly photoetchable material. Lastly, this dissertation contains a perspective on possible avenues of new research on the topics presented.

  9. Highly Conductive Aromatic Functionalized Multi-Walled Carbon Nanotube for Inkjet Printable High Performance Supercapacitor Electrodes.

    Directory of Open Access Journals (Sweden)

    Sanjeev K Ujjain

    Full Text Available We report the functionalization of multiwalled carbon nanotubes (MWCNT via the 1,3-dipolar [3+2] cycloaddition of aromatic azides, which resulted in a detangled CNT as shown by transmission electron microscopy (TEM. Carboxylic moieties (-COOH on aromatic azide result in highly stable aqueous dispersion (max. conc. ~ 10 mg/mL H2O, making the suitable for inkjet printing. Printed patterns on polyethylene terephthalate (PET flexible substrate exhibit low sheet resistivity ~65 Ω. cm, which is attributed to enhanced conductivity. Fabricated Supercapacitors (SC assembled using these printed substrates exhibit good electrochemical performance in organic as well as aqueous electrolytes. High energy and power density (57.8 Wh/kg and 0.85 kW/kg in 1M H2SO4 aqueous electrolyte demonstrate the excellent performance of the proposed supercapacitor. Capacitive retention varies from ~85-94% with columbic efficiency ~95% after 1000 charge/discharge cycles in different electrolytes, demonstrating the excellent potential of the device for futuristic power applications.

  10. Multifunctional and High Affinity Polymer Ligand that Provides Bio-Orthogonal Coating of Quantum Dots.

    Science.gov (United States)

    Wang, Wentao; Kapur, Anshika; Ji, Xin; Zeng, Birong; Mishra, Dinesh; Mattoussi, Hedi

    2016-09-21

    We detail the design of hydrophilic metal-coordinating ligands and their use for the effective coating of luminescent quantum dots (QDs). The ligand design exploits the specific, reagent-free nucleophilic addition reaction of amine-modified molecules toward maleic anhydride to introduce several lipoic acid metal anchors, hydrophilic zwitterion moieties, and specific reactive groups along a poly(isobutylene-alt-maleic anhydride) (PIMA) chain. Tunable reactive groups tested in this study include azide, biotin, carboxyl, and amine. Cap exchange with these multilipoic acid ligands via a photochemical ligation strategy yields homogeneous QD dispersions that are colloidally stable over several biologically relevant conditions and for extended periods of time. The zwitterionic coating yields compact nanoparticle size and imparts nonsticky surface properties onto the QDs, preventing protein absorption. The introduction of a controllable number of reactive groups allows conjugation of the QDs to biomolecules via bio-orthogonal coupling chemistries including (1) attachment of the neurotransmitter dopamine to QDs via amine-isothiocyanate reaction to produce a platform capable of probing interactions with cysteine in proteins, based on charge transfer interactions; (2) self-assembly of biotinylated QDs with streptavidin-dye; and (3) ligation of azide-functionalized QDs to cyclooctyne-modified transferrin via copper-free click chemistry, used for intracellular delivery. This ligand design strategy can be used to prepare an array of metal-coordinating ligands adapted for coating other inorganic nanoparticles, including magnetic and plasmonic nanomaterials. PMID:27482756

  11. Characterization of nucleoside triphosphate diphosphohydrolase activity in Trichomonas gallinae and the influence of penicillin and streptomycin in extracellular nucleotide hydrolysis.

    Science.gov (United States)

    Borges, Fernanda Pires; de Brum Vieira, Patrícia; Wiltuschnig, Renata C M; Tasca, Tiana; De Carli, Geraldo Attilio; Bonan, Carla Denise

    2008-06-01

    Here we described an nucleoside triphosphate diphosphohydrolase (NTPDase) activity in living trophozoites of Trichomonas gallinae. The enzyme hydrolyzes a variety of purine and pyrimidine nucleoside di- and triphosphates in an optimum pH range of 6.0-8.0. This enzyme activity was activated by high concentrations of divalent cations, such as calcium and magnesium. Contaminant activities were ruled out because the enzyme was not inhibited by classical inhibitors of ATPases (ouabain, 5.0 mM sodium azide, oligomycin) and alkaline phosphatases (levamisole). A significant inhibition of ATP hydrolysis (38%) was observed in the presence of 20 mM sodium azide. Sodium orthovanadate inhibited ATP and ADP hydrolysis (24% and 78%), respectively. The apparent K(M) (Michaelis constant) values were 667.62+/-13 microM for ATP and 125+/-5.3 microM for ADP. V(max) (maximum velocity) values were 0.44+/-0.007 nmol Pi min(-1) per 10(6) trichomonads and 0.91+/-0.12 nmol Pi min(-1) per 10(6) trichomonads for ATP and ADP, respectively. Moreover, we showed a marked decrease in ATP, ADP and AMP hydrolysis when the parasites were grown in the presence of penicillin and streptomycin. The existence of an NTPDase activity in T. gallinae may be involved in pathogenicity, protecting the parasite from the cytolytic effects of the extracellular nucleotides. PMID:18422631

  12. Synthesis of hexagonal Ni{sub 3}N using high pressures and temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Guillaume, C [University of Edinburgh, School of Engineering and Electronics and Centre for Materials Science, Kings Buildings, Mayfield Road, EH9 3JL (United Kingdom); Morniroli, J P [Laboratoire de Metallurgie Physique et Genie des Materiaux, UMR CNRS 8517, Universite des Sciences et Technologies de Lille et Ecole Nationale Superieure de Chimie de Lille, Cite Scientifique, 59655 Villeneuve d' Ascq Cedex (France); Frost, D J [Bayerisches Geoinstitut, Universitat Bayreuth, D-95440, Bayreuth (Germany); Serghiou, G [University of Edinburgh, School of Engineering and Electronics and Centre for Materials Science, Kings Buildings, Mayfield Road, EH9 3JL (United Kingdom)

    2006-09-20

    The only known bulk ambient pressure nickel nitride phase is hexagonal Ni{sub 3}N (space group P6{sub 3}22). Multianvil synthesis experiments at 20 GPa and 2000 K using nickel (Ni) and sodium azide (NaN{sub 3}) starting materials, and ex situ analysis using transmission electron microscopy and scanning electron microscopy measurements show that this phase can be recovered at ambient pressure (space group P6{sub 3}22, a = 4.62 A, c = 4.30 A, Z = 2). Formation of this phase is correlated with the repulsive interactions between closely spaced nitrogen ions and with the extent of thermal stability of nickel nitride at ambient and at high densities. These two factors are also important in relating the high temperature and pressure behaviour of nickel nitride to those of several other interstitial nitrides recovered from similar pressures after heating. Further, we report formation of a sodium rhenium nitride phase by reaction of the azide with the rhenium capsule in which the reactants were contained.

  13. Structural, vibrational and bonding properties of hydro-nitrogen solids under high pressure: An ab-initio study

    Indian Academy of Sciences (India)

    G VAITHEESWARAN; N YEDUKONDALU; B MOSES ABRAHAM

    2016-10-01

    Hydro-nitrogen solids are potential high energy density materials (HEDMs) due to high mass ratio of nitrogen which find wide range of applications as propellants and explosives. In the present work, we report the structural and vibrational properties of Tetramethyl Ammonium Azide (TMAA) and HydroZonium Azide(HZA) using density functional theory calculations by treating weak intermolecular interactions. The obtained ground state parameters using vdW-TS method are in good agreement with the experimental data. The pressure dependent lattice constants, compressibility and equation of state are discussed. The obtained equilibrium bulk moduli show the soft nature of these materials. The compressibility curves reveal that these compounds are highly compressible along crystallographic a-axis.We have also calculated the zone-center phonon frequencies and made a complete analysis of vibrational spectra at ambient as well as at high pressure. Contraction and elongation of C-H and N-H (NH₃ stretching) bonds under pressure lead to blue- and red-shift of the frequencies in the mid-IR region for TMAA and HZA compounds, respectively

  14. Hairy carbon nanotube@nano-Pd heterostructures: design, characterization, and application in Suzuki C-C coupling reaction.

    Science.gov (United States)

    Mahouche Chergui, Samia; Ledebt, Alexandre; Mammeri, Fayna; Herbst, Frédéric; Carbonnier, Benjamin; Ben Romdhane, Hatem; Delamar, Michel; Chehimi, Mohamed M

    2010-10-19

    Poly(glycidyl methacrylate), PGMA, was prepared via ATRP in bulk solution, and its epoxy groups were further acid-hydrolyzed in order to obtain a polymer with glycerol moieties (noted POH). The POH chain end C-Br bonds were subjected to a nucleophilic attack by NaN(3), resulting in azide-terminated POH (POH-N(3)). The CNTs were modified by in-situ-generated alkynylated diazonium cations from the para-alkynylated aniline of the formulas H(2)N-C(6)H(4)-C≡C-H, yielding CNT-C(6)H(4)-C≡C-H nanotubes. The azide-functionalized polymer POH-N(3) was clicked to the alkynyl-modified CNTs giving CNT@POH hybrids, which were further subjected to an oxidation resulting in carboxylated polymer-modified CNTs (noted CNT@PCOOH). The as-designed hairy CNTs served as efficient platforms for the in-situ synthesis and massive loading of 3 nm sized palladium nanoparticles (NPs). The CNT@PCOOH@Pd heterostructures prepared so far exhibited an efficient catalytic effect in the C-C Suzuki coupling reaction and were regenerated up to four times without any significant loss of catalytic activity.

  15. Expanding the diversity of unnatural cell surface sialic acids

    Energy Technology Data Exchange (ETDEWEB)

    Luchansky, Sarah J.; Goon, Scarlett; Bertozzi, Carolyn R.

    2003-10-30

    Novel chemical reactivity can be introduced onto cell surfaces through metabolic oligosaccharide engineering. This technique exploits the substrate promiscuity of cellular biosynthetic enzymes to deliver unnatural monosaccharides bearing bioorthogonal functional groups into cellular glycans. For example, derivatives of N-acetylmannosamine (ManNAc) are converted by the cellular biosynthetic machinery into the corresponding sialic acids and subsequently delivered to the cell surface in the form of sialoglycoconjugates. Analogs of N-acetylglucosamine (GlcNAc) and N-acetylgalactosamine (GalNAc) are also metabolized and incorporated into cell surface glycans, likely through the sialic acid and GalNAc salvage pathways, respectively. Furthermore, GlcNAc analogs can be incorporated into nucleocytoplasmic proteins in place of {beta}-O-GlcNAc residues. These pathways have been exploited to integrate unique electrophiles such as ketones and azides into the target glycoconjugate class. These functional groups can be further elaborated in a chemoselective fashion by condensation with hydrazides and by Staudinger ligation, respectively, thereby introducing detectable probes onto the cell. In conclusion, sialic acid derivatives are efficient vehicles for delivery of bulky functional groups to cell surfaces and masking of their hydroxyl groups improves their cellular uptake and utilization. Furthermore, the successful introduction of photoactivatable aryl azides into cell surface glycans opens up new avenues for studying sialic acid-binding proteins and elucidating the role of sialic acid in essential processes such as signaling and cell adhesion.

  16. Investigation of concept of efficient short wavelength laser. Final technical report, April 1, 1977-July 31, 1979

    Energy Technology Data Exchange (ETDEWEB)

    Piper, L.G.; Krech, R.H.; Pugh, E.; Taylor, R.L.

    1979-01-01

    The feasibility of producing an efficient, short wavelength, storage laser for ICF driven applications by making use of certain state-specific reactions of exoergic azide compounds has been investigated. The ultraviolet (approx. 300 nm) photolysis of gaseous ClN/sub 3/ produced prompt emission in the red, which was attributed to the efficient formation of ClN(b/sup 1/..sigma../sup +/) with subsequent ClN(X reverse arrow b) fluorescence. Based on these results, a small-scale laser demonstration experiment was constructed using short duration Xe flash lamps as the photolytic source. The results of this latter experiment were negative. The most plausible explanation was that the flash lamps provided sufficient far-uv radiation to dissociate and/or ionize the ClN(b) produced in the primary photolytic step. In parallel, limited experiments were performed on the rapid pyrolysis of a solid, ionic azide, NaN/sub 3/, to produce gaseous N/sub 3/ radicals and subsequent production of triplet N/sub 2/ molecules.

  17. Novel heterometallic metal–azido complex synthesized by “one-step” reaction: synthetic strategy and magnetic properties

    International Nuclear Information System (INIS)

    A novel heterometallic complex, [Ni2Mn(N3)2(nic)4·(H2O)2]n (1) (nic=nicotinate), was obtained by assembling MnCl2·4H2O, Ni(NO3)2·6H2O, NaN3 and nicotinic acid with a “one step” synthetic strategy—hydrothermal reaction. The 3D structure of the complex can be described as end-on (EO) azido and syn,syn carboxylates mixed bridged by alternate Ni–Mn–Ni trimers linked by the nicotinate. Dominant ferromagnetic interactions were observed between the NiII and MnII ions in the trimer. - Graphical abstract: A novel heterometallic 3D complex [Ni2Mn(N3)2(nic)4·(H2O)2]n (1) (nic=nicotinate) was synthesized by hydrothermal reaction. This complex exhibits interesting structural and magnetic properties. - Highlights: • It is difficult to construct simple coordination complexes with azide as “ligands” to obtain heterometallic metal–azido compounds. • A “one-step” method—hydrothermal reaction— was introduced to avoid the disadvantages of azide mentioned above. • The magnetic property is different with the isostructural homometal–azido complex due to the changed metal center

  18. A versatile click-compatible monolignol probe to study lignin deposition in plant cell walls.

    Science.gov (United States)

    Pandey, Jyotsna L; Wang, Bo; Diehl, Brett G; Richard, Tom L; Chen, Gong; Anderson, Charles T

    2015-01-01

    Lignin plays important structural and functional roles in plants by forming a hydrophobic matrix in secondary cell walls that enhances mechanical strength and resists microbial decay. While the importance of the lignin matrix is well documented and the biosynthetic pathways for monolignols are known, the process by which lignin precursors or monolignols are transported and polymerized to form this matrix remains a subject of considerable debate. In this study, we have synthesized and tested an analog of coniferyl alcohol that has been modified to contain an ethynyl group at the C-3 position. This modification enables fluorescent tagging and imaging of this molecule after its incorporation into plant tissue by click chemistry-assisted covalent labeling with a fluorescent azide dye, and confers a distinct Raman signature that could be used for Raman imaging. We found that this monolignol analog is incorporated into in vitro-polymerized dehydrogenation polymer (DHP) lignin and into root epidermal cell walls of 4-day-old Arabidopsis seedlings. Incorporation of the analog in stem sections of 6-week-old Arabidopsis thaliana plants and labeling with an Alexa-594 azide dye revealed the precise locations of new lignin polymerization. Results from this study indicate that this molecule can provide high-resolution localization of lignification during plant cell wall maturation and lignin matrix assembly. PMID:25884205

  19. Methylene bridge regulated geometrical preferences of ligands in cobalt(III) coordination chemistry and phenoxazinone synthase mimicking activity.

    Science.gov (United States)

    Panja, Anangamohan; Shyamal, Milan; Saha, Amrita; Mandal, Tarun Kanti

    2014-04-14

    Two new azide bound cobalt(III) complexes, [Co(L(1))(N3)3] (fac-1) and [Co(L(2))(N3)3] (mer-2), where L(1) is bis(2-pyridylmethyl)amine and L(2) is (2-pyridylmethyl)(2-pyridylethyl)amine, derived from tridentate reduced Schiff-base ligands have been reported. Interestingly, a methylene bridge regulated preferential coordination mode of ligands is noticed in their crystal structures: it is found in a facial arrangement in fac-1 and has a meridional disposition in mer-2. Both complexes show phenoxazinone synthase-like activity and the role of the structural factor on the catalytic activity is also explored. Moreover, the easily reducible cobalt(III) center in mer-2 favors the oxidation of o-aminophenol. The ESI-MS positive spectra together with UV-vis spectroscopy clearly suggest the formation of a catalyst-substrate adduct by substitution of the coordinated azide ions in the catalytic cycle.

  20. Periodically Grafted Amphiphilic Copolymers: Effects of Steric Crowding and Reversal of Amphiphilicity.

    Science.gov (United States)

    Mandal, Joydeb; Ramakrishnan, S

    2015-06-01

    Two series of periodically clickable polyesters were prepared; one of them carries alkylene segments along its backbone, whereas the other carries poly(ethylene glycol) (PEG) segments. These polyesters were clicked with either MPEG-350 azide or docosyl (C22) azide to yield periodically grafted amphiphilic copolymers (PGACs) carrying either flexible hydrophilic or crystallizable hydrophobic backbone segments. The immiscibility between hydrocarbon and PEG segments causes both of these systems to fold in either a zigzag or hairpin-like conformation; the hairpin-like conformation appears to be preferred when flexible PEG segments are present in the backbone. The folded chains further reorganize in the solid state to develop a lamellar morphology that permits the collocation of the PEG and hydrocarbon (HC) segments within alternate domains; evidence for the self-segregation was gained from DSC, SAXS, and AFM studies. SAXS studies revealed the formation of an extended lamellar structure, whereas AFM images showed uniform layered morphology with layer heights that matched reasonably well with the interlamellar spacing obtained from the SAXS study. Labeling one representative PGAC, carrying crystallizable long alkylene segments in the backbone and pendant PEG-350 side chains, with a small mole fraction of pyrene fluorophore permitted the examination of the conformational transition that occurs upon going from a good to a poor solvent; this single-chain folded conformation, we postulate, is the intermediate that organizes into the lamellar morphology.

  1. Solar energy conversion by green microalgae: a photosystem for hydrogen peroxide production.

    Science.gov (United States)

    de la Rosa, F F; Montes, O; Galván, F

    2001-09-20

    A photosystem for solar energy conversion, comprised of a culture of green microalgae supplemented with methyl viologen, is proposed. The capture of solar energy is based on the Mehler reaction. The reduction of methyl viologen by the photosynthetic apparatus and its subsequent reoxidation by oxygen produces hydrogen peroxide. This is a rich-energy compound that can be used as a nonpollutant and efficient fuel. Four different species of green microalgae, Chlamydomonas reinhardtii (21gr) C. reinhardtii (CW15), Chlorella fusca, and Monoraphidium braunii, were tested as a possible biocatalyst. Each species presented a different efficiency level in the transformation of energy. Azide was an efficient inhibitor of the hydrogen peroxide scavenging system while maintaining photosynthetic activity of the microalgae, and thus significantly increasing the production of the photosystem. The strain C. reinhardtii (21gr), among the species studied, was the most efficient with an initial production rate of 185 micromol H(2)O(2)/h x mg Chl and reaching a maximum of 42.5 micromol H(2)O(2)/mg Chl when assayed in the presence of azide inhibitor. PMID:11494222

  2. Chemical proteomics approaches for identifying the cellular targets of natural products.

    Science.gov (United States)

    Wright, M H; Sieber, S A

    2016-05-01

    Covering: 2010 up to 2016Deconvoluting the mode of action of natural products and drugs remains one of the biggest challenges in chemistry and biology today. Chemical proteomics is a growing area of chemical biology that seeks to design small molecule probes to understand protein function. In the context of natural products, chemical proteomics can be used to identify the protein binding partners or targets of small molecules in live cells. Here, we highlight recent examples of chemical probes based on natural products and their application for target identification. The review focuses on probes that can be covalently linked to their target proteins (either via intrinsic chemical reactivity or via the introduction of photocrosslinkers), and can be applied "in situ" - in living systems rather than cell lysates. We also focus here on strategies that employ a click reaction, the copper-catalysed azide-alkyne cycloaddition reaction (CuAAC), to allow minimal functionalisation of natural product scaffolds with an alkyne or azide tag. We also discuss 'competitive mode' approaches that screen for natural products that compete with a well-characterised chemical probe for binding to a particular set of protein targets. Fuelled by advances in mass spectrometry instrumentation and bioinformatics, many modern strategies are now embracing quantitative proteomics to help define the true interacting partners of probes, and we highlight the opportunities this rapidly evolving technology provides in chemical proteomics. Finally, some of the limitations and challenges of chemical proteomics approaches are discussed.

  3. Thermal and rheological behavior of reactive blends from metallocene olefin elastomers and polypropylene

    Directory of Open Access Journals (Sweden)

    Nei S. Domingues Junior

    2012-01-01

    Full Text Available Reactive blends of metallocene polyolefin elastomers (POE/polypropylene (PP with 60/40 composition were prepared with an organic peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxyhexane, and a bis-azide derivative, diphenyloxid-4,4'-bis(sulfonylazide (BSA. Ethylene-1-butene (EB and ethylene-1-octene (EO copolymers and elastomeric polypropylene (ePP were used as the elastomeric phase. The effect of elastomeric phase on the thermal, rheological, morphological and mechanical properties of the thermoplastic vulcanizates (TPVs or dynamic vulcanizates were studied. All TPVs depicted pseudoplastic behavior and blends cured with azide curative showed higher viscosities. The TPVs showed both dispersed and continuous phase morphology that depends on the elastomeric phase type revealing a limited degree of compatibility between PP and the elastomers EO or EB. On the other hand, the TPV PP/ePP showed a uniform morphology suggesting an improved compatibility. Substantial changes observed in physical properties were explained on the basis of blends' morphology and dynamic vulcanization. The results confirm that the mechanical properties are more influenced by the elastomeric phase than by the curative agent. This study revealed a broad new range of opportunities for POE-based TPVs.

  4. Crystal structure of bis(azido-κNbis[2,5-bis(pyridin-2-yl-1,3,4-thiadiazole-κ2N2,N3]nickel(II

    Directory of Open Access Journals (Sweden)

    Abdelhakim Laachir

    2015-02-01

    Full Text Available Reaction of 2,5-bis(pyridin-2-yl-1,3,4-thiadiazole and sodium azide with nickel(II triflate yielded the mononuclear title complex, [Ni(N32(C12H8N4S2]. The NiII ion is located on a centre of symmetry and is octahedrally coordinated by four N atoms of the two bidentate heterocyclic ligands in the equatorial plane. The axial positions are occupied by the N atoms of two almost linear azide ions [N—N—N = 178.8 (2°]. The thiadiazole and pyridine rings of the heterocyclic ligand are almost coplanar, with a maximum deviation from the mean plane of 0.0802 (9 Å. The cohesion of the crystal structure is ensured by π–π interactions between parallel pyridine rings of neighbouring molecules [centroid-to-centroid distance = 3.6413 (14 Å], leading to a layered arrangement of the molecules parallel to (001.

  5. The challenge of sample-stabilisation in the era of multi-residue analytical methods: a practical guideline for the stabilisation of 46 organic micropollutants in aqueous samples.

    Science.gov (United States)

    Hillebrand, Olav; Musallam, Shadha; Scherer, Laura; Nödler, Karsten; Licha, Tobias

    2013-06-01

    Water sample storage and stabilisation may affect data quality, if samples are managed improperly. In this study three stabilising strategies are evaluated for 46 relevant organic micro-pollutants: addition of the biocides (i) copper sulphate and (ii) sodium azide to water samples directly after sampling with subsequent sample storage as liquid phase and (iii) direct solid phase extraction (SPE), stabilising the samples by reducing the activity of water. River water and treated effluent were chosen as commonly investigated matrices with a high potential of biotransformation activity. Analyses were carried out for sample storage temperatures of 4 and 28°C for water samples stored as liquid phase and for sample storage temperatures of 4, 20 and 40°C for SPE cartridges. Cooling of water samples alone was not sufficient for longer storage times (>24h). While copper sulphate caused detrimental interferences with nitrogen containing heterocyclic compounds, sodium azide proved to be a suitable stabilising agent. The best results could be obtained for SPE cartridges stored cool. Recommendations for samples preservation are provided. PMID:23562683

  6. Cationic micellar nanoparticles for DNA and doxorubicin co-delivery.

    Science.gov (United States)

    Lin, Jian-Tao; Zou, Ying; Wang, Chao; Zhong, Yue-Chun; Zhao, Yi; Zhu, Hui-Er; Wang, Guan-Hai; Zhang, Li-Ming; Zheng, Xue-Bao

    2014-11-01

    Cationic micellar nanoparticles for chemotherapeutic drugs and therapeutic gene co-delivery were prepared based on a poly-(N-ε-carbobenzyloxy-l-lysine) (PZLL) and dendritic polyamidoamine (PAMAM) block copolymer (PZLL-D3). PZLL-D3 was synthesized by a copper-catalyzed azide alkyne cyclization (click) reaction between α-alkyne-PZLL and azide focal point PAMAM dendrons. Its structure was characterized by (1)H NMR and FTIR, and its buffering capability was determined by acid-base titration. MTT, agarose gel electrophoresis and flow cytometry studies showed that PZLL-D3 revealed low in vitro cytotoxicity, strong pDNA condensation ability, protection of pDNA against deoxyribonuclease I degradation and high gene transfection efficiency in 293T and HeLa cells. In addition, the micellar nanoparticles delivered pDNA and anticancer drug doxorubicin (DOX) simultaneously and efficiently to tumor cells, and the DOX loaded nanoparticles showed sustained in vitro release at pH=7.4 and 5.8. PMID:25280725

  7. Simultaneous Photoinduced ATRP and CuAAC Reactions for the Synthesis of Block Copolymers.

    Science.gov (United States)

    Murtezi, Eljesa; Yagci, Yusuf

    2014-09-01

    Atom transfer radical polymerization (ATRP) and copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions, both utilizing copper(I) (Cu(I)) complexes, make a tremendous progress in synthetic polymer chemistry. Independently or in combination with other polymerization processes, they give access to the synthesis of polymers with well-defined structures, desired molecular architectures, and a wide variety of functionalities. Here, a novel in situ photoinduced formation of block copolymers is described by simultaneous ATRP and CuAAC processes. This approach relies on the direct reduction of initially charged copper(II) complexes to Cu(I) complexes to trigger both ATRP and CuAAC reactions coinciding under UV light at ambient temperature in one pot. Its synthetic utility is demonstrated on a model block copolymerization process by photoinduced ATRP of methyl methacrylate (MMA) using an initiator possessing acetylene functionality and concomitant click reaction between thus formed α-acetylene-poly(methyl methacrylate) (Ac-PMMA) and independently prepared azide functional polystyrene (PS-N3 ). Successful formation of PS-b-PMMA block copolymer is confirmed by FT-IR and (1) H NMR spectral analysis and gel permeation chromatography (GPC) measurements. PMID:25200624

  8. Grafting of poly(ethylene glycol) on click chemistry modified Si(100) surfaces.

    Science.gov (United States)

    Flavel, Benjamin S; Jasieniak, Marek; Velleman, Leonora; Ciampi, Simone; Luais, Erwann; Peterson, Joshua R; Griesser, Hans J; Shapter, Joe G; Gooding, J Justin

    2013-07-01

    Poly(ethylene glycol) (PEG) is one of the most extensively studied antifouling coatings due to its ability to reduce protein adsorption and improve biocompatibility. Although the use of PEG for antifouling coatings is well established, the stability and density of PEG layers are often inadequate to provide optimum antifouling properties. To improve on these shortcomings, we employed the stepwise construction of PEG layers onto a silicon surface. Acetylene-terminated alkyl monolayers were attached to nonoxidized crystalline silicon surfaces via a one-step hydrosilylation procedure with 1,8-nonadiyne. The acetylene-terminated surfaces were functionalized via a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction of the surface-bound alkynes with an azide to produce an amine terminated layer. The amine terminated layer was then further conjugated with PEG to produce an antifouling surface. The antifouling surface properties were investigated by testing adsorption of human serum albumin (HSA) and lysozyme (Lys) onto PEG layers from phosphate buffer solutions. Detailed characterization of protein fouling was carried out with X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with principal component analysis (PCA). The results revealed no fouling of albumin onto PEG coatings whereas the smaller protein lysozyme adsorbed to a very low extent. PMID:23790067

  9. Synthesis and Crystal Structure of catena-Poly[[[2,4-dibromo-6-[(3-dimethylaminopropylimino)-methyl]phenolato]copper(Ⅱ)]-μ-azido

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A novel end-to-end azido-bridged polynuclear Schiff-base copper(H) complex,[Cu(C12H15Br2N2O)(N3)]n, was prepared and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction.The crystal belongs to the orthorhombic system, space group Pbcn with a = 24.588(5), b = 10.377(2), c = 13.022(3)(A),V= 3322.6(12)(A)3, Z = 8, Dc = 1.874 g/cm3, Mr= 468.65, λ(MoKα) = 0.71073 (A),μ= 6.130 mm-1, F(000) = 1832, R = 0.0637 and wR = 0.1176.The Cu atom in the complex is five-coordinated in a square pyramidal geometry by three donoratoms of the Schiff-base ligand, and two N atoms from two bridging azide ligands.The [2,4-dibromo-6-[(3-dimethylaminopropylimino)methyl]phenolato]copper(Ⅱ) units are linked by the bridging azide ligands, giving zigzag polymeric chains with backbones of the [-Cu-N-N-N-Cu]n type running along the b axis.

  10. Intramolecular Tetrylene Lewis Adducts: Synthesis and Reactivity.

    Science.gov (United States)

    Schneider, Julia; Krebs, Kilian M; Freitag, Sarah; Eichele, Klaus; Schubert, Hartmut; Wesemann, Lars

    2016-07-01

    A series of benzyl(diphenylphosphino) and o-phenyl(diphenlyphosphino) substituted germylenes and plumbylenes were synthesized by nucleophilic substitution between the respective lithium reagent and tetrylene halide. The Lewis pairs were characterized by X-ray crystallography and NMR spectroscopy. The reactivity of the tetrylenes was investigated with respect to azide addition. In the germylene case, the germaniumimide was formed as the kinetically controlled product, which rearranges upon heating to give the phosphinimide. The stannylene and plumbylene derivatives react with adamantylazide to give the azide adducts. 1-Pentene reacts diastereoselectively with the phosphagermirane to give a cyclic addition product. Trimethysilylacetylene shows an addition with the benzylphosphino-substituted germylene and plumbylene to give the cycloheteropentene molecules. The addition product between phenylacetylene and the four membered Ge-P adduct shows after addition at room temperature a 1,4-phenylmigration to give a cyclic phosphine. Alkylnitrene insertion into a Ge-C bond of the alkyne addition product of the phosphagermirane was found in reaction with adamantylazide. PMID:27273819

  11. A versatile click-compatible monolignol probe to study lignin deposition in plant cell walls.

    Directory of Open Access Journals (Sweden)

    Jyotsna L Pandey

    Full Text Available Lignin plays important structural and functional roles in plants by forming a hydrophobic matrix in secondary cell walls that enhances mechanical strength and resists microbial decay. While the importance of the lignin matrix is well documented and the biosynthetic pathways for monolignols are known, the process by which lignin precursors or monolignols are transported and polymerized to form this matrix remains a subject of considerable debate. In this study, we have synthesized and tested an analog of coniferyl alcohol that has been modified to contain an ethynyl group at the C-3 position. This modification enables fluorescent tagging and imaging of this molecule after its incorporation into plant tissue by click chemistry-assisted covalent labeling with a fluorescent azide dye, and confers a distinct Raman signature that could be used for Raman imaging. We found that this monolignol analog is incorporated into in vitro-polymerized dehydrogenation polymer (DHP lignin and into root epidermal cell walls of 4-day-old Arabidopsis seedlings. Incorporation of the analog in stem sections of 6-week-old Arabidopsis thaliana plants and labeling with an Alexa-594 azide dye revealed the precise locations of new lignin polymerization. Results from this study indicate that this molecule can provide high-resolution localization of lignification during plant cell wall maturation and lignin matrix assembly.

  12. Effects of incense smoke on human lymphocyte DNA.

    Science.gov (United States)

    Szeto, Yim Tong; Sok Wa Leong, Kosca; Keong Lam, Kason; Min Min Hong, Cynthia; Kai Mui Lee, Daphne; Teng Fun Chan, Yui; Benzie, Iris F F

    2009-01-01

    Incense burning is common in Southeast Asia, where it is a traditional and ceremonial practice in deity worship and paying respect to ancestors. However, incense emissions are an important source of indoor air pollution in Asia, and may induce health problems to those exposed. In this in vitro study the effects of incense emissions on human DNA were investigated using the comet assay. Particulates in smoke from six kinds of incense were trapped in saline or ethanol and human lymphocytes were exposed under controlled conditions. Results showed that DNA damage, including strand breaks, was induced by both aqueous and ethanolic extracts of two samples. The ethanolic extract of one sample induced DNA damage, while no significant DNA damage was found in the remaining three samples. The mechanisms underlying DNA damage induced by incense emissions were also investigated. Catalase (CAT), sodium azide, and superoxide dismutase (SOD) were co-incubated with extract, which exerted significant DNA damaging effects. Results showed that CAT with or without SOD diminished DNA damage, whereas sodium azide did not seem able to reduce DNA damage. Data indicate there are potential adverse health effects of such exposure, particularly for temple workers.

  13. Fate of bulk organic matter, nitrogen, and pharmaceutically active compounds in batch experiments simulating soil aquifer treatment (SAT) using primary effluent

    KAUST Repository

    Abel, Chol D T

    2013-06-30

    Reduction of bulk organic matter, nitrogen, and pharmaceutically active compounds from primary effluent during managed aquifer recharge was investigated using laboratory-scale batch reactors. Biologically stable batch reactors were spiked with different concentrations of sodium azide to inhibit biological activity and probe the effect of microbial activity on attenuation of various pollutants of concern. The experimental results obtained revealed that removal of dissolved organic carbon correlated with active microbial biomass. Furthermore, addition of 2 mM of sodium azide affected nitrite-oxidizing bacteria leading to accumulation of nitrite-nitrogen in the reactors while an ammonium-nitrogen reduction of 95.5 % was achieved. Removal efficiencies of the hydrophilic neutral compounds phenacetin, paracetamol, and caffeine were independent of the extent of the active microbial biomass and were >90 % in all reactors, whereas removal of pentoxifylline was dependent on the biological stability of the reactor. However, hydrophobic ionic compounds exhibited removal efficiency >80 % in batch reactors with the highest biological activity as evidenced by high concentration of adenosine triphosphate. © 2013 Springer Science+Business Media Dordrecht.

  14. Click-based synthesis and antitubercular evaluation of novel dibenzo[b,d]thiophene-1,2,3-triazoles with piperidine, piperazine, morpholine and thiomorpholine appendages.

    Science.gov (United States)

    Pulipati, Lokesh; Yogeeswari, Perumal; Sriram, Dharmarajan; Kantevari, Srinivas

    2016-06-01

    A series of novel piperidine, piperazine, morpholine and thiomorpholine appended dibenzo[b,d]thiophene-1,2,3-triazoles were designed and synthesized utilizing azide-alkyne click chemistry in the penultimate step. The required azide building block 6a-e was synthesized from commercial dibenzo[b,d]thiophene in good yields following five step reaction sequence. All the new analogues 8a-f, 9a-f, 10a-f, 11a-f &12a-f were characterized by their NMR and mass spectral analysis. Screening all thirty new compounds for in vitro antimycobacterial activity against Mycobacterium tuberculosis H37Rv, resulted 8a, 8f and 11e as potent analogues with MIC 0.78μg/mL, 0.78μg/mL & 1.56μg/mL, respectively, and has shown lower cytotoxicity. Interestingly, all six piperazine appended dibenzo[b,d]thiophene-1,2,3-triazoles 11a-f exhibited Mtb inhibition activity with MIC 1.56-12.5μg/mL. To some extent, the data observed here indicated Mycobacterium tuberculosis inhibition among the appendages is in the order, piperazine>thiomorpholine>morpholine. PMID:27101894

  15. Controlled Multi-functionalization Facilitates Targeted Delivery of Nanoparticles to Cancer Cells.

    Science.gov (United States)

    Hudlikar, Manish S; Li, Xiuru; Gagarinov, Ivan A; Kolishetti, Nagesh; Wolfert, Margreet A; Boons, Geert-Jan

    2016-01-22

    A major objective of nanomedicine is to combine in a controlled manner multiple functional entities into a single nanoscale device to target particles with great spatial precision, thereby increasing the selectivity and potency of therapeutic drugs. A multifunctional nanoparticle is described for controlled conjugation of a cytotoxic drug, a cancer cell targeting ligand, and an imaging moiety. The approach is based on the chemical synthesis of polyethylene glycol that at one end is modified by a thioctic acid for controlled attachment to a gold core. The other end of the PEG polymers is modified by a hydrazine, amine, or dibenzocyclooctynol moiety for conjugation with functional entities having a ketone, activated ester, or azide moiety, respectively. The conjugation approach allowed the controlled attachment of doxorubicin through an acid-labile hydrazone linkage, an Alexa Fluor dye through an amide bond, and a glycan-based ligand for the cell surface receptor CD22 of B-cells using strain promoted azide-alkyne cycloaddition. The incorporation of the ligand for CD22 led to rapid entry of the nanoparticle by receptor-mediated endocytosis. Covalent attachment of doxorubicin via hydrazone linkage caused pH-responsive intracellular release of doxorubicin and significantly enhanced the cytotoxicity of nanoparticles. A remarkable 60-fold enhancement in cytotoxicity of CD22 (+) lymphoma cells was observed compared to non- targeted nanoparticles. PMID:26683093

  16. Cycloadditions for Studying Nucleic Acids.

    Science.gov (United States)

    Kath-Schorr, Stephanie

    2016-02-01

    Cycloaddition reactions for site-specific or global modification of nucleic acids have enabled the preparation of a plethora of previously inaccessible DNA and RNA constructs for structural and functional studies on naturally occurring nucleic acids, the assembly of nucleic acid nanostructures, therapeutic applications, and recently, the development of novel aptamers. In this chapter, recent progress in nucleic acid functionalization via a range of different cycloaddition (click) chemistries is presented. At first, cycloaddition/click chemistries already used for modifying nucleic acids are summarized, ranging from the well-established copper(I)-catalyzed alkyne-azide cycloaddition reaction to copper free methods, such as the strain-promoted azide-alkyne cycloaddition, tetrazole-based photoclick chemistry and the inverse electron demand Diels-Alder cycloaddition reaction between strained alkenes and tetrazine derivatives. The subsequent sections contain selected applications of nucleic acid functionalization via click chemistry; in particular, site-specific enzymatic labeling in vitro, either via DNA and RNA recognizing enzymes or by introducing unnatural base pairs modified for click reactions. Further sections report recent progress in metabolic labeling and fluorescent detection of DNA and RNA synthesis in vivo, click nucleic acid ligation, click chemistry in nanostructure assembly and click-SELEX as a novel method for the selection of aptamers. PMID:27572987

  17. A systematic study of protein labeling by fluorogenic probes using cysteine targeting vinyl sulfone-cyclooctyne tags.

    Science.gov (United States)

    Söveges, B; Imre, T; Szende, T; Póti, Á L; Cserép, G B; Hegedűs, T; Kele, P; Németh, K

    2016-07-01

    Fluorescent tagging of proteins via accessible cysteine residues is of paramount importance. In this study, model proteins of interest (mitogen-activated protein kinases) were labeled successfully in native state on their free thiols by direct fluorescence derivatization, or in a sequential manner where conjugation of the site specific linker and the fluorophore is carried out in two steps. To this end we designed and prepared two novel chemical reporters carrying vinyl sulfone as Cys targeting function and cyclooctyne motifs, suitable for subsequent conjugation with fluorogenic azides via copper free strain-promoted azide-alkyne click chemistry. Direct and sequential labeling reaction steps were analyzed by native PAGE, capillary zone electrophoresis and tandem mass spectrometry. The efficiency of tagging was correlated with solvent accessibility of the Cys residues. Our results indicated that conjugation of native proteins by vinyl sulfone linkers was fast and thiol-selective. Subsequent click reaction with fluorogenic dyes generates intensive fluorescence signals and fulfills all requirements of bioorthogonality. PMID:27244693

  18. Macrocyclization and labeling of helix-loop-helix peptide with intramolecular bis-thioether linkage.

    Science.gov (United States)

    Nishihara, Toshio; Kitada, Hidekazu; Fujiwara, Daisuke; Fujii, Ikuo

    2016-11-01

    Conformationally constrained peptides have been developed as an inhibitor for protein-protein interactions (PPIs), and we have de novo designed cyclized helix-loop-helix (cHLH) peptide with a disulfide bond consisting of 40 amino acids to generate molecular-targeting peptides. However, synthesis of long peptides has sometimes resulted in low yield according to the respective amino acid sequences. Here we developed a method for efficient synthesis and labeling for cHLH peptides. First, we synthesized two peptide fragments and connected them by the copper-mediated alkyne and azide cycloaddition (CuAAC) reaction. Cyclization was performed by bis-thioether linkage using 1,3-dibromomethyl-5-propargyloxybenzene, and subsequently, the cHLH peptide was labeled with an azide-labeled probe. Finally, we designed and synthesized a peptide inhibitor for the p53-HDM2 interaction using a structure-guided design and successfully labeled it with a fluorescent probe or a functional peptide, respectively, by click chemistry. This macrocyclization and labeling method for cHLH peptide would facilitate the discovery of de novo bioactive ligands and therapeutic leads. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 415-421, 2016. PMID:26917088

  19. Synthesis of alpha- and beta-D-glucopyranosyl triazoles by CuAAC 'click chemistry': reactant tolerance, reaction rate, product structure and glucosidase inhibitory properties.

    Science.gov (United States)

    Dedola, Simone; Hughes, David L; Nepogodiev, Sergey A; Rejzek, Martin; Field, Robert A

    2010-06-16

    Cu(I)-catalysed azide alkyne 1,3-dipolar cycloaddition (CuAAC) 'click chemistry' was used to assemble a library of 21 alpha-D- and beta-D-glucopyranosyl triazoles, which were assessed as potential glycosidase inhibitors. In the course of this work, different reactivities of isomeric alpha- and beta-glucopyranosyl azides under CuAAC conditions were noted. This difference was further investigated using competition reactions and rationalised on the basis of X-ray crystallographic data, which revealed significant differences in bond lengths within the azido groups of the alpha- and beta-anomers. Structural studies also revealed a preference for perpendicular orientation of the sugar and triazole rings in both the alpha- and beta-glucosyl triazoles in the solid state. The triazole library was assayed for inhibition of sweet almond beta-glucosidase (GH1) and yeast alpha-glucosidase (GH13), which led to the identification of a set of glucosidase inhibitors effective in the 100 microM range. The preference for inhibition of one enzyme over the other proved to be dependent on the anomeric configuration of the inhibitor, as expected.

  20. Novel antifouling surface with improved hemocompatibility by immobilization of polyzwitterions onto silicon via click chemistry

    Science.gov (United States)

    Zheng, Sunxiang; Yang, Qian; Mi, Baoxia

    2016-02-01

    A novel procedure is presented to develop an antifouling silicon surface with improved hemocompatibility by using a zwitterionic polymer, poly(sulfobetaine methacrylate) (polySBMA). Functionalization of the silicon surface with polySBMA involved the following three steps: (1) an alkyne terminated polySBMA was synthesized by RAFT polymerization; (2) a self-assembled monolayer with bromine end groups was constructed on the silicon surface, and then the bromine end groups were replaced by azide groups; and (3) the polySBMA was attached to the silicon surface by azide-alkyne cycloaddition click reaction. Membrane characterization confirmed a successful silicon surface modification with almost 100% coverage by polySBMA and an extremely hydrophilic surface after such modification. The polySBMA-modified silicon surface was found to have excellent anti-nonspecific adsorption properties for both bovine serum albumin (BSA) protein and model bacterial cells. Whole blood adsorption experiments showed that the polySBMA-modified silicon surface exhibited excellent hemocompatibility and effective anti-adhesion to blood cells. Silicon membranes with such antifouling and hemocompatible surfaces can be advantageously used to drastically extend the service life of implantable medical devices such as artificial kidney devices.