Sample records for azides

  1. Thiophene-2-carbonyl azide

    Directory of Open Access Journals (Sweden)

    Michael Findlater


    Full Text Available The title compound, C5H3N3OS, is almost planar (r.m.s. deviation for the ten non-H atoms = 0.018 Å and forms an extended layer structure in the (100 plane, held together via hydrogen-bonding interactions between adjacent molecules. Of particular note is the occurrence of RC—H...N−=N+=NR interactions between an aromatic C—H group and an azide moiety which, in conjunction with a complementary C—H...O=C interaction, forms a nine-membered ring.


    Institute of Scientific and Technical Information of China (English)

    Hong-kun Li; Jing-zhi Sun; An-jun Qin; Ben Zhong Tang


    The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field.This review assembles an update of the advances of using azide-alkyne click polymerization to prepare functional polytriazoles (PTAs) with linear and hyperbranched structures.The Cu(Ⅰ)-mediated click polymerization furnishes 1,4-regioregular PTAs,whereas,the metal-free click polymerization of propiolates and azides produces PTAs with 1,4-regioisomer contents up to 90%.The PTAs display advanced functions,such as aggregation-induced emission,thermal stability,biocompatibility and optical nonlinearity.

  3. Towards the Synthesis of Graphene Azide from Graphene Oxide. (United States)

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


    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.

  4. Crystal Structure of 2-Ethylimidazole-1-sulfonyl Azide: A New Azidation Reagent

    Directory of Open Access Journals (Sweden)

    Herwig Schottenberger


    Full Text Available Crystalline 2-ethylimidazole-1-sulfonyl azide was designed as a convenient reagent with improved thermal stability for electrophilic azidation of carbanions. The compound crystallized in the monoclinic space group P21/c. The molecules are arranged into chains by short C–H...O contacts along a two-fold screw axis. The quaternary 1-azidosulfonyl-2-ethyl-3-methylimidazolium tetrafluoroborate crystallized in Fdd2 with two independent ion pairs which engage in C–H...F interactions.

  5. Synthesis of Azide-Functionalized Hydroxyl-Terminated Polybutadiene (United States)

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


    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.

  6. Towards the Synthesis of Graphene Azide from Graphene Oxide



    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...

  7. The Gruneisen parameter for silver azide (United States)

    Zhuravlyov, Yu. N.; Lisitsyn, V. M.


    A first-principle procedure is proposed to determine the Gruneisen parameter for a crystal by calculating the external pressure and the vibration spectrum as functions of the volume of a unit cell. In the gradient approximation of the electron density functional theory, on the basis of a linear combination of atomic orbitals, the elastic and the thermodynamic Gruneisen parameters of silver azide, which decrease with volume (with increasing pressure), are calculated with the use of the CRYSTAL09 code. The equilibrium values of the parameter γ0 for various cold equations of state of crystals and for the thermodynamic models used are, respectively, ~2.3 and 1.6.

  8. Alkali-metal azides interacting with metal-organic frameworks. (United States)

    Armata, Nerina; Cortese, Remedios; Duca, Dario; Triolo, Roberto


    Interactions between alkali-metal azides and metal-organic framework (MOF) derivatives, namely, the first and third members of the isoreticular MOF (IRMOF) family, IRMOF-1 and IRMOF-3, are studied within the density functional theory (DFT) paradigm. The investigations take into account different models of the selected IRMOFs. The mutual influence between the alkali-metal azides and the π rings or Zn centers of the involved MOF derivatives are studied by considering the interactions both of the alkali-metal cations with model aromatic centers and of the alkali-metal azides with distinct sites of differently sized models of IRMOF-1 and IRMOF-3. Several exchange and correlation functionals are employed to calculate the corresponding interaction energies. Remarkably, it is found that, with increasing alkali-metal atom size, the latter decrease for cations interacting with the π-ring systems and increase for the azides interacting with the MOF fragments. The opposite behavior is explained by stabilization effects on the azide moieties and determined by the Zn atoms, which constitute the inorganic vertices of the IRMOF species. Larger cations can, in fact, coordinate more efficiently to both the aromatic center and the azide anion, and thus stabilizing bridging arrangements of the azide between one alkali-metal and two Zn atoms in an η(2) coordination mode are more favored.

  9. Vapor pressures and enthalpies of vaporization of azides

    Energy Technology Data Exchange (ETDEWEB)

    Verevkin, Sergey P., E-mail: [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)


    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.

  10. Preliminary Studies on Pulsed Electric Field Breakdown of Lead Azide (United States)


    1/2 OS CO ton NO. S3L TECHNICAL REPORT 4991 PRELIMINARY SUJDfES ON PULSED ELECTRIC FIELD BREAKDOWN OF LEAD AZIDE L AVRAMI M. BUMS D. DOWNS...Introduction Background A. Contact Effects B. Pulsed Electric Field Measurements Experimental A. Contact Effects B. Pulsed Electric Fields Discussion...B. Pulsed Electric Field Measurements The application of pulsed electric fields to lead azide does not exactly simulate the conditions experienced

  11. Functionalization of carbon nanotubes and other nanocarbons by azide chemistry

    Institute of Scientific and Technical Information of China (English)

    Jin Han; Chao Gao


    Following the conventional carbon allotropes of diamond and graphite, fullerene, carbon nanotubes (CNTs) and graphene as 0D, 1D and 2D graphitic macromolecules have been discovered recently in succession, declaring the unlimited potential of carbon-based nanomaterials and nanotechnology. Although CNTs exhibit significant potential applications in advanced materials and other fields due to their extraordinary mechanical strength and electrical/thermal conductivity properties, their low solubility, poor wettability and bad dispersibility in common solvents and solid matrices have limited their processing and applications. Thus, the attempt to achieve wettable/processable CNTs by functionalization has attracted increasing attention in both scientific and industrial communities. In recent years, azide chemistry has been demonstrated as a powerful means to covalently modify CNTs. It consists of two major approaches: click chemistry and nitrene chemistry, which both involve the usage of various azide compounds. The former one is based on highly reactive and stereospecifical Cu(I) catalyzed azide-alkyne cycloaddition reaction; the latter one is based on the electrophilic attack to unsaturated bonds of CNTs with nitrenes as reactive intermediates formed from thermolysis or photolysis of azides. In this mini-review paper, the azide chemistry to functionalize CNTs is highlighted and the corresponding functionalization routes to build CNT-based complex structures are also discussed. Besides, covalent functionalizations of other graphitic nanomaterials such as fullerence and graphene, via azide chemistry, are commented briefly.

  12. Sensitivity of cuprous azide towards heat and impact

    Directory of Open Access Journals (Sweden)

    Kartar Singh


    Full Text Available "Rates of thermal decomposition of azide at six different temperatures have been measured. The sigmoid shapes of the curves representing increase in pressure with time suggest that a given temperature a fixed number of nuclei are formed at the end of the induction period. The nuclei increase in size in three dimensions. The radius of any nucleus at any instant (tis directly proportional to (t-t/Sub/owhere t/Sub/o is the induction period. The activation energy involved in thermal has been found decomposition to be 26.5K calories. It is suggested that this activation energy corresponds to the energy required for thermal transition of an electron 3 d band to the Fermi level of the metallic copper nuclei. The impact sensitivity and induction period necessary for explosion at various temperatures for crystalline and precipitated samples of cuprous azide have been measured. The results indicate that cuprous azide is more sensitive towards heat and impact than lead azide. The impact sensitivity of cuprous azide is found to increase in crystal size."

  13. Applications of Azide-Based Bioorthogonal Click Chemistry in Glycobiology

    Directory of Open Access Journals (Sweden)

    Xiu Zhang


    Full Text Available Click chemistry is a powerful chemical reaction with excellent bioorthogonality features: biocompatible, rapid and highly specific in biological environments. For glycobiology, bioorthogonal click chemistry has created a new method for glycan non-invasive imaging in living systems, selective metabolic engineering, and offered an elite chemical handle for biological manipulation and glycomics studies. Especially the [3 + 2] dipolar cycloadditions of azides with strained alkynes and the Staudinger ligation of azides and triarylphosphines have been widely used among the extant click reactions. This review focuses on the azide-based bioorthogonal click chemistry, describing the characteristics and development of these reactions, introducing some recent applications in glycobiology research, especially in glycan metabolic engineering, including glycan non-invasive imaging, glycomics studies and viral surface manipulation for drug discovery as well as other applications like activity-based protein profiling and carbohydrate microarrays.

  14. Applications of azide-based bioorthogonal click chemistry in glycobiology. (United States)

    Zhang, Xiu; Zhang, Yan


    Click chemistry is a powerful chemical reaction with excellent bioorthogonality features: biocompatible, rapid and highly specific in biological environments. For glycobiology, bioorthogonal click chemistry has created a new method for glycan non-invasive imaging in living systems, selective metabolic engineering, and offered an elite chemical handle for biological manipulation and glycomics studies. Especially the [3 + 2] dipolar cycloadditions of azides with strained alkynes and the Staudinger ligation of azides and triarylphosphines have been widely used among the extant click reactions. This review focuses on the azide-based bioorthogonal click chemistry, describing the characteristics and development of these reactions, introducing some recent applications in glycobiology research, especially in glycan metabolic engineering, including glycan non-invasive imaging, glycomics studies and viral surface manipulation for drug discovery as well as other applications like activity-based protein profiling and carbohydrate microarrays.

  15. Detonation of the aluminized explosives with sodium azide

    Energy Technology Data Exchange (ETDEWEB)

    Maranda, A.; Nowaczewski, J.; Trzcinski, W. [Military University of Technology Kaliskiego, Warsaw (Poland)


    The velocity of detonation in the aluminized explosives containing sodium azide was measured. he experimental results were compared with those of calculation. Two different explosive components were used in the tests: RDX and ammonium nitrate. The contents of constituents of explosive mixture varied within a wide range. The X-ray analysis of the solid detonation products was also made. The results enable us to predict a behaviour of sodium azide and aluminium during detonation process of the explosive tested and to verify the possibility of reaction between aluminium and nitrogen during that process. (authors) 12 refs.

  16. [Sodium azide--clinical course of the poisoning and treatment]. (United States)

    Łopaciński, Bogdan; Kołacinski, Zbigniew; Winnicka, Renata


    Sodium azide poisonings occur very rarely. The mechanism of sodium azide toxic effect has not yet been fully explained. Despite the lack of an explicit procedure for the cases of sodium azide poisonings, in vitro tests and rare case reports suggest that treatment with antidotes for cyanide poisoning victims can be effective. This study describes two cases of suicidal sodium azide ingestion. Case 1. 30-year-old male ingested ca. 180 mg of sodium azide. On admission to hospital, within 4 hours from poisoning, the man complained of dizziness and anxiety. Physical examination revealed horizontal nystagmus, flapping tremor, HR 135/min. In laboratory tests, higher blood concentration of lactates (3 mmol/l) was detected, as well as lower potassium concentration (3.4 mmol/L) and increased transaminase activity (ALT 74 U/l, AST 90 U/l). Electrocardiographic tests showed a negative T wave in limb lead III. Other results were within normal. As the patient ingested a toxic dose of sodium azide, he was treated according to the therapy prescription for cyanide poisoning (amyl nitrite inhalation followed by intravenous administration of sodium nitrite and sodium thiosulphate). ECG record of the last day of hospitalization (7th day of treatment) showed negative T waves in lead III, V4-V6. He was discharged from hospital in good condition. Case 2.23-year-old male ingested 10 g of sodium azide 1.5 hours prior to admission to hospital. At the beginning, the patient's condition was good, but it changed to critical state within the first hours of hospitalization. He developed a deep coma, respiratory and circulatory insufficiency, metabolic acidosis, cardiac dysrrhythmias and anuria. Cardiac activity monitoring showed alternating tachycardia (140 beats per minute) and bradycardia (48 beats per minute), numerous additional supraventricular and ventricular extrasystoles and sinus dysrrhythmia. Cardiac arrest (asystolia) occurred twice, the second incident with fatal outcome. The patient

  17. Silver-Catalyzed Decarboxylative Azidation of Aliphatic Carboxylic Acids. (United States)

    Zhu, Yuchao; Li, Xinyao; Wang, Xiaoyang; Huang, Xiaoqiang; Shen, Tao; Zhang, Yiqun; Sun, Xiang; Zou, Miancheng; Song, Song; Jiao, Ning


    The catalytic decarboxylative nitrogenation of aliphatic carboxylic acids for the synthesis of alkyl azides is reported. A series of tertiary, secondary, and primary organoazides were prepared from easily available aliphatic carboxylic acids by using K2S2O8 as the oxidant and PhSO2N3 as the nitrogen source. The EPR experiment sufficiently proved that an alkyl radical process was generated in the process, and DFT calculations further supported the SET process followed by a stepwise SH2 reaction to afford azide product.

  18. Novel sensors for detection of azide and dopamine: Electrochemical studies (United States)

    Dalmia, Avinash

    Electrochemical amperometric sensors have been used sucessfully for monitoring a wide variety of hazardous species. Electrochemical studies of azides have been conducted at carbon, platinum and gold to evaluate their sensing properties. The differences in electrochemical behavior of azides at carbon, platinum and gold are elucidated with rotating disc, ring-disc and DEMS (Differential Electrochemical mass spectroscopy). It has been observed that the electrooxidation of azides at carbon electrode results in formation of only nitrogen, whereas at platinum electrode, the electrooxidation of azides results in formation of both nitrogen and nitrogen oxides. Gold in presence of azide ions undergoes electrooxidation forming soluble gold azide complexes at lower potentials and nitrogen and nitrogen oxides at higher potentials. It was demonstrated that azides are much more electroactive than hydrazoic acid. This work has implication for design of electrochemical sensors to detect and monitor azide ions. Gold electrodes modified with self assembled monolayers offer possibilities of sensors with higher selectivity, stability, fast response time and higher sensitivity. In the second part of this thesis, gold electrodes modified with SAM (self assembled monolayer) with acidic end group for selective detection of catecholamines were evaluated. SAM modified substrates have been characterized using different techniques, i.e., electrochemical desorption, capacitance measurements, angle resolved XPS measurements, potentiometric measurements and cyclic voltammetric measurements. The electrochemical desorption measurements show that the coverage of SAM molecules corresponds to a monolayer. Capacitance measurements demonstrate that the capacitance depends on the length, end group and defects present in monolayers. Angle resolved XPS has been demonstrated as a powerful tool for studying the anisotropic atomic distribution in monolayer film. The cyclic voltammetric measurements show that

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

    Indian Academy of Sciences (India)

    Lalthazuala Rokhum; Ghanashyam Bez


    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.

  20. Influence of acids on the decomposition of azide polymers

    Energy Technology Data Exchange (ETDEWEB)

    Stawinski, T.; Syczewski, M. [Warsaw University of Technology, Warsaw (Poland)


    This work studies the influence of carboxylic acids upon azido-polyethers (GAP, BAMO/THF), into which they are introduced, and the influence of carboxyl-end groups on polyesters with azido groups. It has been noted that the stability of the studied azide polymers depended on their structure, synthesis method and the type of acidic group. (author) 6 refs.

  1. Proceedings of the Symposium on Lead and Copper Azides (United States)


    free from unhydrolysed polyvinyl acetate. The degree of polymerisation does not appear to be critical. An effective procedure is to add simultaneously...session was concerned with the hazards involved in the manufacture and subsequent usage of lead azide. A study had been undertaken of the explosions

  2. Periodic DFT approaches to crystalline alkali metal azides

    Institute of Scientific and Technical Information of China (English)


    The energy bands, electronic structures andrelationship between structures and properties of the crys-talline alkali metal azides, LiN3, α-NaN3 and KN3, are investigated at the DFT-B3LYP level. The crystalline bulks arepredicted to be insulator, speculated from their band gaps ofca. 0.23-0.25 a.u. and from their level frontier bands. Theatomic overlaps and electron densities show that the metalsand the azides are combined by ionic bonds. The crystal lat-tice energies, being corrected for the basis set superpositionerrors, are -852.30, -771.45 and - 614.78 kJ @ mol-1 for LiN3,α-NaN3 and KN3 respectively. These values are similar tothose by Gray's approximate method. The frontier crystalorbital mainly consists of the atomic orbital of the terminalnitrogen of azides. The contribution of the metallic orbital tothe LUMO is very small. The electron transition from theHOMO to the LUMO is difficult to occur. Hence all the al-kali metal azides are expected to be insensitive explosives,according to the "principle of easiest electron transition".

  3. The Manufacture of Silver Azide R.D. 1336 (United States)


    0fricc Scetion Libro ry (3) lifor,,-tion Burc.u (2 + stock) Furthur coupis of this rcport co-n bc 21 toimd from tho Chicf SupLrintndnt, Explosive_s...confirmed and chemical analyses indicate that R.D.1336 is virtually pure silver azide which is to be expected in a process where an additive is not included

  4. Silver-Catalyzed Decarboxylative Radical Azidation of Aliphatic Carboxylic Acids in Aqueous Solution. (United States)

    Liu, Chao; Wang, Xiaoqing; Li, Zhaodong; Cui, Lei; Li, Chaozhong


    We report herein an efficient and general method for the decarboxylative azidation of aliphatic carboxylic acids. Thus, with AgNO3 as the catalyst and K2S2O8 as the oxidant, the reactions of various aliphatic carboxylic acids with tosyl azide or pyridine-3-sulfonyl azide in aqueous CH3CN solution afforded the corresponding alkyl azides under mild conditions. A broad substrate scope and wide functional group compatibility were observed. A radical mechanism is proposed for this site-specific azidation.

  5. Sensitization of High Density Silver Azide to Stab Initiation (United States)


    minimise differential effects of pressing load between compositions, and to study 20:1 admixtures. The grit action of aluminium oxide was also studied, this...and 20:1 silver azide- aluminium oxide readily pressed at 240 MPa then re-pressed at 560 MPa. The effect of grit concentration was investigated for...silicide (entry 3) performs significantly better than aluminium oxide (entry 8) at 20:1 by weight pressed at 560 MPa, despite the much greater hardness

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

    Indian Academy of Sciences (India)



    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.

  7. Azidated Ether-Butadiene-Ether Block Copolymers as Binders for Solid Propellants (United States)

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


    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.

  8. Copper-chelating azides for efficient click conjugation reactions in complex media. (United States)

    Bevilacqua, Valentina; King, Mathias; Chaumontet, Manon; Nothisen, Marc; Gabillet, Sandra; Buisson, David; Puente, Céline; Wagner, Alain; Taran, Frédéric


    The concept of chelation-assisted copper catalysis was employed for the development of new azides that display unprecedented reactivity in the copper(I)-catalyzed azide-alkyne [3+2] cycloaddition (CuAAC) reaction. Azides that bear strong copper-chelating moieties were synthesized; these functional groups allow the formation of azide copper complexes that react almost instantaneously with alkynes under diluted conditions. Efficient ligation occurred at low concentration and in complex media with only one equivalent of copper, which improves the biocompatibility of the CuAAC reaction. Furthermore, such a click reaction allowed the localization of a bioactive compound inside living cells by fluorescence measurements.

  9. Study of selected benzyl azides by UV photoelectron spectroscopy and mass spectrometry (United States)

    Pinto, R. M.; Olariu, R. I.; Lameiras, J.; Martins, F. T.; Dias, A. A.; Langley, G. J.; Rodrigues, P.; Maycock, C. D.; Santos, J. P.; Duarte, M. F.; Fernandez, M. T.; Costa, M. L.


    Benzyl azide and the three methylbenzyl azides were synthesized and characterized by mass spectrometry (MS) and ultraviolet photoelectron spectroscopy (UVPES). The electron ionization fragmentation mechanisms for benzyl azide and their methyl derivatives were studied by accurate mass measurements and linked scans at constant B/ E. For benzyl azide, in order to clarify the fragmentation mechanism, labelling experiments were performed. From the mass analysis of methylbenzyl azides isomers it was possible to differentiate the isomers ortho, meta and para. The abundance and nature of the ions resulting from the molecular ion fragmentation, for the three distinct isomers of substituted benzyl azides, were rationalized in terms of the electronic properties of the substituent. Concerning the para-isomer, IRC calculations were performed at UHF/6-31G(d) level. The photoionization study of benzyl azide, with He(I) radiation, revealed five bands in the 8-21 eV ionization energies region. From every photoelectron spectrum of methylbenzyl azides isomers it has been identified seven bands, on the same range as the benzyl azide. Interpretation of the photoelectron spectra was accomplished applying Koopmans' theorem to the SCF orbital energies obtained at HF/6-311++G(d, p) level.

  10. 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


    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.

  11. Evolving Structural Diversity and Metallicity in Compressed Lithium Azide

    KAUST Repository

    Prasad, Dasari L. V. K.


    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.

  12. 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)


    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.

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

    DEFF Research Database (Denmark)

    Gromov, I; Marchesini, A; Farver, O


    Azide binding to the blue copper oxidases laccase and ascorbate oxidase (AO) was investigated by electron paramagnetic resonance (EPR) and pulsed electron-nuclear double resonance (ENDOR) spectroscopies. As the laccase : azide molar ratio decreases from 1:1 to 1:7, the intensity of the type 2 (T2...

  14. Tylosin and chlortetracycline effects during swine manure digestion: influence of sodium azide. (United States)

    Stone, James J; Clay, Sharon A; Spellman, Garth M


    The antibiotics tylosin and chlortetracycline (CTC), which are commonly used in pig production, were studied to determine their effects on swine manure digestion in the presence and absence of biocide sodium azide. CTC enhanced initial hydrolysis reactions through volatile suspended solids production, while inhibiting methane and carbon dioxide production. Tylosin did not affect methane and carbon dioxide production; however, the relative abundance of both hydrogen utilizing and acetate-only utilizing microbial populations was significantly compromised. Sodium azide in the absence of antibiotics enhanced metabolic output and initial biomass production, and this observation suggests that populations of Methanobacteriales and Methanosaetaceae spp. appeared to contain sufficient periplasmic bound reductase to effectively utilize acetate and hydrogen in the presence of sodium azide. However, the combination of sodium azide and either CTC or tylosin was a very effective metabolic inhibitor, inhibiting methane and carbon dioxide production and VSS consumption compared to their no-azide counterpart.

  15. A DFT study of the mechanism of copper-catalyzed synthesis of 2H-indazoles from aryl azide. (United States)

    Li, Juan; Zhang, Qi; Wu, Caihong; Gu, Honghong; Yan, Bo


    DFT calculations have been performed to study the reaction mechanism of N-N bond formation from aryl azide catalyzed by the copper(I) iodide complex. We studied various activation modes for the azide group, and found that the azide group is activated by the Cu(μ-I)2Cu(TMEDA) dimer coordinating to the N-atom of phenyl imine and the internal N-atom of azide.

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

    Directory of Open Access Journals (Sweden)

    Sharma Anuj


    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.

  17. Electrochemically protected copper(I)-catalyzed azide-alkyne cycloaddition. (United States)

    Hong, Vu; Udit, Andrew K; Evans, Richard A; Finn, M G


    The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction has found broad application in myriad fields. For the most demanding applications that require high yields at low substrate concentrations, highly active but air-sensitive copper complexes must be used. We describe here the use of an electrochemical potential to maintain catalysts in the active Cu(I) oxidation state in the presence of air. This simple procedure efficiently achieves excellent yields of CuAAC products from both small-molecule and protein substrates without the use of potentially damaging chemical reducing agents. A new water-soluble carboxylated version of the popular tris(benzyltriazolylmethyl)amine (TBTA) ligand is also described. Cyclic voltammetry revealed reversible or quasi-reversible electrochemical redox behavior of copper complexes of the TBTA derivative (2; E(1/2)=60 mV vs. Ag/AgCl), sulfonated bathophenanthroline (3; E(1/2)=-60 mV), and sulfonated tris(benzimidazoylmethyl)amine (4; E(1/2) approximately -70 mV), and showed catalytic turnover to be rapid relative to the voltammetry time scale. Under the influence of a -200 mV potential that was established by using a reticulated vitreous carbon working electrode, CuSO4 and 3 formed a superior catalyst. Electrochemically protected bioconjugations in air were performed by using bacteriophage Qbeta that was derivatized with azide moieties at surface lysine residues. Complete derivatization of more than 600 reactive sites per particle was demonstrated within 12 h of electrolysis with substoichiometric quantities of Cu3.

  18. Azide resistance in Rhizobium ciceri linked with superior symbiotic nitrogen fixation. (United States)

    Bhaskar, V Vijay


    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.

  19. Kinetics and mechanism of the reaction of sodium azide with hypochlorite in aqueous solution. (United States)

    Betterton, Eric A; Lowry, Joe; Ingamells, Robin; Venner, Brad


    Production of toxic sodium azide (NaN(3)) surged worldwide over the past two decades to meet the demand for automobile air bag inflator propellant. Industrial activity and the return of millions of inflators to automobile recycling facilities are leading to increasing release of NaN(3) to the environment so there is considerable interest in learning more about its environmental fate. Water soluble NaN(3) could conceivably be found in drinking water supplies so here we describe the kinetics and mechanism of the reaction of azide with hypochlorite, which is often used in water treatment plants. The reaction stoichiometry is: HOCl + 2N(3)(-) = 3N(2) + Cl(-) + OH(-), and proceeds by a key intermediate chlorine azide, ClN(3), which subsequently decomposes by reaction with a second azide molecule in the rate determining step: ClN(3) + N(3)(-) --> 3N(2) + Cl(-) (k = 0.52+/-0.04 M(-1) s(-1), 25 degrees C, mu = 0.1 M). We estimate that the half-life of azide would be approximately 15 s at the point of chlorination in a water treatment plant and approximately 24 days at some point downstream where only residual chlorine remains. Hypochlorite is not recommended for treatment of concentrated azide waste due to formation of the toxic chlorine azide intermediate under acidic conditions and the slow kinetics under basic conditions.

  20. 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.


    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.

  1. Influence of azide incorporation on binding affinity by small papain inhibitors. (United States)

    Wammes, Angelique E M; Hendriks, Tom G; Amatdjais-Groenen, Helene I V; Wijdeven, Marloes A; van Hest, Jan C M; van Delft, Floris L; Ritschel, Tina; Rutjes, Floris P J T


    In order to develop affinity-based biosensor platforms, appropriate ligands with a functional handle for immobilization onto a biosensor surface are required. To this end, a library of papain inhibitors was designed and synthesized, containing different azide linkers for subsequent immobilization by 'click' chemistry, in this particular case by copper-free, strain-promoted azide-alkyne cycloaddition (SPAAC). Furthermore, a molecular docking study was performed to obtain a better insight as to at which position such azide handles could be tolerated without affecting binding affinity. Although the azide moiety is small, in some cases its introduction strongly influenced the binding affinity. For one class of inhibitors a swapped binding mode was proposed to explain the results. In addition, a specific site for linker introduction was identified, which did not significantly affect the binding affinity.

  2. Substitution Reactions by Azide and Thiocyanide Anions in Room Temperature Ionic Liquids

    Institute of Scientific and Technical Information of China (English)


    Conducted in the ionic liquids, activated and inactivated halides, acyl chlorides, tosylate, and bezotriazolyl acylates were converted to corresponding azide and thiocyanide compounds in high yields under mild conditions.

  3. The Relevance of the De Broglie Velocity (V sub 1 = h/2md sub 1) to Shock Loading Induced Reactions in Lead Azide (United States)


    induced reactive pressure levels for dextrinated and single crystal lead azide are compared to predicted Pv1 magnitudes. PV1 = P. CL V1 where V, = h...EXPERIMENTAL REACTIVE SHOCK PRESSURES AND COMPARISON WITH Pv1 PREDICTIONS .................. 4 A. Dextrinated Lead Azide (DLA... Dextrinated Lead Azide (DLA) DLA is a mixture of lead azide and dextrin . Dextrination of lead azide provides han- dling and safety benefits 15, Vol. 2, Chpt

  4. Synthesis of guanidines from azides: a general and straightforward methodology in carbohydrate chemistry. (United States)

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


    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.

  5. Effect of sodium azide on cell processes in the embryonic barley shoot

    Energy Technology Data Exchange (ETDEWEB)

    Pearson, O.W.; Sander, C.; Nilan, R.A.


    Sodium azide has been utilized recently both as an agent for the study of repair of radiation-induced chromosome damage, and as a mutagen in barley caryopses (seeds). However, the effect of this agent on the cell cycle and optimum time of treatment during the cell cycle in these studies is not known. To better understand the effects of sodium azide on the embryonic barley shoot cells, a detailed study of the effect of azide on the cell cycle was conducted. Himalaya barley seeds were treated for 2 hr with 10/sup -4/, 5 x 10/sup -4/, and 10/sup -3/ M oxygenated sodium azide solutions at pH 3. The principal effect on the cell cycle due to sodium azide treatment was a delay in the initiation of metabolism following germination. This resulted in a uniform delay in the following parameters: mitotic activity, seedling growth, and ATP and DNA syntheses. This delay was interpreted as being due to an ATP deficiency which when alleviated allows the cells to progress normally through mitosis. Chromosome damage caused by sodium azide was not reflected in the seedling heights as the reduction in height was due entirely to mitotic delay. No variation occurred in the progression of cells through mitosis between various regions of the shoot within the first 29 hr of germination.

  6. Structural Determinants of Alkyne Reactivity in Copper-Catalyzed Azide-Alkyne Cycloadditions

    Directory of Open Access Journals (Sweden)

    Xiaoguang Zhang


    Full Text Available This work represents our initial effort in identifying azide/alkyne pairs for optimal reactivity in copper-catalyzed azide-alkyne cycloaddition (CuAAC reactions. In previous works, we have identified chelating azides, in particular 2-picolyl azide, as “privileged” azide substrates with high CuAAC reactivity. In the current work, two types of alkynes are shown to undergo rapid CuAAC reactions under both copper(II- (via an induction period and copper(I-catalyzed conditions. The first type of the alkynes bears relatively acidic ethynyl C-H bonds, while the second type contains an N-(triazolylmethylpropargylic moiety that produces a self-accelerating effect. The rankings of reactivity under both copper(II- and copper(I-catalyzed conditions are provided. The observations on how other reaction parameters such as accelerating ligand, reducing agent, or identity of azide alter the relative reactivity of alkynes are described and, to the best of our ability, explained.

  7. Accelerating Strain-Promoted Azide-Alkyne Cycloaddition Using Micellar Catalysis. (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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Yagmurcukardes, M., E-mail:; Senger, R. T., E-mail: [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)


    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.

  9. Copper-catalyzed azide alkyne cycloaddition polymer networks (United States)

    Alzahrani, Abeer Ahmed

    The click reaction concept, introduced in 2001, has since spurred the rapid development and reexamination of efficient, high yield reactions which proceed rapidly under mild conditions. Prior to the discovery of facile copper catalysis in 2002, the thermally activated azide-alkyne or Huisgen cycloaddition reaction was largely ignored following its discovery in large part due to its slow kinetics, requirement for elevated temperature and limited selectivity. Now, arguably, the most prolific and capable of the click reactions, the copper-catalyzed azide alkyne cycloaddition (CuAAC) reaction is extremely efficient and affords exquisite control of the reaction. The orthogonally and chemoselectivity of this reaction enable its wide utility across varied scientific fields. Despite numerous inherent advantages and widespread use for small molecule synthesis and solution-based polymer chemistry, it has only recently and rarely been utilized to form polymer networks. This work focuses on the synthesis, mechanisms, and unique attributes of the CuAAC reaction for the fabrication of functional polymer networks. The photo-reduction of a series of copper(II)/amine complexes via ligand metal charge transfer was examined to determine their relative efficiency and selectivity in catalyzing the CuAAC reaction. The aliphatic amine ligands were used as an electron transfer species to reduce Cu(II) upon irradiation with 365 nm light while also functioning as an accelerating agent and as protecting ligands for the Cu(I) that was formed. Among the aliphatic amines studied, tertiary amines such as triethylamine (TEA), tetramethyldiamine (TMDA), N,N,N',N",N"-pentamethyldiethylenetriamine (PMDTA), and hexamethylenetetramine (HMTETA) were found to be the most effective. The reaction kinetics were accelerated by increasing the PMDETA : Cu(II) ratio with a ratio of ligand to Cu(II) of 4:1 yielding the maximum conversion in the shortest time. The sequential and orthogonal nature of the photo

  10. Azide as a competitor of chloride in oxygen evolution by Photosystem II. (United States)

    Haddy, A; Hatchell, J A; Kimel, R A; Thomas, R


    Oxygen evolution by higher plants requires chloride, which binds to a site associated with the oxygen-evolving complex of photosystem II (PSII). In this study, the inhibitory effect of the anion azide was characterized using steady state measurements of oxygen evolution activity in PSII-enriched thylakoid membranes. N3- (7.8 mM) inhibited O2 evolution activity by 50% when a standard buffer containing chloride was used. By considering Cl- as the substrate in O2 evolution assays, we found azide to be primarily competitive with Cl- with an inhibitor dissociation constant Ki of about 0.6 mM. An uncompetitive component with a Ki ' of 11 mM was also found. Removal of the 17 and 23 kDa polypeptides resulted in a decrease in each inhibition constant. A pH dependence study of O2 evolution activity showed that the pH maximum became narrower and shifted to a higher pH in the presence of azide. Analysis of the data indicated that an acidic residue defined the low side of the pH maximum with an apparent pKa of 6.7 in the presence of azide compared with 5.5 for the control. A basic residue was also affected, exhibiting an apparent pKa of 7.1 compared with a value of 7.6 for the control. This result can be explained by a simple model in which azide binding to the chloride site moves negative charge of the anion away from the basic residue and toward the acidic residue relative to chloride. As a competitor of chloride, azide may provide an interesting probe of the oxygen-evolving complex in future studies.

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

  12. Coulometric determination of dithiphosphates with the use of the induced iodine-azide reaction


    Ciesielski, Witold; Jędrzejewski, Włodzimierz


    The characteristics of potassium diethyl- and dibuthyldithiophosphates as the inductors of iodine-azide reaction carried out electrolytically have been presented. The influence of the pH and concentrations of azide and iodide ions on the course of reaction was examined. The determinations have been carried out in the range of 1-20 nmol. Przedstawiono charakterystykę dietylo- i dibutyloditiofosforanów jako induktorów reakcji jodo-azydkowej. Zbadano wpływ pH oraz stężeń azy...

  13. Synthesis of radiolabelled aryl azides from diazonium salts: experimental and computational results permit the identification of the preferred mechanism. (United States)

    Joshi, Sameer M; de Cózar, Abel; Gómez-Vallejo, Vanessa; Koziorowski, Jacek; Llop, Jordi; Cossío, Fernando P


    Experimental and computational studies on the formation of aryl azides from the corresponding diazonium salts support a stepwise mechanism via acyclic zwitterionic intermediates. The low energy barriers associated with both transition structures are compatible with very fast and efficient processes, thus making this method suitable for the chemical synthesis of radiolabelled aryl azides.

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


    NARCIS (Netherlands)

    Wijnen, J.W; Steiner, R.A.; Engberts, J.B.F.N.


    Second-order rate constants for the cycloaddition of phenyl azide to norbornene were determined in aqueous solutions. In organic solvents this reaction shows a very small solvent effect. In highly aqueous media, however, remarkable accelerations are observed. The solvent dependence of the rate const

  16. Reaction-based azide gas sensing with tailored ionic liquids measured by quartz crystal microbalance. (United States)

    Tseng, Ming-Chung; Chu, Yen-Ho


    On the basis of the strain-promoted [3 + 2] cycloaddition reaction performed at ambient temperature, a label-free, online, and chemospecific gas-phase measurement of organic azides in real time was efficiently achieved on QCM chips thin-coated with tailored ionic liquid TIL 1.

  17. Determination of primary explosive azides in environmental samples by sequential injection amperometry.

    Energy Technology Data Exchange (ETDEWEB)

    Echols, R. T.; James, R. R.; Aldstadt, J. H.; Environmental Research; Univ.of Minnesota; Univ of Minnesota


    The application of flow injection methodology to the determination of trace concentrations of primary explosives is presented. The approach is demonstrated with a sequential injection amperometric method for the determination of the azide ion (N{sub 3}{sup -}). The proposed method can be applied to the determination of sodium azide or lead azide, a primary explosive, without regard to other sources of lead in environmental samples. The sequential injection system used for the analysis forms the basis for a proposed field-portable instrument for the analysis of primary explosives. A microporous gas permeable membrane in a gas diffusion unit (GDU) is used to separate the analyte from other anions that can also be oxidized at the amperometric cell. The behavior of the GDU was optimized with respect to the pH of the donor stream and the timing of the preconcentration step. A study of anions that are commonly found in environmental samples showed that the species that will interfere with the analytical signal can be removed by the GDU. Results from three water samples that were spiked with 0.40 ppm of azide are presented. RSDs in the range 3-5% were typically obtained using the method. The useful working range of the method was linear up to 0.5 ppm and non-linear up to 20 ppm (second-order model). The limit of detection was 24.6 ppb.

  18. Inhibitory effects of sodium azide on microbial growth in experimental resuspension of marine sediment. (United States)

    Cabrol, Léa; Quéméneur, Marianne; Misson, Benjamin


    Sodium azide (NaN3) was evaluated as inhibitor of microbial growth and activity in marine sediment resuspensions by monitoring the abundance of free-living and sessile bacteria using both flow cytometry and qPCR methods. Results show that 50mM of NaN3 strongly inhibits bacterial growth under natural and enriched resource conditions.

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

    DEFF Research Database (Denmark)

    Jepsen, Tue Heesgaard; Kristensen, Jesper Langgaard


    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...

  20. Copper-free 'click' : 1,3-dipolar cycloaddition of azides and arynes

    NARCIS (Netherlands)

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


    Arynes formed through fluoride-promoted ortho-elimination of o-(trimethylsilyl)aryl triflates can undergo [3 + 2] cycloaddition with various azides to form substituted benzotriazoles. The rapid reaction times and mild conditions make this an attractive variation of the classical 'click' reaction of

  1. 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.


    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

  2. clickECM: Development of a cell-derived extracellular matrix with azide functionalities. (United States)

    Ruff, S M; Keller, S; Wieland, D E; Wittmann, V; Tovar, G E M; Bach, M; Kluger, P J


    In vitro cultured cells produce a complex extracellular matrix (ECM) that remains intact after decellularization. The biological complexity derived from the variety of distinct ECM molecules makes these matrices ideal candidates for biomaterials. Biomaterials with the ability to guide cell function are a topic of high interest in biomaterial development. However, these matrices lack specific addressable functional groups, which are often required for their use as a biomaterial. Due to the biological complexity of the cell-derived ECM, it is a challenge to incorporate such functional groups without affecting the integrity of the biomolecules within the ECM. The azide-alkyne cycloaddition (click reaction, Huisgen-reaction) is an efficient and specific ligation reaction that is known to be biocompatible when strained alkynes are used to avoid the use of copper (I) as a catalyst. In our work, the ubiquitous modification of a fibroblast cell-derived ECM with azides was achieved through metabolic oligosaccharide engineering by adding the azide-modified monosaccharide Ac4GalNAz (1,3,4,6-tetra-O-acetyl-N-azidoacetylgalactosamine) to the cell culture medium. The resulting azide-modified network remained intact after removing the cells by lysis and the molecular structure of the ECM proteins was unimpaired after a gentle homogenization process. The biological composition was characterized in order to show that the functionalization does not impair the complexity and integrity of the ECM. The azides within this "clickECM" could be accessed by small molecules (such as an alkyne-modified fluorophore) or by surface-bound cyclooctynes to achieve a covalent coating with clickECM.

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

    Energy Technology Data Exchange (ETDEWEB)

    Rosen, R.K.


    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}.

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

    Directory of Open Access Journals (Sweden)

    Živković Suzana


    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.

  5. 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


    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.

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

    KAUST Repository

    Johansson, Johan R.


    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.

  7. 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


    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.

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

    Directory of Open Access Journals (Sweden)

    Perakis F.


    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.

  9. Investigation of Analytical Techniques for the Rapid Determination of the Moisture Content of NOL 130 Primer Mix and Lead Azide (United States)


    the presence of NOL 130 6 Determination of moisture content of dextrinated lead azide 14 containing known amounts of water, by the Karl Fisher method...maLhiod, extraction mode 8 Determinatiov) of moisture content of special purpose and 16 dextrinated lead atide, containing known amounts of water by the...water in special purpose and dextrinated lead azides were determined by the method described in the experimen- tal section of this report, data shown

  10. Intramolecular azide to alkene cycloadditions for the construction of pyrrolobenzodiazepines and azetidino-benzodiazepines. (United States)

    Hemming, Karl; Chambers, Christopher S; Jamshaid, Faisal; O'Gorman, Paul A


    The coupling of proline- and azetidinone-substituted alkenes to 2-azidobenzoic and 2-azidobenzenesulfonic acid gives precursors that undergo intramolecular azide to alkene 1,3-dipolar cycloadditions to give imine-, triazoline- or aziridine-containing pyrrolo[1,4]benzodiazepines (PBDs), pyrrolo[1,2,5]benzothiadiazepines (PBTDs), and azetidino[1,4]benzodiazepines. The imines and aziridines are formed after loss of nitrogen from a triazoline cycloadduct. The PBDs are a potent class of antitumour antibiotics.

  11. Intramolecular Azide to Alkene Cycloadditions for the Construction of Pyrrolobenzodiazepines and Azetidino-Benzodiazepines

    Directory of Open Access Journals (Sweden)

    Karl Hemming


    Full Text Available The coupling of proline- and azetidinone-substituted alkenes to 2-azidobenzoic and 2-azidobenzenesulfonic acid gives precursors that undergo intramolecular azide to alkene 1,3-dipolar cycloadditions to give imine-, triazoline- or aziridine-containing pyrrolo[1,4]benzodiazepines (PBDs, pyrrolo[1,2,5]benzothiadiazepines (PBTDs, and azetidino[1,4]benzodiazepines. The imines and aziridines are formed after loss of nitrogen from a triazoline cycloadduct. The PBDs are a potent class of antitumour antibiotics.

  12. Sensitivity of Lead Azide to Electric Spark (Chuvstvitelnost Azida Svintsa k Elektricheskoi Iskre) (United States)


    On supplying a voltage pulse to the Incendiary electrode of the triple - electrode v.clay P, it operated, one of the specimen electrodes got connected...azide to electric spark. Substances which can cover particles of explosive materials (paraffin, ceresin, wax, castor oil, camphor , etc.) are often...modern concepts, excitation of explosion in an explo- sive material leads to the formation of "hot points " and to thermal trigger- ing. Increase of

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

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


    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

  14. Functionalization of Graphene Nanoplatelets Using Sugar Azide for Graphene/Epoxy Nanocomposites (United States)


    cell according to the ASTM D790. The morphology of the fracture surface was observed by Scanning electron microscopy (Carl Zeiss Varible Pressure...SEM EVO LS25). Samples were sputter-coated with tungsten prior to their SEM observation. 3. Proposed Mechanism Sugar azide (SA), a highly reactive...SEM Fractured surfaces (from flexural tests) of neat epoxy and epoxy nanocomposites were investigated by SEM and the micrographs are presented in

  15. 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


    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.

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

    Directory of Open Access Journals (Sweden)

    Stefanie Wolfram


    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.

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

    Directory of Open Access Journals (Sweden)

    Timothy W. Schmidt


    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.

  18. The decomposition of benzenesulfonyl azide: a matrix isolation and computational study. (United States)

    Deng, Guohai; Dong, Xuelin; Liu, Qifan; Li, Dingqing; Li, Hongmin; Sun, Qiao; Zeng, Xiaoqing


    The thermal-decomposition and photo-decomposition of benzenesulfonyl azide, PhS(O)2N3, have been studied by combining matrix-isolation IR spectroscopy and quantum chemical calculations. Upon flash vacuum pyrolysis at 800 K, the azide splits off molecular nitrogen and exclusively furnishes phenylnitrene (PhN) and SO2 in the gas phase. In contrast, the azide favors stepwise photodecomposition in solid Ar and Ne matrices at 2.8 K. Specifically, the UV laser photolysis (193 and 266 nm) of PhS(O)2N3 results in the formation of the key nitrene intermediate PhS(O)2N in the triplet ground state, which undergoes pseudo-Curtius rearrangement into N-sulfonyl imine PhNSO2 under subsequent visible light irradiation (380-450 nm). Further fragmentation of PhNSO2 into SO2 and PhN followed by ring-expansion to didehydroazepine also occurs upon visible light irradiation. The preference of the stepwise mechanism for the decomposition of PhS(O)2N3 is supported by quantum chemical calculations using DFT B3LYP/6-311++G(3df,3pd) and CBS-QB3 methods.

  19. Pressure-accelerated azide-alkyne cycloaddition: micro capillary versus autoclave reactor performance. (United States)

    Borukhova, Svetlana; Seeger, Andreas D; Noël, Timothy; Wang, Qi; Busch, Markus; Hessel, Volker


    Pressure effects on regioselectivity and yield of cycloaddition reactions have been shown to exist. Nevertheless, high pressure synthetic applications with subsequent benefits in the production of natural products are limited by the general availability of the equipment. In addition, the virtues and limitations of microflow equipment under standard conditions are well established. Herein, we apply novel-process-window (NPWs) principles, such as intensification of intrinsic kinetics of a reaction using high temperature, pressure, and concentration, on azide-alkyne cycloaddition towards synthesis of Rufinamide precursor. We applied three main activation methods (i.e., uncatalyzed batch, uncatalyzed flow, and catalyzed flow) on uncatalyzed and catalyzed azide-alkyne cycloaddition. We compare the performance of two reactors, a specialized autoclave batch reactor for high-pressure operation up to 1800 bar and a capillary flow reactor (up to 400 bar). A differentiated and comprehensive picture is given for the two reactors and the three methods of activation. Reaction speedup and consequent increases in space-time yields is achieved, while the process window for favorable operation to selectively produce Rufinamide precursor in good yields is widened. The best conditions thus determined are applied to several azide-alkyne cycloadditions to widen the scope of the presented methodology.

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

    Directory of Open Access Journals (Sweden)

    Ting Huang


    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.

  1. Functionalisation of lanthanide complexes via microwave-enhanced Cu(I)-catalysed azide-alkyne cycloaddition. (United States)

    Szíjjártó, Csongor; Pershagen, Elias; Borbas, K Eszter


    Cu(I)-catalysed azide-alkyne cycloaddition reactions were used to functionalise lanthanide(III)-complexes (Ln; La, Eu and Tb) incorporating alkyne or azide reactive groups. Microwave irradiation significantly accelerated the reactions, enabling full conversion to the triazole products in some cases in 5 min. Alkyl and aryl azides and alkyl and aryl alkynes could all serve as coupling partners. These reaction conditions proved efficient for cyclen-tricarboxylates and previously unreactive cyclen-tris-primary amide chelates. The synthesis of heterobimetallic (Eu/Tb, EuTb17 and Eu/La, EuLa17) and heterotrimetallic (Eu/La/Eu) complexes was achieved in up to 60% isolated yield starting from coumarin 2-appended alkynyl complexes Tb16 or La16 and an azido-Eu complex Eu4, and bis-alkynyl La-complex La5 and Eu4, respectively. EuTb17 displayed dual Eu(III) and Tb(III)-emission upon antenna-centred excitation.

  2. Biocompatible Azide-Alkyne "Click" Reactions for Surface Decoration of Glyco-Engineered Cells. (United States)

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


    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.

  3. Millimeter-wave spectroscopy of syn formyl azide (HC(O)N3) in seven vibrational states (United States)

    Walters, Nicholas A.; Amberger, Brent K.; Esselman, Brian J.; Woods, R. Claude; McMahon, Robert J.


    Millimeter-wave spectra for formyl azide (HC(O)N3) were obtained from 240 to 360 GHz at ambient temperature. For the ground state of syn formyl azide, over 1500 independent rotational transitions were measured and least-squares fit to a complete S-reduced 8th order centrifugal distortion/rigid rotor Hamiltonian. The decomposition of formyl azide was monitored over a period of several hours, the half-life (t½ = 30 min) was determined, and its decomposition products were investigated. Transitions from five vibrational satellites of syn formyl azide (ν9, ν12, 2ν9, ν9 + ν12, and ν11) were observed, measured, and least-squares fit to complete or nearly complete octic centrifugally-distorted, single-state S-reduced models. A less complete single-state fit of 3ν9 (509.3 cm-1) was obtained from an unperturbed subset of its assignable transitions. This state is apparently coupled to the fundamental ν8 (489.4 cm-1) and the overtone 2ν12 (503.6 cm-1), but the coupling remains unanalyzed. Anharmonic CCSD(T)/ANO1 estimates of the vibrational frequencies of syn formyl azide were in close agreement with previously published experimental and computational values. Experimentally determined vibration-rotation interaction (αi) values were in excellent agreement with coupled-cluster predicted αi values for the fundamentals ν9, ν12, and ν11.

  4. Azide anions inhibit GH-18 endochitinase and GH-20 Exo β-N-acetylglucosaminidase from the marine bacterium Vibrio harveyi. (United States)

    Sirimontree, Paknisa; Fukamizo, Tamo; Suginta, Wipa


    Vibrio harveyi is a bioluminescent marine bacterium that utilizes chitin as its sole source of energy. In the course of chitin degradation, the bacterium primarily secretes an endochitinase A (VhChiA) to hydrolyze chitin, generating chitooligosaccharide fragments that are readily transported into the cell and broken down to GlcNAc monomers by an exo β-N-acetylglucosaminidase (VhGlcNAcase). Here we report that sodium salts, especially sodium azide, inhibit two classes of these chitin-degrading enzymes (VhChiA and VhGlcNAcase) with distinct modes of action. Kinetic analysis of the enzymatic hydrolysis of pNP-glycoside substrates reveals that sodium azide inhibition of VhChiA has a mixed-type mode, but that it inhibits VhGlcNAcase competitively. We propose that azide anions inhibit chitinase activity by acting as strong nucleophiles that attack Cγ of the catalytic Glu or Cβ of the neighbouring Asp residues. Azide anions may bind not only to the catalytic centre, but also to the other subsites in the substrate-binding cleft of VhChiA. In contrast, azide anions may merely occupy the small-binding pocket of VhGlcNAcase, thereby blocking the accessibility of its active site by short-chain substrates.

  5. Bone marrow cells stained by azide-conjugated Alexa fluors in the absence of an alkyne label. (United States)

    Lin, Guiting; Ning, Hongxiu; Banie, Lia; Qiu, Xuefeng; Zhang, Haiyang; Lue, Tom F; Lin, Ching-Shwun


    Thymidine analog 5-ethynyl-2'-deoxyuridine (EdU) has recently been introduced as an alternative to 5-bromo-2-deoxyuridine (BrdU) for cell labeling and tracking. Incorporation of EdU into replicating DNA can be detected by azide-conjugated fluors (eg, Alexa-azide) through a Cu(i)-catalyzed click reaction between EdU's alkyne moiety and azide. While this cell labeling method has proven to be valuable for tracking transplanted stem cells in various tissues, we have found that some bone marrow cells could be stained by Alexa-azide in the absence of EdU label. In intact rat femoral bone marrow, ~3% of nucleated cells were false-positively stained, and in isolated bone marrow cells, ~13%. In contrast to true-positive stains, which localize in the nucleus, the false-positive stains were cytoplasmic. Furthermore, while true-positive staining requires Cu(i), false-positive staining does not. Reducing the click reaction time or reducing the Alexa-azide concentration failed to improve the distinction between true- and false-positive staining. Hematopoietic and mesenchymal stem cell markers CD34 and Stro-1 did not co-localize with the false-positively stained cells, and these cells' identity remains unknown.

  6. Bis[2-(8-quinolyliminomethylphenolato-κ3N,N′,O]iron(III azide

    Directory of Open Access Journals (Sweden)

    Yoshihiro Kojima


    Full Text Available The title compound, [Fe(C16H11N2O2]N3, consists of a [Fe(qsal2]+ cation [Hqsal = N-(8-quinolylsalicylaldimine] and an azide anion. The FeIII ion, lying on a twofold rotation axis, is coordinated by four N atoms and two O atoms from two tridentate qsal ligands in an octahedral geometry. The molecules are connected into a three-dimensional network by intermolecular C—H...N and C—H...O interactions. π–π interactions [interplanar distance = 3.58 (1 Å] between the quinoline rings of adjacent molecules further stabilize the crystal structure.

  7. 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


    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.

  8. Ring opening of donor-acceptor cyclopropanes with the azide ion: a tool for construction of N-heterocycles. (United States)

    Ivanov, Konstantin L; Villemson, Elena V; Budynina, Ekaterina M; Ivanova, Olga A; Trushkov, Igor V; Melnikov, Mikhail Ya


    A general method for ring opening of various donor-acceptor cyclopropanes with the azide ion through an SN 2-like reaction has been developed. This highly regioselective and stereospecific process proceeds through nucleophilic attack on the more-substituted C2 atom of a cyclopropane with complete inversion of configuration at this center. Results of DFT calculations support the SN 2 mechanism and demonstrate good qualitative correlation between the relative experimental reactivity of cyclopropanes and the calculated energy barriers. The reaction provides a straightforward approach to a variety of polyfunctional azides in up to 91 % yield. The high synthetic utility of these azides and the possibilities of their involvement in diversity-oriented synthesis were demonstrated by the developed multipath strategy of their transformations into five-, six-, and seven-membered N-heterocycles, as well as complex annulated compounds, including natural products and medicines such as (-)-nicotine and atorvastatin.

  9. Sodium Azide (United States)

    ... too. Seal the bag, and then seal that bag inside another plastic bag. Disposing of your clothing in this way will ... arrange for further disposal. Do not handle the plastic bags yourself. For more information about cleaning your body ...

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

    Indian Academy of Sciences (India)

    G Vaitheeswaran; K Ramesh Babu


    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.

  11. Why do p-nitro-substituted aryl azides provide unintended dark reactions with proteins? (United States)

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


    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.

  12. White emitting polyfluorene functionalized with azide hybridized on near-UV light emitting diode for high color rendering index. (United States)

    Huyal, Ilkem Ozge; Ozel, Tuncay; Koldemir, Unsal; Nizamoglu, Sedat; Tuncel, Donus; Demir, Hilmi Volkan


    We develop and demonstrate high-quality white light generation that relies on the use of a single-type simple conjugated polymer of polyfluorene functionalized with azide groups (PFA) integrated on a near-UV LED platform. The high-quality white emission from the polyfluorene is achieved by using the azide functionalization to facilitate cross-linking intentionally when cast into solid-state form. Hybridized on n-UV InGaN/GaN LED at 378 nm, the PFA emitters collectively generate a very broad down-converting photoluminescence at longer wavelengths across the entirety of the visible spectrum, yielding high color rendering indices up to 91.

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

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


    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. Conjugation of transferrin to azide-modified CdSe/ZnS core-shell quantum dots using cyclooctyne click chemistry. (United States)

    Schieber, Christine; Bestetti, Alessandra; Lim, Jet Phey; Ryan, Anneke D; Nguyen, Tich-Lam; Eldridge, Robert; White, Anthony R; Gleeson, Paul A; Donnelly, Paul S; Williams, Spencer J; Mulvaney, Paul


    Twinkle twinkle quantum dot: Conjugation of biomolecules to azide-modified quantum dots (QDs) through a bifunctional linker, using strain-promoted azide-alkyne cycloaddition with the QD and a squaramide linkage to the biomolecule (see scheme). Transferrin-conjugated QDs were internalized by transferrin-receptor expressing HeLa cells.

  15. Development of a general methodology for labelling peptide-morpholino oligonucleotide conjugates using alkyne-azide click chemistry. (United States)

    Shabanpoor, Fazel; Gait, Michael J


    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.

  16. 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


    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-triazoles...

  17. A metal-free turn-on fluorescent probe for the fast and sensitive detection of inorganic azides

    NARCIS (Netherlands)

    Wang, Ke; Friscourt, Frédéric; Dai, Chaofeng; Wang, Lifang; Zheng, Yueqin; Boons, Geert-Jan; Wang, Siming; Wang, Binghe


    Sodium azide is toxic and widely used in agricultural, commercial products, and research laboratories. Thus it is of a significant environmental concern and there is a need for the development of a rapid detection method. A fluorogenic dibenzylcyclooctyne derivative (Fl-DIBO) is herein described as


    Directory of Open Access Journals (Sweden)

    I Gusti Agung Eka Saraswati


    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

  19. Highly efficient coupling of beta-substituted aminoethane sulfonyl azides with thio acids, toward a new chemical ligation reaction. (United States)

    Merkx, Remco; Brouwer, Arwin J; Rijkers, Dirk T S; Liskamp, Rob M J


    [reaction: see text] A highly efficient coupling of protected beta-substituted aminoethane sulfonyl azides with thio acids is reported. In the case of peptide thio acids, this method encompasses a new chemoselective ligation method. Furthermore, the resulting alpha-amino acyl sulfonamides can be alkylated with suitable electrophiles to obtain densely functionalized sulfonamide scaffolds.

  20. A biomolecule-compatible visible-light-induced azide reduction from a DNA-encoded reaction-discovery system. (United States)

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


    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.

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

    KAUST Repository

    Hou, Duenren


    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.

  2. Hybrid NS ligands supported Cu(I)/(II) complexes for azide-alkyne cycloaddition reactions. (United States)

    Bai, Shi-Qiang; Jiang, Lu; Zuo, Jing-Lin; Hor, T S Andy


    Three copper complexes of nitrogen-sulfur donor ligands, [CuBr₂(L1)] (1), [CuCl₂(L2)₂] (2) and [Cu₂I₂(L3)]n (3) (L1 = bis(2-cyclohexylsulfanylethyl)amine, L2 = 2-(benzylsulfanylmethyl)pyridine and L3 = 2-(4-pyridylsulfanylmethyl)pyridine), have been synthesized and characterized by single-crystal X-ray diffraction (XRD), powder XRD and TGA analysis. Complexes 1 and 2 are mononuclear Cu(II) complexes and are EPR active with distorted square-pyramidal and octahedral geometry, respectively. Complex 3 is a two-dimensional tetrahedral Cu(I) coordination polymer with 16- and 20-membered metallocycles. These complexes show good catalytic activities for one-pot azide-alkyne cycloaddition reactions in CH₃OH-H₂O.

  3. Solvent-free copper-catalyzed azide-alkyne cycloaddition under mechanochemical activation. (United States)

    Rinaldi, Laura; Martina, Katia; Baricco, Francesca; Rotolo, Laura; Cravotto, Giancarlo


    The ball-mill-based mechanochemical activation of metallic copper powder facilitates solvent-free alkyne-azide click reactions (CuAAC). All parameters that affect reaction rate (i.e., milling time, revolutions/min, size and milling ball number) have been optimized. This new, efficient, facile and eco-friendly procedure has been tested on a number of different substrates and in all cases afforded the corresponding 1,4-disubstituted 1,2,3-triazole derivatives in high yields and purities. The final compounds were isolated in almost quantitative overall yields after simple filtration, making this procedure facile and rapid. The optimized CuAAC protocol was efficiently applied even with bulky functionalized β-cyclodextrins (β-CD) and scaled-up to 10 g of isolated product.

  4. Solvent-Free Copper-Catalyzed Azide-Alkyne Cycloaddition under Mechanochemical Activation

    Directory of Open Access Journals (Sweden)

    Laura Rinaldi


    Full Text Available The ball-mill-based mechanochemical activation of metallic copper powder facilitates solvent-free alkyne-azide click reactions (CuAAC. All parameters that affect reaction rate (i.e., milling time, revolutions/min, size and milling ball number have been optimized. This new, efficient, facile and eco-friendly procedure has been tested on a number of different substrates and in all cases afforded the corresponding 1,4-disubstituted 1,2,3-triazole derivatives in high yields and purities. The final compounds were isolated in almost quantitative overall yields after simple filtration, making this procedure facile and rapid. The optimized CuAAC protocol was efficiently applied even with bulky functionalized β-cyclodextrins (β-CD and scaled-up to 10 g of isolated product.

  5. Exploring the flexible chemistry of 4-fluoro-3-nitrophenyl azide for biomolecule immobilization and bioconjugation. (United States)

    Kumar, Saroj; Kumar, Dileep; Ahirwar, Rajesh; Nahar, Pradip


    Bioconjugation and functionalization of polymer surfaces are two major tasks in materials chemistry which are accomplished using a variety of coupling agents. Immobilization of biomolecules onto polymer surfaces and the construction of bioconjugates are essential requirements of many biochemical assays and chemical syntheses. Different linkers with a variety of functional groups are used for these purposes. Among them, the benzophenones, aryldiazirines, and arylazides represent the most commonly used photolinker to produce the desired chemical linkage upon their photo-irradiation. In this review, we describe the versatile applications of 4-fluoro-3-nitrophenyl azide, one of the oldest photolinkers used for photoaffinity labeling in the late 1960s. Surprisingly, this photolinker, historically known as 1-fluoro-2-nitro-4-azidobenzene (FNAB), has remained unexplored for a long time because of apprehension that FNAB forms ring-expanded dehydroazepine as a major product and hence cannot activate an inert polymer. The first evidence of photochemical activation of an inert surface by FNAB through nitrene insertion reaction was reported in 2001, and the FNAB-activated surface was found to conjugate a biomolecule without any catalyst, reagent, or modification. FNAB has distinct advantages over perfluorophenyl azide derivatives, which are contemporary nitrene-generating photolinkers, because of its simple, single-step preparation and ease of thermochemical and photochemical reactions with versatile polymers and biomolecules. Covering these aspects, the present review highlights the flexible chemistry of FNAB and its applications in the field of surface engineering, immobilization of biomolecules such as antibodies, enzymes, cells, carbohydrates, oligonucleotides, and DNA aptamers, and rapid diagnostics. Graphical Abstract An overview of the FNAB-engineered activated polymer surfaces for covalent ligation of versatile biomolecules.

  6. Finding new equilibria: Directed synthesis of lanthanide materials via sodium azide mediated pathways (United States)

    Moore, Brian Freeman

    This dissertation covers the synthesis and characterization of three unique classes of lanthanide materials produced exclusively by the addition of sodium azide (NaN3) into solution based lanthanide reactions. The products were achieved through transmetallation and redox reactions between rare earth chalcogenolate reagents (Lnx(EPh)y), NaN 3 and elemental chalcogenides (E = O, S, Se, Te). The products displayed atypical structural and physical properties including; unique coordination geometries, high nuclearities, tunable detonation/deflagration, strong NIR emissions, and unexpected magnetic ordering behaviors. The introduction of NaN3, Na2O, Cd, elemental Se and Te into Ln (EPh)2 and Ln(EPh)3 pyridine (py) solutions led to the production of (py) 2Na2(EPh)2 and 5 structurally distinct azide encapsulated rare earth clusters; (Py) 10Sm6O2(N3)16Na2, (py)8Ln6O2(N3)12(SePh) 2, (py)10Ln6O2(Se2) 2(N3)10 (Ln=Er, Ho), and (py)16Sm 8Se(O2)Na2(Te2)6(N 3)8. Each system was encapsulated by a variety of azide bridging moieties, while exhibiting a [Ln]/[N3] dependent correlation with detonation and deflagration temperatures. The inclusion of NaN3 in Ln(SePh)3 pyridine solutions with elemental Se, led to the discovery of the (py)16Ln17 NaSe18(SePh)16; (Ln= Ce, Pr, and Nd). Emission studies of the Nd17 analogue, revealed a 35% quantum efficiency for the 4F3/2 - 4I11/2 transition (1070 nm emission), and a near solid state emission intensity for the 4F3/2 → 4I15/2 transition (1822 nm emission). The novel Eu(EPh)4Na2•2DME; (E=S,Se), specimens were synthesized by the combination of Eu(EPh)2 with NaN3 in dimethoxyethane (DME). The europium coordination sphere was solvent free and resembles the coordinations of europium monochalcogenides (EuE). Comparative structural analysis and magnetic susceptibility studies of the Eu3+ product, ((py)6Eu2(mu4-S 2)2(OC6F5)2) revealed paramagnetic ordering at low temperature for Eu(EPh)4Na2•2DME; (E=S,Se), while ferrimagnetic ordering was found

  7. Effect of glutathione L-cystein and L-djenkolic acid in the synthesis and mutagenicity of azide metabolite in Bacillus subtilis ATCC 6633 strain. (United States)

    Elbetieha, A; Owais, W M; Saadoun, I; Hussein, E


    The Bacillus subtilis ATCC 6633 strain synthesizes a mutagenic metabolite from sodium azide and O-acetylserine. Mutagenicity of azide was decreased in growth media containing 10(-4) M glutathione, L-cysteine or L-djenkolic acid whereas dithiothritol (DTT) added at the same concentration did not reduce the mutagenicity of azide. Likewise, glutathione, L-cysteine, L-djenkolic acid, and DTT were found to have no effect in reducing the mutagenicity of the in vitro produced metabolite using bacterial cell-free extract. These results suggest that O-acetyl-serine sulfhydrylase catalyzes the reaction of azide and O-acetylserine to form a mutagenic metabolite, which is ninhydrin positive and migrates in TLC to an Rf value similar to that of azidoalanine in both acidic and basic solvent systems.

  8. Ionic liquids/[bmim][N3] mixtures: promising media for the synthesis of aryl azides by SNAr. (United States)

    D'Anna, Francesca; Marullo, Salvatore; Noto, Renato


    The nucleophilic aromatic substitution of some activated aryl or heteroaryl halides has been performed in ionic liquid solution, using the 1-butyl-3-methylimidazolium azide as a nucleophile. The reaction course was studied varying the structures of both substrates and ionic liquids. In particular, in the latter case, the reaction of 2-bromo-5-nitrothiophene was carried out in five different ionic liquids ([bmim][BF 4], [bmim][PF 6], [bmim][NTf 2], [bm 2im][NTf 2], and [bmpyrr][NTf 2]). Finally, for all the substrates considered, a comparison with data obtained in MeOH solution in the presence of NaN 3 was also performed. Data collected indicate that in some cases it is possible to obtain aromatic or heteroaromatic azide derivatives in satisfactory yield by means of a S NAr reaction using [bmim][N 3] as the nucleophile.

  9. "Bis-Click" Ligation of DNA: Template-Controlled Assembly, Circularisation and Functionalisation with Bifunctional and Trifunctional Azides. (United States)

    Yang, Haozhe; Seela, Frank


    Ligation and circularisation of oligonucleotides containing terminal triple bonds was performed with bifunctional or trifunctional azides. Both reactions are high yielding. Template-assisted bis-click ligation of two individual non-complementary oligonucleotide strands was accomplished to yield heterodimers exclusively. In this context, the template fulfils two functions: it accelerates the ligation reaction and controls product assembly (heterodimer vs. homodimer formation). Intermolecular bis-click circularisation of one oligonucleotide strand took place without template assistance. For construction of oligonucleotides with terminal triple bonds in the nucleobase side chain, 7- or 5-functionalised 7-deaza-dA and dU residues were used. These oligonucleotides are directly accessible by solid-phase synthesis. When trifunctional azides were employed instead of bifunctional linkers, functionalisation of the remaining azido group was performed with small molecules such as 1-ethynyl pyrene, biotin propargyl amide or with ethynylated oligonucleotides. By this means, branched DNA was constructed.

  10. Ribosome-Templated Azide-Alkyne Cycloadditions: Synthesis of Potent Macrolide Antibiotics by In Situ Click Chemistry. (United States)

    Glassford, Ian; Teijaro, Christiana N; Daher, Samer S; Weil, Amy; Small, Meagan C; Redhu, Shiv K; Colussi, Dennis J; Jacobson, Marlene A; Childers, Wayne E; Buttaro, Bettina; Nicholson, Allen W; MacKerell, Alexander D; Cooperman, Barry S; Andrade, Rodrigo B


    Over half of all antibiotics target the bacterial ribosome-nature's complex, 2.5 MDa nanomachine responsible for decoding mRNA and synthesizing proteins. Macrolide antibiotics, exemplified by erythromycin, bind the 50S subunit with nM affinity and inhibit protein synthesis by blocking the passage of nascent oligopeptides. Solithromycin (1), a third-generation semisynthetic macrolide discovered by combinatorial copper-catalyzed click chemistry, was synthesized in situ by incubating either E. coli 70S ribosomes or 50S subunits with macrolide-functionalized azide 2 and 3-ethynylaniline (3) precursors. The ribosome-templated in situ click method was expanded from a binary reaction (i.e., one azide and one alkyne) to a six-component reaction (i.e., azide 2 and five alkynes) and ultimately to a 16-component reaction (i.e., azide 2 and 15 alkynes). The extent of triazole formation correlated with ribosome affinity for the anti (1,4)-regioisomers as revealed by measured Kd values. Computational analysis using the site-identification by ligand competitive saturation (SILCS) approach indicated that the relative affinity of the ligands was associated with the alteration of macrolactone+desosamine-ribosome interactions caused by the different alkynes. Protein synthesis inhibition experiments confirmed the mechanism of action. Evaluation of the minimal inhibitory concentrations (MIC) quantified the potency of the in situ click products and demonstrated the efficacy of this method in the triaging and prioritization of potent antibiotics that target the bacterial ribosome. Cell viability assays in human fibroblasts confirmed 2 and four analogues with therapeutic indices for bactericidal activity over in vitro mammalian cytotoxicity as essentially identical to solithromycin (1).

  11. Recent Advances in Recoverable Systems for the Copper-Catalyzed Azide-Alkyne Cycloaddition Reaction (CuAAC

    Directory of Open Access Journals (Sweden)

    Alessandro Mandoli


    Full Text Available The explosively-growing applications of the Cu-catalyzed Huisgen 1,3-dipolar cycloaddition reaction between organic azides and alkynes (CuAAC have stimulated an impressive number of reports, in the last years, focusing on recoverable variants of the homogeneous or quasi-homogeneous catalysts. Recent advances in the field are reviewed, with particular emphasis on systems immobilized onto polymeric organic or inorganic supports.

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

    Directory of Open Access Journals (Sweden)

    Aldo I. Ortega-Arizmendi


    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.

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

    KAUST Repository

    Mehenni, Hakim


    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.

  14. Properties of Poly(ethylene glycol) Hydrogels Cross-Linked via Strain-Promoted Alkyne-Azide Cycloaddition (SPAAC). (United States)

    Hodgson, Sabrina M; Bakaic, Emilia; Stewart, S Alison; Hoare, Todd; Adronov, Alex


    A series of poly(ethylene glycol) (PEG) hydrogels was synthesized using strain-promoted alkyne-azide cycloaddition (SPAAC) between PEG chains terminated with either aza-dibenzocyclooctynes or azide functionalities. The gelation process was found to occur rapidly upon mixing the two components in aqueous solution without the need for external stimuli or catalysts, making the system a candidate for use as an injectable hydrogel. The mechanical and rheological properties of these hydrogels were found to be tunable by varying the polymer molecular weight and the number of cross-linking groups per chain. The gelation times of these hydrogels ranged from 10 to 60 s at room temperature. The mass-based swelling ratios varied from 45 to 76 at maximum swelling (relative to the dry state), while the weight percent of polymer in these hydrogels ranged from 1.31 to 2.05%, demonstrating the variations in amount of polymer required to maintain the structural integrity of the gel. Each hydrogel degraded at a different rate in PBS at pH = 7.4, with degradation times ranging from 1 to 35 days. By changing the composition of the two starting components, it was found that the Young's modulus of each hydrogel could be varied from 1 to 18 kPa. Hydrogel incubation with bovine serum albumin showed minimal protein adsorption. Finally, a cell cytotoxicity study of the precursor polymers with 3T3 fibroblasts demonstrated that the azide- and strained alkyne-functionalized PEGs are noncytotoxic.

  15. Fluorescent labelling of in situ hybridisation probes through the copper-catalysed azide-alkyne cycloaddition reaction. (United States)

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


    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.

  16. Sweet graphene I: toward hydrophilic graphene nanosheets via click grafting alkyne-saccharides onto azide-functionalized graphene oxide. (United States)

    Namvari, Mina; Namazi, Hassan


    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.

  17. Hydrophilic block azidation of PCL-b-PEO block copolymers from epichlorohydrin. (United States)

    Liu, Junjie; Gan, Zhihua


    Amphiphilic diblock copolymers poly(ϵ-caprolactone)-b-poly(ethylene oxide) (PCL-b-PEO) with well-controlled pendant azido groups along the hydrophilic PEO block, that is, poly(ϵ-caprolactone)-b-poly(ethylene oxide-co-glycidyl azide) (PCL-b-P(EO-co-GA)), are synthesized from poly(ϵ-caprolactone)-b-poly(ethylene oxide-co-epichlorohydrin) (PCL-b-P(EO-co-ECH)). The further conversion of those azido groups along the hydrophilic block of copolymers into amino or carboxyl groups via click chemistry is studied. The micelles self-assembled from PCL-b-P(EO-co-GA) with azido groups on the shell are crosslinked by the dialkynyl-PEO. The micelles with crosslinked shell show better stability, higher drug loading capacities, subsequent faster drug release rate, and higher cytotoxicity to cancer cells. The introduction of azido groups into PCL-b-PEO amphiphilic diblock copolymers from epichlorohydrin in PEO hydrophilic block in this work provides a new method for biofunctionalization of micelles via mild click chemistry.

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

    KAUST Repository

    Du, Naiying


    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.

  19. Observation of inductive effects that cause a change in the rate-determining step for the conversion of rhenium azides to imido complexes. (United States)

    Travia, Nicholas E; Xu, Zhenggang; Keith, Jason M; Ison, Elon A; Fanwick, Phillip E; Hall, Michael B; Abu-Omar, Mahdi M


    The cationic oxorhenium(V) complex [Re(O)(hoz)(2)(CH(3)CN)][B(C(6)F(5))(4)] [1; Hhoz = 2-(2'-hydroxyphenyl)-2-oxazoline] reacts with aryl azides (N(3)Ar) to give cationic cis-rhenium(VII) oxoimido complexes of the general formula [Re(O)(NAr)(hoz)(2)][B(C(6)F(5))(4)] [2a-2f; Ar = 4-methoxyphenyl, 4-methylphenyl, phenyl, 3-methoxyphenyl, 4-chlorophenyl, and 4-(trifluoromethyl)phenyl]. The kinetics of formation of 2 in CH(3)CN are first-order in both azide (N(3)Ar) and oxorhenium(V) complex 1, with second-order rate constants ranging from 3.5 × 10(-2) to 1.7 × 10(-1) M(-1) s(-1). A strong inductive effect is observed for electron-withdrawing substituents, leading to a negative Hammett reaction constant ρ = -1.3. However, electron-donating substituents on phenyl azide deviate significantly from this trend. Enthalpic barriers (ΔH(‡)) determined by the Eyring-Polanyi equation are in the range 14-19 kcal mol(-1) for all aryl azides studied. However, electron-donating 4-methoxyphenyl azide exhibits a large negative entropy of activation, ΔS(‡) = -21 cal mol(-1) K(-1), which is in sharp contrast to the near zero ΔS(‡) observed for phenyl azide and 4-(trifluoromethyl)phenyl azide. The Hammett linear free-energy relationship and the activation parameters support a change in the mechanism between electron-withdrawing and electron-donating aryl azides. Density functional theory predicts that the aryl azides coordinate via N(α) and extrude N(2) directly. For the electron-withdrawing substituents, N(2) extrusion is rate-determining, while for the electron-donating substituents, the rate-determining step becomes the initial attack of the azide. The barriers for these two steps are inverted in their order with respect to the Hammett σ values; thus, the Hammett plot appears with a break in its slope.

  20. The use of azide-alkyne click chemistry in recent syntheses and applications of polytriazole-based nanostructured polymers (United States)

    Shi, Yi; Cao, Xiaosong; Gao, Haifeng


    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.

  1. 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


    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.

  2. Effect of gamma-radiation and sodium azide on quantitative characters in rice (Oryza sativa L.

    Directory of Open Access Journals (Sweden)

    Ricardo Montalván


    Full Text Available Seeds of rice cultivar IAC-1246 received single and combined treatments of 10 or 20 Krad gamma-rays and 0.5 mM sodium azide (SA. The experiments were carried out to assess the effect of treatments on the mean and variance in second generation plants of the following quantitative traits: number of days to flowering (NDF, culm length (CL and tiller number (TN. In general, the mutagenic treatments increased variance, but did not change the mean for the characters NDF and CL in the M2 generation. There was no increase in the mean or variance of TN. The combined treatments of gamma-rays and SA resulted in larger variance in CL than for the treatments with gamma-rays alone, but not higher than obtained with SA alone. Combined treatments with gamma-rays and SA did not increase the variance of NDF and TN when compared with the corresponding single treatments.Sementes do cultivar de arroz IAC-1246 receberam tratamento individual e combinado de 10 e 20 Krad de raios-gama e 0,5 de azida sódica (SA. O experimento foi realizado para avaliar o efeito dos tratamentos sobre a média e a variância de plantas M2 nos seguintes caracteres quantitativos: número de dias para a maturação (NDF, comprimento de colmo (CL e número de perfílhos (TN. Em geral, os tratamentos mutagênicos incrementaram a variância, sem mudar a média para os caracteres NDF e CL na geração M2. Todavia, não foi encontrado nenhum incremento seja para a média ou para a variância no caráter TN. Para o caráter CL, os tratamentos combinados de raios-gama e SA mostraram maior variância que aquela observada no tratamento individual com raios-gama, não sendo superior que aquela correspondente ao tratamento individual com SA. Para os caracteres NDF e TN, os tratamentos combinados de raios-gama e SA não incrementaram a variância, quando comparados aos correspondentes tratamentos individuais.

  3. Synthesis and Structural Characterization of Bis(2, 2′-bpy)bis(azide)cobalt(III) nitrate dihydrate

    Institute of Scientific and Technical Information of China (English)



    The title complex [CoIII(2, 2?-bpy)2(N3)2]@NO3@2H2O was obtained by an auto-oxidization reaction of cobalt nitrate with 2, 2?-bpy and sodium azide in aqueous solution at room temperature, and violet single crystals were prepared in ethanol solution. The structure was determined by X-ray crystallography. The crystal is of triclinic, space group P ī with a = 8.285(4), b = 11.990(8), c = 12.596(7) ?, ( = 86.630(3), ( = 86.280(5), ( = 71.130(10)°, C20H20CoN11O5, Mr = 553.40, Z = 2, V = 1180.6(12) ?3, F(000) = 568, Dc = 1.557 g/cm3, ( = 0.784 mm-1, R = 0.0403 and wR = 0.1008. The title complex consists of a [CoⅢ(2, 2?-bpy)2(N3)2]+ cation, a NO3- anion and two lattice water molecules. The center CoⅢ ion coordinated by two chelating 2, 2?-bpy ligands and two terminal azide groups with a CoN6 coordination environment exhibits a distorted octahedral geometry.

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

    Indian Academy of Sciences (India)



    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.

  5. Computational study of the Curtius-like rearrangements of phosphoryl, phosphinyl, and phosphinoyl azides and their corresponding nitrenes. (United States)

    McCulla, Ryan D; Gohar, Gamal A; Hadad, Christopher M; Platz, Matthew S


    The free energies of reaction (DeltaG) and activation (DeltaG) were determined for the Curtius-like rearrangement of dimethylphosphinoyl, dimethylphosphinyl, and dimethylphosphoryl azides as well as the corresponding singlet and triplet nitrenes by CBS-QB3 and B3LYP computational methods. From CASSCF calculations, it was established that the closed-shell configuration was the lower energy singlet state for each of these nitrenes. The triplet states of dimethylphosphinyl- and dimethylphosphorylnitrene are the preferred ground states. However, the closed-shell singlet state is the ground state for dimethylphosphinoylnitrene. The CBS-QB3 DeltaG values for the Curtius-like rearrangements of dimethylphosphinyl and dimethylphosphoryl azides were 45.4 and 47.0 kcal mol-1, respectively. For the closed-shell singlet dimethylphosphinyl- and dimethylphosphorylnitrene, the CBS-QB3 DeltaG values for the rate-limiting step of the Curtius-like rearrangement were 22.9 and 18.0 kcal mol-1, respectively. It is unlikely that the nitrenes will undergo a Curtius-like rearrangement because of competing bimolecular reactions that have lower activation barriers. The pharmacology of weaponized organophosphorus compounds can be investigated using phosphorylnitrenes as photoaffinity labels. Dominant bimolecular reactivity is a desirable quality for a photoaffinity label to possess, and thus, the resistance of phosphorylnitrenes to intramolecular Curtius-like rearrangements increases their usefulness as photoaffinity labels.

  6. A theoretical DFT study on the structural parameters and azide-tetrazole equilibrium in substituted azidothiazole systems (United States)

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


    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.

  7. Azide SHS of aluminium nitride nanopowder and its application for obtaining Al-Cu-AlN cast nanocomposite (United States)

    Titova, Y. V.; Sholomova, A. V.; Kuzina, A. A.; Maidan, D. A.; Amosov, A. P.


    Method of azide self-propagating high-temperature synthesis (SHS-Az), using sodium azide (NaN3) as a nitriding reagent, was used for obtaining the nanopowder of aluminum nitride (AlN) from precursor that was sodium hexafluoroaluminate (Na3AlF6). The product of burning the mixture of Na3AlF6 + 3NaN3 after water rinsing consisted of micro - and nanoparticles of AlN (65%) and the residue of salt Na3AlF6 (35%). This product of SHS-Az was mixed with copper powder and pressed into a briquette of nanopowdery master alloy Cu- 4%(65%AlN+35%Na3AlF6), which was successfully introduced into aluminium melt at a temperature of 850°C. The salt Na3AlF6 in the product of combustion played a role of flux during introducing into the aluminum melt and was not included in the final composition of the composite alloy. The microstructure of the obtained cast composite aluminum alloy with the calculated composition of Al-1.2%Cu-0.035%AlN showed that the reinforcing particles of AlN of different sizes, including nanoparticles, were distributed mainly along the grain boundaries of the aluminum alloy.

  8. Novel carbamoyl type quinine and quinidine based chiral anion exchangers implementing alkyne-azide cycloaddition immobilization chemistry. (United States)

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


    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.

  9. Chronological comparison of root dentin moisture in extracted human teeth stored in formalin, sodium azide, and distilled water (United States)

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


    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

  10. 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.;


    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......-opening polymerization of E-caprolactone initiated by 5-hexyn-1-ol and Mitsunobu coupling with 4-pentenoic acid provide hetero-telechelic poly(epsilon-caprolactone) bearing terminal alkyne and alkene groups. It is then employed in the sequential "click" reactions with the azide-functionalized dendritic wedge...

  11. 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


    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.

  12. Synthesis of phosphine and antibody-azide probes for in vivo Staudinger ligation in a pretargeted imaging and therapy approach. (United States)

    Vugts, Danielle J; Vervoort, Annelies; Stigter-van Walsum, Marijke; Visser, Gerard W M; Robillard, Marc S; Versteegen, Ron M; Vulders, Roland C M; Herscheid, J Koos D M; van Dongen, Guus A M S


    The application of intact monoclonal antibodies (mAbs) as targeting agents in nuclear imaging and radioimmunotherapy is hampered by the slow pharmacokinetics of these molecules. Pretargeting with mAbs could be beneficial to reduce the radiation burden to the patient, while using the excellent targeting capacity of the mAbs. In this study, we evaluated the applicability of the Staudinger ligation as pretargeting strategy using an antibody-azide conjugate as tumor-targeting molecule in combination with a small phosphine-containing imaging/therapeutic probe. Up to 8 triazide molecules were attached to the antibody without seriously affecting its immunoreactivity, pharmacokinetics, and tumor uptake in tumor bearing nude mice. In addition, two (89)Zr- and (67/68)Ga-labeled desferrioxamine (DFO)-phosphines, a (177)Lu-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-phosphine and a (123)I-cubyl phosphine probe were synthesized and characterized for their pharmacokinetic behavior in nude mice. With respect to the phosphine probes, blood levels at 30 min after injection were phosphine, relative to the azide, in aqueous solution resulted in 20-25% efficiency after 2 h. The presence of 37% human serum resulted in a reduced ligation efficiency (reduction max. 30% at 2 h), while the phosphines were still >80% intact. No in vivo Staudinger ligation was observed in a mouse model after injection of 500 μg antibody-azide, followed by 68 μg DFO-phosphine at t = 2 h, and evaluation in blood at t = 7 h. To explain negative results in mice, Staudinger ligation was performed in vitro in mouse serum. Under these conditions, a side product with the phosphine was formed and ligation efficiency was severely reduced. It is concluded that in vivo application of the Staudinger ligation in a pretargeting approach in mice is not feasible, since this ligation reaction is not bioorthogonal and efficient enough. Slow reaction kinetics will also severely restrict the applicability

  13. 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


    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 compatibility...

  14. Synthesis of 3-tetrazolylmethyl-4H-chromen-4-ones via Ugi-azide and biological evaluation against Entamoeba histolytica, Giardia lamblia and Trichomona vaginalis. (United States)

    Cano, Pedro A; Islas-Jácome, Alejandro; González-Marrero, Joaquín; Yépez-Mulia, Lilian; Calzada, Fernando; Gámez-Montaño, Rocío


    The synthesis of novel 3-tetrazolylmethyl-4H-chromen-4-ones via an Ugi-azide multicomponent reaction and their biological evaluation against Entamoeba histolytica, Giardia lamblia and Trichomona vaginalis are described. Reported yields are moderate to good and biological results show that these compounds could be considered as candidates to anti-parasitic drugs, especially against G. lamblia.

  15. 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). (United States)

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


    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.

  16. Just Click It: Undergraduate Procedures for the Copper(I)-Catalyzed Formation of 1,2,3-Triazoles from Azides and Terminal Acetylenes (United States)

    Sharpless, William D.; Peng Wu; Hansen, Trond Vidar; Lindberg, James G.


    The click chemistry uses only the most reliable reactions to build complex molecules from olefins, electrophiles and heteroatom linkers. A variation on Huisgen's azide-alkyne 1,2,3-triazole synthesis, the addition of the copper (I), the premium example of the click reaction, catalyst strongly activates terminal acetylenes towards the 1,3-dipole in…

  17. A highly active and reusable copper(I)-tren catalyst for the "click" 1,3-dipolar cycloaddition of azides and alkynes. (United States)

    Candelon, Nicolas; Lastécouères, Dominique; Diallo, Abdou Khadri; Aranzaes, Jaime Ruiz; Astruc, Didier; Vincent, Jean-Marc


    The copper(I) complex [Cu(C18(6)tren)]Br 1 (C18(6)tren = tris(2-dioctadecylaminoethyl)amine) which exhibits a good stability towards aerobic conditions is a versatile, highly reactive and recyclable catalyst for the Huisgen cycloaddition of azides with terminal or internal alkynes and is a useful catalyst for the preparation of "click" dendrimers.

  18. 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


    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...

  19. Amine-free approach toward N-toluenesulfonyl amidine construction: a phosphite-mediated Beckmann-like coupling of oximes and p-toluenesulfonyl azide. (United States)

    Fleury, Lauren M; Wilson, Erin E; Vogt, Monika; Fan, Tiffany J; Oliver, Allen G; Ashfeld, Brandon L


    Atom hopping: A chlorophosphite-mediated Beckmann ligation of oximes and p-toluenesulfonyl azide gives access to N-sulfonyl phosphoramidines in good to excellent yields. The reaction proceeds under exceptionally mild conditions and constitutes a bioorthogonal approach toward amidines by avoiding the use of amines and transition-metal catalysts. dmp-ol=3,3-dimethylpropanediol.

  20. Theoretical studies on N-O or N-N bond formation from aryl azide catalyzed by iron(II) bromide complex. (United States)

    Li, Juan; Zhang, Qi; Zhou, Lixin


    DFT calculations have been carried out to study the reaction mechanism on N-O or N-N bond formation from aryl azide catalyzed by iron(II) bromide complex. A favorable reaction pathway is proposed to account for the construction of the core structure of 2H-indazoles or 2,1-benzisoxazoles.

  1. 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


    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, wit...

  2. Optimization of a ligand immobilization and azide group endcapping concept via "Click-Chemistry" for the preparation of adsorbents for antibody purification. (United States)

    Horak, Jeannie; Hofer, Stefan; Lindner, Wolfgang


    This report describes and compares different strategies to deactivate (endcap) epoxide groups and azide groups on bio-chromatographic support surfaces, before and after ligand attachment. Adsorbents possessing epoxide groups were deactivated using acidic hydrolysis or were endcapped with 2-mercaptoethanol or 2-ethanolamine. The influence of surface-bound 2-ethanolamine was demonstrated for the triazine-type affinity adsorbent B14-2LP-FractoAIMs-1, which was tested in combination with the weak anion exchange material 3-aminoquinuclidine-FractoAIMs-3 (AQ-FA3). Azide groups were modified with 2-propargylalcohol using Click-Chemistry. Besides the conventional one-pot Click reaction, an alternative approach was introduced. This optimized Click protocol was employed (i) for the preparation of the weak anion exchange material AdQ-triazole-Fractogel (AdQ-TRZ-FG) and (ii) for the endcapping of residual azide groups with 3-propargyl alcohol. Using the new Click reaction protocol the ligand immobilization rate was doubled from 250 to 500 μmol/g dry adsorbent. Furthermore, the modified support surface was proven to be inert towards the binding of immunoglobulin G (IgG) as well as feed impurities. A thorough evaluation of modified surfaces and adsorbents was performed with dynamic binding experiments using cell culture supernatant containing monoclonal human immunoglobulin G (h-IgG-1). Besides SDS-Page, a recently introduced Protein A-size exclusion HPLC method (PSEC-HPLC) was used to visualize the feed impurity composition and the IgG content of all collected sample fractions in simple PSEC-Plots. A surprising outcome of this study was the irreversible binding of IgG to azide modified surfaces. It was found that organic azide compounds, e.g. 1-azide-3-(2-propen-1-yloxy)-2-propanol (AGE-N3) promote antibody aggregation to a slightly higher extent than the inorganic sodium azide. The possibility that the Hofmeister Series of salt anions may be applicable to predict the

  3. Ammonium azide: a commented example of an Ab initio structure (Re-) determination from X-ray powder diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Salim de Amorim, H.; Amaral, M.R. do [Instituto de Fisica, Universidade Federal do Rio de Janeiro, CP 68528, 21495-970 Rio de Janeiro (Brazil); Pattison, P. [Institute of Crystallography, BSP, University of Laussane, CH-1015, Laussane (Switzerland); Pereira L, I.; Mendes, J.C. [Departamento de Geologia, Universidade Federal do Rio de Janeiro, 21949-900, Rio de Janeiro (Brazil)


    The structure of ammonium azide (NH{sub 4})N{sub 3} was (re-)determined ab initio from x-ray powder diffraction experiment using synchrotron radiation. We tried to detail and comment the different steps involved in the structure determination. The compound crystallize in the orthorhombic Pmna space group (no.53) with a = 8.937(1) A, b= 3.8070(5) A, c = 8.664(1) A, V = 294.79(7) A{sup 3}; Z= 4. It was possible to locate and refine the hydrogen coordinates, in two different approaches, and to establish the H-bonds. The final structural parameters are in good agreement with previous results based on three-dimensional neutron diffraction. (Author)

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

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


    `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.

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


    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.

  6. Suppression of signal sequence defects and azide resistance in Escherichia coli commonly result from the same mutations in secA. (United States)

    Huie, J L; Silhavy, T J


    The SecA protein of Escherichia coli is required for protein translocation from the cytoplasm. The complexity of SecA function is reflected by missense mutations in the secA gene that confer several different phenotypes: (i) conditional-lethal alleles cause a generalized block in protein secretion, resulting in the cytoplasmic accumulation of the precursor forms of secreted proteins; (ii) azi alleles confer resistance to azide at concentrations up to 4 mM; and (iii) prlD alleles suppress a number of signal sequence mutations in several different genes. To gain further insights into the role of SecA in protein secretion, we have isolated and characterized a large number of prlD mutations, reasoning that these mutations alter a normal function of wild-type SecA. Our results reveal a striking coincidence of signal sequence suppression and azide resistance: the majority of prlD alleles also confer azide resistance, and all azi alleles tested are suppressors. We suggest that this correlation reflects the mechanism(s) of signal sequence suppression. There are two particularly interesting subclasses of prlD and azi alleles. First, four of the prlD and azi alleles exhibit special properties: (i) as suppressors they are potent enough to allow PrlD (SecA) inactivation by a toxic LacZ fusion protein marked with a signal sequence mutation (suppressor-directed inactivation), (ii) they confer azide resistance, and (iii) they cause modest defects in the secretion of wild-type proteins. Sequence analysis reveals that all four of these alleles alter Tyr-134 in SecA, changing it to Ser, Cys, or Asn. The second subclass consists of seven prlD alleles that confer azide supersensitivity, and sequence analysis reveals that six of these alleles are changes of Ala-507 to Val. Both of the affected amino acids are located within different putative ATP-binding regions of SecA and thus may affect ATPase activities of SecA. We suggest that the four azide-resistant mutations slow an ATPase

  7. 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.

    (Arrora Matthey), L-proline, glycine, dimethylacetylene dicarboxylate (DMD), diethylacetylene 3    dicarboxylate (DED) and sodium azide (Sigma Aldrich), were used as received. NMR spectra were recorded on a Bruker Avance 300 MHz spectrometer at 300.13 (1...

  8. 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. (United States)

    Shin, Kwangmin; Kim, Hyunwoo; Chang, Sukbok


    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

  9. Improved synthesis of [(18)F]FLETT via a fully automated vacuum distillation method for [(18)F]2-fluoroethyl azide purification. (United States)

    Ackermann, Uwe; Plougastel, Lucie; Goh, Yit Wooi; Yeoh, Shinn Dee; Scott, Andrew M


    The synthesis of [(18)F]2-fluoroethyl azide and its subsequent click reaction with 5-ethynyl-2'-deoxyuridine (EDU) to form [(18)F]FLETT was performed using an iPhase FlexLab module. The implementation of a vacuum distillation method afforded [(18)F]2-fluoroethyl azide in 87±5.3% radiochemical yield. The use of Cu(CH3CN)4PF6 and TBTA as catalyst enabled us to fully automate the [(18)F]FLETT synthesis without the need for the operator to enter the radiation field. [(18)F]FLETT was produced in higher overall yield (41.3±6.5%) and shorter synthesis time (67min) than with our previously reported manual method (32.5±2.5% in 130min).

  10. 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


    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.

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

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


    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.

  12. Macrokinetic calculation of the ignition of a solid-fuel charge of glycidyl azide polymer in the mini-engine of a microelectromechanical system (United States)

    Fut'ko, S. I.; Ermolaeva, E. M.; Dobrego, K. V.; Bondarenko, V. P.; Dolgii, L. N.


    The process of ignition of the solid fuel from glycidyl azide polymer in the mini-engine of a microelectromechanical system has been considered. Macrokinetic calculations of the self-ignition temperature of the fuel and the induction period for different heat transfer conditions have been made. On the basis of the critical thermal flux determination, recommendations on the choice of the minimum power and size of the thermistor in the igniter of the solid-fuel mini-engine have been formulated.

  13. Synthesis of ferrocene-labeled steroids via copper-catalyzed azide-alkyne cycloaddition. Reactivity difference between 2β-, 6β- and 16β-azido-androstanes. (United States)

    Fehér, Klaudia; Balogh, János; Csók, Zsolt; Kégl, Tamás; Kollár, László; Skoda-Földes, Rita


    Copper-catalyzed cycloaddition of steroidal azides and ferrocenyl-alkynes were found to be an efficient methodology for the synthesis of ferrocene-labeled steroids. At the same time, a great difference between the reactivity of 2β- or 16β-azido-androstanes and a sterically hindered 6β-azido steroid toward both ferrocenyl-alkynes and simple alkynes, such as phenylacetylene, 1-octyne, propargyl acetate and methyl propiolate, was observed.

  14. Synthesis and post-synthetic modification of amine-, alkyne-, azide- and nitro-functionalized metal-organic frameworks based on DUT-5. (United States)

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


    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.

  15. Preparation of 18F-labeled peptides using the copper(I)-catalyzed azide-alkyne 1,3-dipolar cycloaddition. (United States)

    Gill, Herman S; Marik, Jan


    An optimized procedure for preparing fluorine-18 ((18)F)-labeled peptides by the copper-catalyzed azide-alkyne 1,3-dipolar cyloaddition (CuAAC) is presented here. The two-step radiosynthesis begins with the microwave-assisted nucleophilic (18)F-fluorination of a precursor containing a terminal p-toluenesulfonyl, terminal azide and polyethylene glycol backbone. The resulting (18)F-fluorinated azide-containing building block is coupled to an alkyne-decorated peptide by the CuAAC. The reaction is accelerated by the copper(I)-stabilizing ligand bathophenanthroline disulfonate and can be performed in either reducing or nonreducing conditions (e.g., to preserve disulfide bonds). After an HPLC purification, (18)F-labeled peptide can be obtained with a 31 ± 6% radiochemical yield (n = 4, decay-corrected from (18)F-fluoride elution) and a specific activity of 39.0 ± 12.4 Ci μmol(-1) within 77 ± 4 min.

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

    KAUST Repository

    Alkayal, Nazeeha


    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).

  17. 3例叠氮化钠中毒病例临床分析%Analysis on Three Clinical Cases of Sodium Azide Poisoning

    Institute of Scientific and Technical Information of China (English)

    胡川笑; 邵志华; 余清卿; 余小忠; 何燕霞


    [ Objective ] To study the clinical characteristics of sodium azide poisoning. [ Methods ] Study the clinical manifestation and course of 3 cases of acute sodium azide poisoning. [ Results ] Various clinical manifestations including toxic encephalopathy, peripheral neuropathy and etc. were presented in sodium azide poisoning. [ Conclusion ] There is no specific treatment for acute toxic encephalopathy and peripheral neuropathy, at present. Methyl-prednisolone, hyperbaric oxygen inhalation,oral vitamin B12, and kinesiatrics are the major supportive treatments.%[目的]探讨叠氮化钠中毒的临床特点.[方法]对3例急性叠氮化钠中毒患者的临床表现、治疗情况等进行分析.[结果]叠氮化钠中毒可有不同临床表现,急性中毒表现有中毒性脑病、周围神经病变等.[结论]急性叠氮化钠中毒性脑病、周围神经病变目前尚无特效药物治疗,主要以激素、高压氧、维生素B12运动疗法等对症支持治疗为主.

  18. 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


    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.

  19. Structural Stability and Vibrational Analyses of Haloselenonyl Azides, XSeO2-NNN, where X is F, Cl, Br

    Directory of Open Access Journals (Sweden)

    Wolfgang Förِner


    Full Text Available The structural stability of haloselenonyl azides was investigated by quantum mechanical Møller-Plesset perturbation theory of second order and density functional theory calculations. The 6-311+G** basis set was used to include polarization and diffuse functions in the calculations at the DFT-B3LYP level. The potential scans for the rotation of the -NNN rotor were calculated and found to be consistent with a single minimum that corresponds to a gauche conformation (-NNN moiety nearly eclipses one of the two selenonyl Se=O bonds for the three halogens at ambient temperature. The structural parameters for the minima calculated by MP2 and DFT turned out to be very similar. The vibrational modes, infrared and Raman intensities as well as depolarization ratios were calculated at DFT-B3LYP/6-311+G** level for the three molecules in their gauche conformations. The potential energy distributions among symmetry coordinates of the normal modes of the molecules in their gauche conformation were then computed from normal coordinate analyses.

  20. 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


    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.

  1. Chemically directed assembly of photoactive metal oxide nanoparticle heterojunctions via the copper-catalyzed azide-alkyne cycloaddition "click" reaction. (United States)

    Cardiel, Allison C; Benson, Michelle C; Bishop, Lee M; Louis, Kacie M; Yeager, Joseph C; Tan, Yizheng; Hamers, Robert J


    Metal oxides play a key role in many emerging applications in renewable energy, such as dye-sensitized solar cells and photocatalysts. Because the separation of charge can often be facilitated at junctions between different materials, there is great interest in the formation of heterojunctions between metal oxides. Here, we demonstrate use of the copper-catalyzed azide-alkyne cycloaddition reaction, widely referred to as "click" chemistry, to chemically assemble photoactive heterojunctions between metal oxide nanoparticles, using WO(3) and TiO(2) as a model system. X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy verify the nature and selectivity of the chemical linkages, while scanning electron microscopy reveals that the TiO(2) nanoparticles form a high-density, conformal coating on the larger WO(3) nanoparticles. Time-resolved surface photoresponse measurements show that the resulting dyadic structures support photoactivated charge transfer, while measurements of the photocatalytic degradation of methylene blue show that chemical grafting of TiO(2) nanoparticles to WO(3) increases the photocatalytic activity compared with the bare WO(3) film.

  2. Preparation and Characterization of the Binary Group 13 Azides M(N3)3 and M(N3)3’CH3CN (M = Ga, In, TI), [Ga(N3)5](2-), and [M(N3)6](3-) (M = In, TI) (Preprint) (United States)


    semiconductor and optoelectronic applications. Although most of these efforts were devoted to gallium azides, aluminium and indium azides were also...their usefulness for semiconductor and optoelectronic applications. Although most of these efforts were devoted to gallium azides,[20,21] aluminium and...4253 -1471 44 H(22) 3736 3825 -1326 52 H(23) 4209 3248 -466 58 H(24) 3087 3112 263 54 H(26) 3906 4945 5420 37 H(27) 5618 5178 5700 46 H(28) 6061

  3. Convenient synthesis of a propargylated cyclic (3'-5') diguanylic acid and its "click" conjugation to a biotinylated azide. (United States)

    Grajkowski, Andrzej; Cieślak, Jacek; Gapeev, Alexei; Schindler, Christian; Beaucage, Serge L


    The ribonucleoside building block, N²-isobutyryl-2'-O-propargyl-3'-O-levulinyl guanosine, was prepared from commercial N²-isobutyryl-5'-O-(4,4'-dimethoxytrityl)-2'-O-propargyl guanosine in a yield of 91%. The propargylated guanylyl(3'-5')guanosine phosphotriester was synthesized from the reaction of N²-isobutyryl-2'-O-propargyl-3'-O-levulinyl guanosine with N²-isobutyryl-5'-O-(4,4'-dimethoxytrityl)-2'-O-tert-butyldimethylsilyl-3'-O-[(2-cyanoethyl)-N,N-diisopropylaminophosphinyl] guanosine and isolated in a yield of 88% after P(III) oxidation, 3'-/5'-deprotection, and purification. The propargylated guanylyl(3'-5')guanosine phosphotriester was phosphitylated using 2-cyanoethyl tetraisopropylphosphordiamidite and 1H-tetrazole and was followed by an in situ intramolecular cyclization to give a propargylated c-di-GMP triester, which was isolated in a yield of 40% after P(III) oxidation and purification. Complete N-deacylation of the guanine bases and removal of the 2-cyanoethyl phosphate protecting groups from the propargylated c-di-GMP triester were performed by treatment with aqueous ammonia at ambient temperature. The final 2'-desilylation reaction was effected by exposure to triethylammonium trihydrofluoride affording the desired propargylated c-di-GMP diester, the purity of which exceeded 95%. Biotinylation of the propargylated c-di-GMP diester was easily accomplished through its cycloaddition reaction with a biotinylated azide derivative under click conditions to produce the biotinylated c-di-GMP conjugate of interest in an isolated yield of 62%.

  4. Investigation of possibility to fabricate Si3N4-TiN ceramic nanocomposite powder by azide SHS method (United States)

    Kondratieva, L. A.; Kerson, I. A.; Illarionov, A. Yu; Amosov, A. P.; Bichurov, G. V.


    The process of self-propagating high-temperature synthesis with use of a powder of sodium azide NaN3 as a nitriding agent (the SHS-Az method) was applied to fabricate a nanocomposite powder Si3N4-TiN. Combustion of the initial mixtures of NaN3 only with precursors that are halides of silicon and titanium: Na2SiF6, (NH4)2SiF6, Na2TiF6, (NH4)2TiF6 did not allow us to synthesize the composite powder of Si3N4-TiN, as the phases of silicon nitride Si3N4 were not formed. After water washing, the ultrafine powdered product of combustion consisted of one target phase of titanium nitride only and a large amount of impurity of side phases. Replacement of the halide salt of one of the elements (Si or Ti) by the powder of this element in the initial mixture of SHS-Az system resulted in formation of silicon nitride together with the titanium nitride and impurities. The least amount of impurities was obtained by burning the initial mixtures of xSi + y(NH4)2TiF6 + zNaN3 system. Only the initial mixture of 9Si + (NH4)2TiF6 + 6NaN3 allowed us to obtain as a result of the SHS-Az process the nanostructured composite powder of Si3N4-TiN without impurities.

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

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


    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.

  6. 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.

  7. Moderating strain without sacrificing reactivity: design of fast and tunable noncatalyzed alkyne-azide cycloadditions via stereoelectronically controlled transition state stabilization. (United States)

    Gold, Brian; Dudley, Gregory B; Alabugin, Igor V


    Recently, we have identified two strategies for selective transition state (TS) stabilization in catalyst-free azide/alkyne cycloadditions. In particular, the transition states for the formation of both 1,4- and 1,5-isomers can be stabilized via hyperconjugative assistance for the C···N bond formation, whereas the 1,5-TS can be stabilized via C-H···X H-bonding interactions. When the hyperconjugative assistance is maximized by the antiperiplanar arrangement of propargylic σ-acceptors relative to the forming bonds, the combination of these TS-stabilizing effects was predicted to lead to ~1 million fold acceleration of the cycloaddition with methyl azide. The present work investigated whether hyperconjugative assistance and H-bonding can be combined with strain activation for the design of even more reactive alkynes and whether reactivity can be turned "on demand." When stereoelectronic amplification is achieved by optimal positioning of σ-acceptors at the endocyclic bonds antiperiplanar to the breaking alkyne π-bonds, the stabilization of the bent alkyne geometry leads to a significant decrease in strain in cyclic alkynes without compromising their reactivity in alkyne-azide cycloadditions. The approach can be used in a modular fashion where the TS stabilizing effects are introduced sequentially until the desired level of reactivity is achieved. A significant increase in reactivity upon the protonation of an endocyclic NH-group suggests a new strategy for the design of click reactions triggered by a pH-change or introduction of an external Lewis acid.

  8. Novel Synthesis of 1,2,3-Triazoles via 1,3-Dipolar Cycloadditions of Alkynes to Azides in Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    ZHONG,Ping(钟平); GUO,Sheng-Rong(郭圣荣)


    2-Azido-3,5-dichloropyridine and 2-azido-5-chloro-3-fluoropyridine were given by reaction of sodium azide with 2,3,5-trichloropyridine, 3,5-dichloro-2-fluoropyridine or 5-chloro-2,3-difiuoropyridine in ionic liquids.1,3-Dipolar cycloaddition of 2-azido-3,5-dichloropyridine or 2-azido-5-chloro-3-fluoropyridine to alkynes in ionic liquids afforded the corresponding 1,4,5-trisubstituted [1,2,3]-triazoles in good yields and regioselectivities.

  9. Azide-enolate 1,3-dipolar cycloaddition in the synthesis of novel triazole-based miconazole analogues as promising antifungal agents. (United States)

    González-Calderón, Davir; Mejía-Dionicio, María G; Morales-Reza, Marco A; Ramírez-Villalva, Alejandra; Morales-Rodríguez, Macario; Jauregui-Rodríguez, Bertha; Díaz-Torres, Eduardo; González-Romero, Carlos; Fuentes-Benítes, Aydeé


    Seven miconazole analogs involving 1,4,5-tri and 1,5-disubstituted triazole moieties were synthesized by azide-enolate 1,3-dipolar cycloaddition. The antifungal activity of these compounds was evaluated in vitro against four filamentous fungi, including Aspergillus fumigatus, Trichosporon cutaneum, Rhizopus oryzae, and Mucor hiemalis as well as three species of Candida spp. as yeast specimens. These pre-clinical studies suggest that compounds 4b, 4d and 7b can be considered as drug candidates for future complementary biological studies due to their good/excellent antifungal activities.

  10. Efficient microwave assisted synthesis of novel 1,2,3-triazole-sucrose derivatives by cycloaddition reaction of sucrose azides and terminal alkynes. (United States)

    Potewar, Taterao M; Petrova, Krasimira T; Barros, M Teresa


    Novel 1-(1',2,3,3',4,4',6-hepta-O-acetyl-6'-deoxy-sucros-6'-yl)-4-substituted-1,2,3-triazoles were synthesized by microwave assisted copper catalyzed 1,3-dipolar cycloaddition of sucrose derived azides with terminal alkynes in excellent yields and in short reaction times. The compound 1',2,3,3',4,4',6-hepta-O-acetyl-6'-azido-6'-deoxy-sucrose was regioselectively synthesized from sucrose by improved procedure and used for the cycloadditions. By combining carbohydrate and 1,2,3-triazole structural motifs, a library of 1,2,3-triazole-sucrose conjugates have been obtained.

  11. Transition-state structure for the quintessential SN2 reaction of a carbohydrate: reaction of α-glucopyranosyl fluoride with azide ion in water. (United States)

    Chan, Jefferson; Sannikova, Natalia; Tang, Ariel; Bennet, Andrew J


    We report that the SN2 reaction of α-d-glucopyranosyl fluoride with azide ion proceeds through a loose (exploded) transition-state (TS) structure. We reached this conclusion by modeling the TS using a suite of five experimental kinetic isotope effects (KIEs) as constraints for the calculations. We also report that the anomeric (13)C-KIE is not abnormally large (k12/k13 = 1.024 ± 0.006), a finding which is at variance with the previous literature value (Zhang et al. J. Am. Chem. Soc. 1994, 116, 7557).

  12. Conventional and microwave-assisted multicomponent reaction of alkyne, halide and sodium azide catalyzed by copper apatite as heterogeneous base and catalyst in water

    Directory of Open Access Journals (Sweden)

    Sandip Kale


    Full Text Available The conventional and microwave assisted multicomponent synthesis of disubstituted 1,2,3-triazoles from terminal alkynes and in situ generated organic azide using copper apatite catalyst in water is reported. The catalytic activity is intimately connected to the basicity of the catalyst. The best activities were observed with the copper hydroxyapatite. The catalyst could be used ten times without further treatment and activation under controlled microwave heating. The protocol was also applicable for various alkynes and halides which affords desired product in good to excellent yield.

  13. Radical substitution with azide

    DEFF Research Database (Denmark)

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


    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....

  14. An azide-insensitive low-affinity ATPase stimulated by Ca2+ or Mg2+ in basal-lateral and brush border membranes of kidney cortex. (United States)

    Ilsbroux, I; Vanduffel, L; Teuchy, H; De Cuyper, M


    Basal-lateral and brush border membranes from pig kidney cortex were prepared by differential centrifugation followed by free-flow electrophoresis. In each type of membrane, azide-insensitive, low-affinity Ca2+-ATPase and Mg2+-ATPase activities are demonstrated. A comparative study for both membranes further reveals the following analogies between these ATPases: (a) they show maximal activity between pH 8 and 8.5; (b) they exhibit Km values for Ca-ATP or Mg-ATP in the millimolar range and have a comparable low substrate specificity; (c) they are insensitive to 10 microM of vanadate, N,N'-dicyclohexylcarbodiimide, e diethylstilbestrol, quercetin, harmaline and amiloride. The partial inhibition by 1 mM of the various compounds is rather aspecific. In view of these similarities it is concluded that only one enzyme entity is responsible for the activity which is measured in both membrane types. The HCO3-stimulated Mg2+-ATPase activity in pig kidney cortex was also studied. This enzyme, however, is clearly of mitochondrial origin since the HCO3-stimulation coincides with the distribution profile of succinate dehydrogenase, a mitochondrial marker; and since it is inhibited by azide.

  15. Analysis of enterococci using portable testing equipment for developing countries--variance of Azide NutriDisk medium under variable time and temperature. (United States)

    Godfrey, S; Watkins, J; Toop, K; Francis, C


    This report compares the enterococci count on samples obtained with Azide NutriDisk (AND) (sterile, dehydrated culture medium) and Slanetz and Bartley (SB) medium when exposed to a variable in incubation time and temperature. Three experiments were performed to examine the recovery of enterococci on AND and SB media using membrane filtration with respect to: (a) incubation time; (b) incubation temperature; and (c) a combination of the two. Presumptive counts were observed at 37, 41, 46 and 47 degrees C and at 20, 24, 28 and 48 h. These were compared to AWWA standard method 9230 C (44 degrees C, 44 h). Samples were confirmed using Kanamycin Aesculin Azide (KAA) agar. Friedman's ANOVA and Students t-test analysis indicated higher enumeration of enterococci when grown on AND (p = 0.45) than SB (p = < 0.001) at all temperatures with a survival threshold at 47 degrees C. Significant results for AND medium were noted at 20 h (p = 0.021), 24 h (p = 0.278) and 28 h (p = 0.543). The study concluded that the accuracy of the AND medium at a greater time and temperature range provided flexibility in incubator technology making it an appropriate alternative to SB medium for monitoring drinking water using field testing kits in developing countries.

  16. Combining oximes with azides to create a novel 1-D [NaCo(III)(2)] system: synthesis, structure and solid-state NMR. (United States)

    Pathmalingam, Thushan; Habib, Fatemah; Widdifield, Cory M; Loiseau, Francis; Burchell, Tara J; Gorelsky, Serge I; Beauchemin, André M; Bryce, David L; Murugesu, Muralee


    The synthesis and structure of a novel complex with the formula [NaCo(III)(2)(dmo)(2)(mu-N(3))(3)(N(3))(2)](infinity), , are reported. Complex was synthesized from the reaction of 1-(dimethylamino)propan-2-one oxime (Hdmo), CoCl(2).6H(2)O, and NaN(3) in MeOH. It crystallizes in the monoclinic space group C2/c. The molecular structure consists of one Na(I) and two Co(III) ions bridged by two oxime ligands, two end-to-end azide and three end-on azide anions. The units are linked, forming a 1-D chain. This complex was characterized by UV-Vis spectroscopy where the data confirm the presence of low-spin Co(III) ions. Solid-state (23)Na NMR experiments indicate the presence of one magnetically unique site in the repeating unit, that sample purity in the bulk powdered form is high, and that it possesses microcrystalline order. Solid-state (59)Co NMR experiments at ultra-high field (B(0) = 21.1 T) are in agreement with the structure obtained through X-ray crystallography where the Co(III) ions are coordinated to five nitrogen atoms as well as an oxygen atom.

  17. A theoretical study on the reaction pathways and the mechanism of 1,3- dipolar cycloaddition of vinyl acetylene and methyl azide. (United States)

    Siadati, Seyyed Amir; Mahboobifar, Ali; Nasiri, Ramin


    1,3-dipolar cycloaddition procedure is one of the most widely practiced methods in order to synthesize heterocyclic compounds. Although, it seems very simple, but, there are numerous precursors of heterocyclic molecules who have more than one positions to react with a 1,3-dipole species. As a result, while using a precursor with more than one position for reaction, it is probable to synthesize several products with different structures. This paper studies all possible interactions of vinyl acetylene, which has two positions for reaction, with methyl azide. This reaction could lead to the emergence of any 1,3-dipolar cycloaddition products. Our ultimate goal is to help researchers to find out how precursors containing both carbon-carbon double, and the triple bonds interact with 1,3- dipolar species. The present study used the DFT calculations at B3LYP/6-311++G(3df,pd) level to check all probable interactions between vinyl acetylene and methyl azide, and determined Potential Energy Surface, and optimized all species.

  18. Synthesis and Crystal Structure of a Three-dimensional Mn(Ⅱ) Coordination Polymer with 3-(Pyrazin-2-yloxy)-pyridine and Azide Anion as Mixed Bridge Ligand

    Institute of Scientific and Technical Information of China (English)


    A three-dimensional coordination polymer [Mn2((1,3-N3)4(μ-PP)2]n (PP = 3-(pyra- zin-2-yloxy)-pyridine) has been synthesized with 3-(pyrazin-2-yloxy)-pyridine and azide anion as mixed bridge ligand, and its crystal structure was determined by X-ray crystallography. The crystal data: triclinic system, space group P, with a = 6.794(4), b = 9.885(6), c = 9.947(6)A, α = 64.170(6),β = 84.190(8),γ = 85.319(8)°, V = 597.7(6)(A)3, Z = 1, C18H14Mn2N18O2, Mr = 624.35, Dc = 1.735 g/cm3, F(000) = 314 andμ= 1.117 mm-1. In the crystal, the azide anion acts as a bridge ligand and makes adjacent Mn(Ⅱ) ions connect into a two-dimensional sheet on the ab plane, then 3-(pyrazin-2-yloxy)-pyridine serves as a bidentate bridge ligand to connect neighboring sheets along the c axis, and finally a three-dimensional structure is formed.

  19. A Theoretical Study of the Relationship between the Electrophilicity ω Index and Hammett Constant σp in [3+2] Cycloaddition Reactions of Aryl Azide/Alkyne Derivatives

    Directory of Open Access Journals (Sweden)

    Hicham Ben El Ayouchia


    Full Text Available The relationship between the electrophilicity ω index and the Hammett constant σp has been studied for the [2+3] cycloaddition reactions of a series of para-substituted phenyl azides towards para-substituted phenyl alkynes. The electrophilicity ω index—a reactivity density functional theory (DFT descriptor evaluated at the ground state of the molecules—shows a good linear relationship with the Hammett substituent constants σp. The theoretical scale of reactivity correctly explains the electrophilic activation/deactivation effects promoted by electron-withdrawing and electron-releasing substituents in both azide and alkyne components.

  20. 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


    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

  1. 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


    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.

  2. 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


    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.

  3. 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. (United States)

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


    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.

  4. 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


    [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.

  5. Covalently linked plasticizers: triazole analogues of phthalate plasticizers prepared by mild copper-free “click” reactions with azide-functionalized PVC. (United States)

    Earla, Aruna; Braslau, Rebecca


    Copper-free azide-alkyne click chemistry is utilized to covalently modify polyvinyl chloride(PVC). Phthalate plasticizer mimics di(2-ethylhexyl)-1H-triazole-4,5 dicarboxylate (DEHT), di(nbutyl)-1H-1,2,3-triazole-4,5-dicarboxylate (DBT), and dimethyl-1H-triazole-4,5-dicarboxylate(DMT) are covalently attached to PVC. DEHT, DBT, and DMT have similar chemical structures to traditional plasticizers di(2-ethylhexyl) phthalate (DEHP), di(n-butyl) phthalate (DBP), and dimethyl phthalate (DMP), but pose no danger of leaching from the polymer matrix and forming small endocrine disrupting chemicals. The synthesis of these covalent plasticizers is expected to be scalable, providing a viable alternative to the use of phthalates, thus mitigating dangers to human health and the environment.

  6. 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


    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.

  7. Functionalization of Multi-Walled Carbon Nanotubes with Thermo-Responsive Azide-Terminated Poly(N-isopropylacrylamide via Click Reactions

    Directory of Open Access Journals (Sweden)

    Yujun Feng


    Full Text Available Covalently functionalized multi-walled carbon nanotubes (MWNTs were prepared by grafting well-defined thermo-responsive poly(N-isopropylacrylamide (PNIPAM via click reactions. First, azide-terminated poly(N-isopropylacrylamide (N3-PNIPAM was synthesized by reversible addition fragmentation chain-transfer (RAFT polymerization, and then the N3-PNIPAM moiety was connected onto MWNTs by click chemistry. The products were characterized by means of FT-IR, TGA and TEM. The results show that the modification of MWNTs is very successful and MWNTs functionalized by N3-PNIPAM (MWNTs-PNIPAM have good solubility and stability in water. TEM images show the functionalized MWNTs are dispersed individually, indicating that the bundles of original MWNTs are separated into individual tubes by surface modification with polymer chains. These MWNTs modified with PNIPAM represent a potential nano-material for preparation of hydrophilic composite materials.

  8. Synthesis and Crystal Structure of a Spiral-chain Manganese(Ⅲ) Complex Containing Azide Bridge, [Mn(bzan)N3]n

    Institute of Scientific and Technical Information of China (English)



    The title complex, C22H22MnN5O2, crystallizes in orthorhombic system, space group P212121 with a = 6.887(1), b = 11.718(2), c = 25.721(5) (A。), V = 2075.7(7) (A。)3, Z = 4, Mr = 443.39, F(000) = 920, Dc = 1.419 g/cm3 and ( = 0.665mm(1 (MoK(). The structure was refined to R = 0.0593 and wR = 0.1427 for 3576 observed reflections with I ≥ 2((I). The Mn(Ⅲ) atom is coordinated to one bzan2-[bzan2- = N,N-ethylenebis(benzoylacetoneiminato)] ligand binding in the equatorial mode and two N3- ions in the axial positions. The azide acts as a trans-μ-(1, 3) bridge, resulting in an infinite helical chain propagating along the b axis.

  9. Continuous-Flow Electrophilic Amination of Arenes and Schmidt Reaction of Carboxylic Acids Utilizing the Superacidic Trimethylsilyl Azide/Triflic Acid Reagent System. (United States)

    Chen, Yuesu; Gutmann, Bernhard; Kappe, C Oliver


    A continuous flow protocol for the direct stoichiometric electrophilic amination of aromatic hydrocarbons and the Schmidt reaction of aromatic carboxylic acids using the superacidic trimethylsilyl azide/triflic acid system is described. Optimization of reagent stoichiometry, solvent, reaction time, and temperature led to an intensified protocol at elevated temperatures that allows the direct amination of arenes to be completed within 3 min at 90 °C. In order to improve the selectivity and scope of this direct amination protocol, aromatic carboxylic acids were additionally chosen as substrates. Selected carboxylic acids could be converted to their corresponding amine counterparts in good to excellent yields (11 examples, 55-83%) via a Schmidt reaction employing similar flow reaction conditions (acid intermediate, the corrosive nature of triflic acid, and the exothermic quenching were addressed by designing a suitable continuous flow reaction setup for both types of transformations.

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


    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.

  11. Regioselective Sequential Modification of Chitosan via Azide-Alkyne Click Reaction: Synthesis, Characterization, and Antimicrobial Activity of Chitosan Derivatives and Nanoparticles. (United States)

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


    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

  12. 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

  13. 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


    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.

  14. 碘、溴和叠氮化物水溶液中的声化学反应%Sonochemical Behavior of Aqueous Solutions of Iodide,Bromide and Azide

    Institute of Scientific and Technical Information of China (English)


    The sonolysis of azide solutions was investigated. The main product is nitrogen, which is formed in the reaction of N3 with OH radicals in the millimolar concentration range. At higher azide concentration, additional nitrogen is formed as hydrogen atoms are scavenged. Ammonia and hydrazine are minor products of the N3 sonolysis. Solutions of iodide and bromide are also irradiated under pH conditions where reactions of the products, i. e., hydrogen per oxide and iodide (or bromide) do not occur. The total yield of the products as well as the hydrogen yield is independent of the solute concentration. The results are understood in terms of the competition of the OH + OH and the OH + solute reactions. A local concentration of 4 × 10- 3 mol/L of the OH radicals in an interfacial region between the cavitation bubbles and the liquid is derived from the data obtained.

  15. Synthesis of 3-tetrazolylmethyl-azepino[4,5-b]indol-4-ones in two reaction steps: (Ugi-azide/N-acylation/SN2)/free radical cyclization and docking studies to a 5-Ht(6) model. (United States)

    Gordillo-Cruz, Raul E; Rentería-Gómez, Angel; Islas-Jácome, Alejandro; Cortes-García, Carlos J; Díaz-Cervantes, Erik; Robles, Juvencio; Gámez-Montaño, Rocío


    A series of nine novel 3-tetrazolylmethyl-azepino[4,5-b]indol-4-ones were prepared in moderate to good overall yields in only two reaction steps. The first step consisted of a one-pot sequential process of an Ugi-azide multicomponent reaction, N-acylation and SN2 to give the xanthates. The second step was an intramolecular cyclization under free radical conditions. Also, their binding modes have been modelled using docking techniques.

  16. 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. (United States)

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


    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.

  17. 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)


    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.

  18. 含醛基及叠氮基氮杂糖中间体的合成%Syntheses of Azasugar Intermediates Containing Aldehyde Group or Azide Group

    Institute of Scientific and Technical Information of China (English)

    李小六; 魏思楠; 张宏波; 张平竹; 王玮; 陈华


    以D-甘露糖为原料,分别利用苄胺双取代和aza-Wittig反应,再经氧化和亲核取代反应,合成了带保护基的含叠氮基及醛基的五元及六元氮杂糖中间体,对相关反应条件、基团保护及反应机理等进行了探讨,并提供了一种选择性脱除三苯甲基保护基的方法.%Protected five and six membered azasugar intermediates containing aldehyde group or azide group were synthesized using D-mannose as starting material via benzyl amine disubstitution or aza-Wittig reaction, then the oxidation and SN2 substitution reactions, respectively. The studies on the reaction conditions, the protecting groups and the reaction mechanism were also carried out, providing a protocol to remove trityl (Tr) group selectively.

  19. Synthesis, Crystal Structure and Magnetic Properties of a Novel Azide-bridged Copper(Ⅱ) Coordination Polymers Containing Nitroxy Nitroxide

    Institute of Scientific and Technical Information of China (English)

    WANG Yu-Fang; ZHANG Yong-Hua; WANG Li-Ya


    A novel azide-bridged copper(Ⅱ) coordination polymer, [Cu3(NITpPy)4(N3)6]n (NITpPy = 4-pyridyl-4,4,5,5-tetramethylimidazline-3-oxide-1-oxyl), was structurally and magnetically characterized. It crystallizes in the triclinic space group P with a = 7.6932(10), b = 14.5556(19), c = 16.122(2) , α = 108.443(2), β = 95.251(2), γ = 104.236(2)°, V = 1631.7(4) 3, C48H64Cu3N30O8, Mr = 1379.87, Z = 1, Dc = 1.404 g/cm3, μ(MoKα) = 1.041 mm-1, F(000) = 713, the R = 0.0510 and wR = 0.1185 for 4285 observed reflections with I 2σ(I). X-ray analysis reveals that the Cu(Ⅱ) ions are linked by nitrogen atom of μ1,1 azido ligands to form a Cu-Cu-Cu unit. The units are linked by μ1,3 azido ligands through a bridging style to form a one-dimensional coordination polymer. The variable-temperature magnetic susceptibility data of the complex show ferromagnetic interactions in the complex.

  20. Circular DNA by "Bis-Click" Ligation: Template-Independent Intramolecular Circularization of Oligonucleotides with Terminal Alkynyl Groups Utilizing Bifunctional Azides. (United States)

    Yang, Haozhe; Seela, Frank


    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.

  1. 含氮杂环结构叠氮固化剂的合成与性能%Synthesis and properties of azide curing agent with nitrogen heterocyclic ring

    Institute of Scientific and Technical Information of China (English)

    卢先明; 甘孝贤; 韩涛; 莫洪昌; 李娜; 栗磊


    为改善叠氮聚醚推进剂的力学性能,拟在叠氮固化剂结构中引入极性强的氮杂环结构,通过增强分子间的作用力,来提高叠氮聚氨酯弹性体的力学性能.以氮杂环结构三元醇三羟乙基异氰尿酸酯(THEIC)为起始荆,环氧氯丙烷(ECH)为单体,按阳离子开环聚合反应制得氯化聚醚多元醇(CPP);CPP经叠氮化取代反应制备出叠氮聚醚多元醇(APP);APP与六次甲基二异氰酸酯(HDI)加成反应制得未见文献报导的叠氮固化荆(HAP).通过对红外光谱、VPO数均相对分子质量(Mr)、羟值(OH)和异氰酸酯基含量(wNCO)等分析,对产物进行了结构鉴定与性能表征.胶片测试结果表明,在叠氮固化剂中引入强极性的氮杂环结构后,叠氮聚氨酯弹性体的力学性能有较大提高.GAP/HAP弹性体的拉伸强度和断裂伸长率分别为0.945 MPa和149.4%.引入乙二醇作扩链刑,相应弹性体的力学性能分别提高到1.438 MPa和161.16%.%To improve the mechanical property of the azide polyether propellant, nitrogen heterocyclic ring was introduced to the azide curing agent to enhance the intermolecular force, which would develop the mechanical property of the azide polyurethane elastomer. At the present of initiator of trihydroxyethyl isocyanurate(THEIC), the chloride polyether polyol (CPP) was synthesized by cationic ring-opening polymerization of epichlorohydrin. CPP reacted with NaN3 to give the azide polyether polyol(APP). The azide curing agent(HAP) was prepared by the addition of APP with HDI. These products were identified by IR, Mr(VPO), hydroxyl number(OH) and NCO group content(wNCO). The test data show that the mechanical property of azide polyurethane elastomer increased much by introducing nitrogen heterocyclic ring to the azide curing agent. The tensile strength and elongation at break of GAP/HAP are 0. 945 MPa and 149.4%. When adding ethylene glycol as chain extender, the tensile strength and elongation at break of

  2. Convenient Synthesis of a Propargylated Cyclic (3′-5′) Diguanylic Acid and its “Click” Conjugation to a Biotinylated Azide (United States)

    Grajkowski, Andrzej; Cieślak, Jacek; Gapeev, Alexei; Schindler, Christian; Beaucage, Serge L.


    The ribonucleoside building block, N2-isobutyryl-2′-O-propargyl-3′-O-levulinyl guanosine (Scheme 1), was prepared from commercial N2-isobutyryl-5′-O-(4,4′-dimethoxytrityl)-2′-O-propargyl guanosine in a yield of 91%. The propargylated guanylyl(3′-5′)guanosine phosphotriester shown in Scheme 2 was synthesized from the reaction of N2-isobutyryl-2′-O-propargyl-3′-O-levulinyl guanosine with N2-isobutyryl-5′-O-(4,4′-dimethoxytrityl)-2′-O-tert-butyldimethylsilyl-3′-O-[(2-cyanoethyl)-N,N-diisopropylaminophosphinyl] guanosine and isolated in a yield of 88% after P(III) oxidation, 3′-/5′-deprotection and purification. The propargylated guanylyl(3′-5′)guanosine phosphotriester was phosphitylated using 2-cyanoethyl tetraisopropylphosphordiamidite and 1H-tetrazole and was followed by an in situ intramolecular cyclization to give a propargylated c-di-GMP triester (Scheme 3), which was isolated in a yield of 40% after P(III) oxidation and purification. Complete N-deacylation of the guanine bases and removal of the 2-cyanoethyl phosphate protecting groups from the propargylated c-di-GMP triester were performed by treatment with aqueous ammonia at ambient temperature. The final 2′-desilylation reaction was effected by exposure to triethylammonium trihydrofluoride to give the desired propargylated c-di-GMP diester, the purity of which exceeded 95% (Figure 2B). Biotinylation of the propargylated c-di-GMP diester was easily accomplished through its cycloaddition reaction with a biotinylated azide derivative (Scheme 4) under click conditions to produce the biotinylated c-di-GMP conjugate of interest in an isolated yield of 62%. PMID:20942415

  3. Characterization of non-specific protein adsorption induced by triazole groups on the chromatography media using Cu (I)-catalyzed alkyne-azide cycloaddition reaction for ligand immobilization. (United States)

    Gao, Ming; Ren, Jun; Tian, Kaikai; Jia, Lingyun


    As an efficient and facile reaction, click chemistry has been growingly used in the preparation of chromatography media for immobilizing varying types of ligands. For the widely used Cu (I)-catalyzed alkyne-azide click reaction, a 1, 2, 3-triazole group will be inevitably introduced in the molecular linkage, which could give rise to unexpected non-specific adsorption especially for the media employing small compound ligands or high ligand density. Triazole-induced non-specific protein adsorption on sepharose resins was evaluated systematically in this work, by considering the effects of triazole content, length of spacer arm, and solution conditions. We found that triazole content of a resin played the key role. Protein adsorption became significant when the media was coupled with triazole at a medium density (about 60μmol/mL gel), and the binding amount further increased with triazole density. The resin with triazole content of about 100μmol/mL gel could adsorb human IgG, bovine serum albumin and lysozyme at the amount of 13.6, 30.0, and 5.1mg/mL respectively. Proteins tended to be adsorbed at higher amount as the pH of solution approached their isoelectric points, and increasing salt concentration could reduce triazole-induced adsorption but only within limited extent. This study can facilitate reasonable application of click chemistry in the synthesis of chromatography media, by providing some basic principles for optimizing structural properties of separation media and choosing suitable solution conditions.

  4. 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


    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

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

  6. Synthesis and characterization of cyclic polystyrene using copper-catalyzed alkyne-azide cycloaddition coupling - evaluation of physical properties and optimization of cyclization conditions (United States)

    Elupula, Ravinder

    Polymers with a cyclic topology exhibit a range of unique and potentially useful physical properties, including reduced rates of degradation and increased rates of diffusion in bulk relative to linear analogs. However the synthesis of high purity cyclic polymers, and verification of their structural purity remains challenging. The copper-catalyzed azide-alkyne "click" cyclization route toward cyclic polymers has been used widely, due to its synthetic ease and its compatibility with diverse polymer backbones. Yet unoptimized click cyclization conditions have been observed to generate oligomeric byproducts. In order to optimize these cyclization conditions, and to better understand the structure of the higher molecular weight oligomers, these impurities have been isolated by size exclusion chromatography (SEC) and characterized by mass spectrometry (MS). Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry (MALDI-ToF) MS is a particularly valuable characterization tool and was used to determine that the high molecular weight impurities are predominantly cyclic oligomers. It should also be noted that the rapid analysis and small analyte requirements of this MS technique make it particularly attractive as a general tool for elucidating polymer architecture. Ability to tailor the physical properties of polymers by changing the architecture alone has garnered a lot of attention over the past few decades. Compared to their linear analogues, these novel polymer architectures behave completely different in nanoscale regime. Cyclic polymers are especially intriguing since we can compare the differences in the physical properties with that of the linear chains. One of the major physical property changes are T g-confinement effect. Using ATRP and "click chemistry" we have produced highly pure cyclic PS (c-PS) with number-average molecular weight (MW) of 3.4 kg/mol and 9.1 kg/mol. Bulk glass transition temperatures for c-PS were weakly depended on MWs

  7. 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 (United States)

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


    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.

  8. 糊精氮化铅球形化工艺参数的研究%Research on Technological Parameters of Spherical Dextrin Lead Azide

    Institute of Scientific and Technical Information of China (English)

    许勇; 王日强; 徐晓峰; 裴刚


    Through the charge-pressing floating test and fluxion property determination of initiating charge in organic glass shell, it is found that reduction of loading performance, bad fluxion property and easy floating of charge-pressing would occur with the increasing of mass fraction of particles with grain size less than 45μm in spherical dextrin lead azide. It is also found that charge-pressing floating will be caused by frequently burst pressure and instantaneous-explosion of MS delay electric detonator. Two quantity control indexes were proposed including bulk density≥2. 00 g/cm3 , and mass frac-tion of particles with grain size less than 45 μm ≤20%. Preparation process is as follows:3% ( mass fraction) sodium nitrite solution is added into 8% (mass fraction) lead nitrate solution, the mass ratio of water and charge is 30︰1, addi-tional amount of industry acidity dextrin is 5% (mass fraction) , alkalinity of sodium nitride solution is 0. 080%, and the certain feeding speed and stirring intensity are maintained at the temperature of 60℃. The manufactured initiating charge can meet the requirements of detonator assembly.%通过起爆药在有机玻璃管壳中压药上浮试验和流散性测定,发现球形糊精氮化铅中粒径<45μm颗粒的含量增多,使药剂装药性能下降、流散性变差,压药容易上浮;频繁压爆、毫秒延期电雷管瞬爆是压药上浮所致。提出两项质量控制指标:药剂堆积密度≥2.00 g/cm3;粒径<45μm颗粒的质量分数≤20%。工艺参数:3%(质量分数)氮化钠溶液加入8%(质量分数)硝酸铅溶液,水药质量比30︰1,工业酸性糊精质量分数(外加)5%,氮化钠溶液碱度0.080%,化合温度60℃。保持一定的加料速度和搅拌强度,能稳定生产出满足雷管装配需求的起爆药。

  9. A fluorogenic probe for the copper(I)-catalyzed azide-alkyne ligation reaction: modulation of the fluorescence emission via 3(n,pi)-1(pi,pi) inversion. (United States)

    Zhou, Zhen; Fahrni, Christoph J


    Chemoselective ligation reactions represent a powerful approach for labeling of proteins or small molecules in a biological environment. We report here a fluorogenic probe that is activated by click chemistry, a highly versatile bio-orthogonal and chemoselective ligation reaction which is based on the azide moiety as the functional group. The electron-donating properties of the triazole ring that is formed in the course of the coupling reaction was effectively utilized to modulate the fluorescence output of an electronically coupled coumarin fluorophore. Under physiological conditions the probe is essentially nonfluorescent and undergoes a bright emission enhancement upon ligation with an azide. Time-resolved emission spectroscopy and semiempirical quantum-mechanical calculations suggest that the fluorescence switching is due to an inversion of the energy ordering of the emissive 1(pi,pi*) and nonemissive 3(n,pi*) excited states. The rapid kinetics of the ligation reaction render the probe attractive for a wide range of applications in biology, analytical chemistry, or material science.

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

  11. 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:; Jassal, Amanpreet Kaur; Chawla, S.K., E-mail:


    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

  12. Síntese e atividade citotóxica de alguns azido-ciclopaladados estabilizados com ligantes bifosfínicos Synthesis and cytotoxicity of some cyclometallated palladium (II complexes containing coordinated azide and diphosphines

    Directory of Open Access Journals (Sweden)

    Antonio Carlos Fávero Caires


    Full Text Available Some cyclopalladated compounds containing the azido group ligand and the (C-N ring of N,N-dimethylbenzylamine have been prepared by bridge opening reactions of dimmer azide complex precursor with some diphosphines in different stoichiometric quantities. The neutral or ionic, mono or binuclear complexes synthesized were characterized by elemental analyses, I. R. spectroscopy and NMR techniques. The series of complexes was screened for cytotoxicity against a panel three human tumour cells lines(C6,Hep-2,HeLa. All complexes were found to be cytotoxic (IC50 at µM concentrations while one complex having the coordination bond N-Pd ruptured also displayed some differential cytotoxicity.

  13. 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)


    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).

  14. 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)



    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

  15. 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


    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.

  16. Effect of sadiron azide on morphology and biomechanics of rite decellular tissue-engineered cardiac valves%叠氮钠对脱细胞组织工程心脏瓣膜形态学及生物力学的影响

    Institute of Scientific and Technical Information of China (English)

    马金本; 钟竑; 韩绍先; 单根法; 林峰


    目的 对比加叠氮钠和传统的去氧胆酸钠法去除细胞后心脏瓣膜形态学及生物力学差别,为构建理想的组织工程心脏瓣膜提供实验依据.方法 应用两种方法处理6~7月龄新鲜猪主动脉心脏瓣膜.光学显微镜、透射电镜观察脱细胞基质改变,厚度仪测量组织厚度,行拉力测试观察两种方法处理后力学变化上的差异.结果 两种方法处理后组织厚度差异无统计学意义(P>0.01).显微镜检和透射电镜见叠氮钠-去氧胆酸钠法对基质破坏较少,处理后生物力学优于传统去氧胆酸钠法,差异有统计学意义(P 0.01), but biomechanics properties-maximum deflection, elongation rate, max tensile stress and max load-were increased significantly in the group with sodium azide (P <0.01). Same results could be obtained through Tensile deflection-Tensile stress and Tensile deflection-Load curve. Although complete decellularization was achieved, matrix structure was comparative integrity in the group treated with sodium azide. Intact, dense collagen fibers and plush-like fibers were seen in the experimental Stoup, while sparse collagen fibers and less velvet-like fibers were present in the control group. Complete and continuous elastic fibers were preserved in the specimens treated with sodium azide while discontinuous, broken and thin fibers were seen in the control group. The pattern d ultrastructure in the sodimn azide group revealed matrix in high density and more fiber bundles in the field. In the com-trol group, the quality of the matrix decreased significantly, and loose fibers with apparent gap were seen. Conclusion Sodium azide can preserve the matrix structure efficiently during the decellurazation procedure and improve the bio-mechanical properties of tissue engineered cardiac valves.

  17. Mutagenic effectiveness and efficiency of sodium azide versus ethyl methanesulfonate in maize: induction of somatic mutations at the yg/sub 2/ locus by treatment of seeds differing in metabolic state and cell population

    Energy Technology Data Exchange (ETDEWEB)

    Conger, B.V.; Carabia, J.V.


    This study was conducted to compare the effectiveness and efficiency of sodium azide (NaN/sub 3/) and ethyl methanesulfonate (EMS) for inducing somatic mutations at the yg/sub 2/ locus in maize seeds of two different metabolic states and cell populations. Dormant or presoaked (72 h at 20/sup 0/C) seeds heterozygous for yg/sub 2/ locus were treated with different concentrations of either EMS or NaN/sub 3/. The cell populations with respect to the percentage of cells in G/sub 1/, S, G/sub 2/, and M were also determined for seeds of the two metabolic states. Dormant seeds possessed a higher percentage of cells in G/sub 1/ and the presoaked seeds a higher percentage of cells in S, G/sub 2/, and M. The frequency of yg/sub 2/ sectors in leaves 4 and 5 increased with increasing concentration of both mutagens in both dormant and presoaked seeds. Both mutagens were more effective and efficient in the presoaked seeds. NaN/sub 3/ was more effective than EMS in terms of number of sectors induced per unit of dose. However, EMS was more efficient as determined by sectors induced per unit of seedling injury and clearly had the ability to induce much higher sector frequencies (more than 10 times greater) than NaN/sub 3/. The low ability of NaN/sub 3/ (compared to EMS) to induce mutant sectors may be related to the cells not being treated at the optimum time during the cell cycle, but it is more likely due to its low effectiveness for inducing chromosome aberrations.

  18. Synthesis and Crystal Structure of an Azide Bridged Binuclear Zinc(II) Complex Including the Reduced Derivative of Nitronyl Nitroxide,[Zn(Him2Py)(N3)2]2

    Institute of Scientific and Technical Information of China (English)

    王利亚; 张晨曦; 廖代正; 姜宗慧; 阎世平


    The title compound [Zn(Him2Py)(N3)2]2 (Zn2C26H38N18O2, Mr = 765.48) has been prepared and structurally characterized by X-ray diffraction methods. It crystallizes in monoclinic, space group P21/n with a = 10.989(3), b = 11.519(3), c = 13.812(4) A, β = 101.700(5)°,V = 1711.9(9) A3, Z = 2, Dc = 1.485 g/cm3,μ(MoKα) = 1.456 mm~1, F(000) = 792, the final R =0.0401 and wR = 0.0861 for 2054 observed reflections with I>2σ(I). The imino nitroxide 2-(3 ′-methyl-2′-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-lH-imidazolyl-l-oxyl (im2Py) was reduced to obtain 2-(3′-methyl -2′-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-lH-imidazole-1-ydroxy (Him2Py)coordinating to the zinc (Ⅱ) ion, around which the coordination geometry is a square-based pyramid with a terminal nitrogen atom located at the apical position. The four basal sites are occupied by two μ1,1 nitrogen atoms from two different bridging azide ions and two nitrogen atoms from Him2Py.The units of [Zn(Him2Py)(N3)2]2 were connected as two dimension planes by intermolecular hydrogen bonds.

  19. 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


    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.

  20. 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


    María Teresa Ramírez-Palma; Jesús Segura-Arzate; Gustavo López-Téllez; Erick Cuevas-Yañez


    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.

  1. Application of azides in chemoselective amidation reactions

    NARCIS (Netherlands)

    Merkx, N.S.M.


    Chemical methods that enable the synthesis and the site-selective modification of biomolecules offer great possibilities for studying their biological function and have found widespread use in chemical biology. Most often these methods employ chemoselective ligation reactions which feature mutually

  2. Application of azides in chemoselective amidation reactions


    Merkx, N.S.M.


    Chemical methods that enable the synthesis and the site-selective modification of biomolecules offer great possibilities for studying their biological function and have found widespread use in chemical biology. Most often these methods employ chemoselective ligation reactions which feature mutually and uniquely reactive functional groups to enable the covalent coupling of unprotected biomolecules without interference of any other functional groups either present in the biomolecule to be coupl...

  3. Site-directed spin-labeling of DNA by the azide-alkyne 'click' reaction: nanometer distance measurements on 7-deaza-2'-deoxyadenosine and 2'-deoxyuridine nitroxide conjugates spatially separated or linked to a 'dA-dT' base pair. (United States)

    Ding, Ping; Wunnicke, Dorith; Steinhoff, Heinz-Jürgen; Seela, Frank


    Nucleobase-directed spin-labeling by the azide-alkyne 'click' (CuAAC) reaction has been performed for the first time with oligonucleotides. 7-Deaza-7-ethynyl-2'-deoxyadenosine (1) and 5-ethynyl-2'-deoxyuridine (2) were chosen to incorporate terminal triple bonds into DNA. Oligonucleotides containing 1 or 2 were synthesized on a solid phase and spin labeling with 4-azido-2,2,6,6-tetramethylpiperidine 1-oxyl (4-azido-TEMPO, 3) was performed by post-modification in solution. Two spin labels (3) were incorporated with high efficiency into the DNA duplex at spatially separated positions or into a 'dA-dT' base pair. Modification at the 5-position of the pyrimidine base or at the 7-position of the 7-deazapurine residue gave steric freedom to the spin label in the major groove of duplex DNA. By applying cw and pulse EPR spectroscopy, very accurate distances between spin labels, within the range of 1-2 nm, were measured. The spin-spin distance was 1.8±0.2 nm for DNA duplex 17(dA*(7,10))⋅11 containing two spin labels that are separated by two nucleotides within one individual strand. A distance of 1.4±0.2 nm was found for the spin-labeled 'dA-dT' base pair 15(dA*(7))⋅16(dT*(6)). The 'click' approach has the potential to be applied to all four constituents of DNA, which indicates the universal applicability of the method. New insights into the structural changes of canonical or modified DNA are expected to provide additional information on novel DNA structures, protein interaction, DNA architecture, and synthetic biology.

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


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


    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...

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

    Directory of Open Access Journals (Sweden)

    R. R. Sanghavi


    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.

  6. Astaxanthin inhibits sodium azide-induced cytotoxicity in hepatocyte L-02 cells probably by H+ transferring function%虾青素可能通过H+传递功能保护NaN3损伤的人胎肝L-02细胞

    Institute of Scientific and Technical Information of China (English)

    马建; 陈海敏; 严小军; 王峰; 徐炜烽


    观察虾青素(astaxanthin)对呼吸链复合体Ⅳ抑制剂叠氮钠(NaN)损伤的人胎肝L-02细胞保护作用,并初步探讨其作用机制.100 mmol·L NaN用于构建肝损伤细胞模型,通过测定不同浓度虾青素(0.01、0.10、1.00及10.00 nmol·L)对损伤细胞存活率(MTT检测)、细胞内活性氧(reactive oxygen species,ROS)水平(DCFH-DA检测)、细胞凋亡率(Annexin V-FITC/PI双染法)以及线粒体膜电位(mitochondrial membranepotential,MMP)水平(JC-1法)的影响,发现虾青素能抑制损伤细胞晚期凋亡;对细胞存活率和MMP的保护作用呈现先增加后降低的非剂量依赖性关系,其中0.10 nmol·L虾青素表现为较强的保护作用;实验浓度范围内的虾青素并不能显著降低细胞内ROS水平(P>0.05).为进一步探讨虾青素对损伤细胞的保护作用,人工制备平面双层磷脂膜(planar bilaycr lipid membrane,BLM)模拟线粒体膜,测定不同浓度虾青素(0.1%、2.0%、10.0%)对H的传递能力.结果显示,虾青素对H传递效率无剂量依赖性,中等浓度(2.0%)的虾青素能够较高效率地传递H.结果提示,虾青素对NaN损伤的人胎肝细胞的保护作用与其直接淬灭ROS的抗氧化功能无关,而可能是通过适当浓度下的虾青素对H的高效传递进而维持线粒体膜电位实现的.%This study is to investigate the protective effect of astaxanthin against injured hepatocyte L-02 cells induced by sodium azide (NaN3) and reveal the possible mechanisms. Hepatocyte L-02 cells were exposed to 100 mmol·L-1 NaN3 with various concentrations of astaxanthin pre-incubated, then the cell viability was measured by MTT method; The level of reactive oxygen species (ROS) was determined by DCFH-DA method; The changes of mitochondrial membrane potential (MMP) and apoptosis ratio were detected by JC-1 method and Annexin V-FITC/PI double stain method, respectively. Results showed that after cells were exposed to 100 mmol·L-1 NaN3 for 3 hours, the cell

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

    DEFF Research Database (Denmark)

    Bendix, Jesper; Birk, Torben; Weyhermüller, Thomas


    .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...

  8. Acid-base jointly promoted copper(I)-catalyzed azide-alkyne cycloaddition. (United States)

    Shao, Changwei; Wang, Xinyan; Zhang, Qun; Luo, Sheng; Zhao, Jichen; Hu, Yuefei


    In this novel acid-base jointly promoted CuAAC, the combination of CuI/DIPEA/HOAc was developed as a highly efficient catalytic system. The functions of DIPEA and HOAc have been assigned, and HOAc was recognized to accelerate the conversions of the C-Cu bond-containing intermediates and buffer the basicity of DIPEA. As a result, all drawbacks occurring in the popular catalytic system CuI/NR(3) were overcome easily.

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

    Directory of Open Access Journals (Sweden)

    Zachary L. Palchak


    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.

  10. Synthesis of Quinoxaline Derivatives via Tandem Oxidative Azidation/Cyclization Reaction of N-Arylenamines. (United States)

    Ma, Haichao; Li, Dianjun; Yu, Wei


    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.

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

    DEFF Research Database (Denmark)

    Sminia, T.J.; Pedersen, Daniel Sejer


    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...

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


    Hartdegen, Vera


    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...

  13. Citrus Peel Additives for One-Pot Triazole Formation by Decarboxylation, Nucleophilic Substitution, and Azide-Alkyne Cycloaddition Reactions (United States)

    Mendes, Desiree E.; Schoffstall, Allen M.


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

  14. 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


    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 bulk...... studies showed increasing film thickness with increasing DMSO content, with the measured thickness in pure DMSO being >250% of the thickness in pure water. A similar, but less pronounced, behavior was observed for unmodified poly(3,4-ethylenedioxythiophene) tosylate (PEDOT). High-density grafting...

  15. A Versatile Strategy to Synthesize Perfluoropolyether-Based Thermoplastic Fluoropolymers by Alkyne-Azide Step-Growth Polymerization. (United States)

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


    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).

  16. Azide derivatized anticancer agents of Vitamin K 3: X-ray structural, DSC, resonance spectral and API studies (United States)

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


    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.

  17. 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.

    sub (2)O sub (4)(7) or C sub (2)CH sub (2)O sub (4)(10)] have been prepared by the reaction of [(p-cymene)RuCl sub (2)]sub (2) with the corresponding sodium salts of the carboxylic acids. Treatment of (eta sup (6)-p-cymene) ruthenium(II) carboxylato...

  18. 1,5 iodonaphthyl Azide Inactivated V3526 Protects against Aerosol Challenge with Virulent Venezuelan Equine Encephalitis Virus. (United States)


    Research Institute of Infectious Diseases , Fort Detrick, MD 21702. *Correspondence should be addressed to: Dr. Radha K. Maheshwari, 4301 Jones Bridge...immunization was done with equal volumes of saline for each route of immunization. Serum was collected by retro-orbital bleed from animals in all the groups...United States Army Medical Research Institute of Infectious Diseases (USAMRIID), Frederick, MD. Research was conducted under an IACUC approved protocol

  19. High-density functionalization and cross-linking of DNA: "click" and "bis-click" cycloadditions performed on alkynylated oligonucleotides with fluorogenic anthracene azides. (United States)

    Pujari, Suresh S; Ingale, Sachin A; Seela, Frank


    High density functionalization of DNA with ethynyl and octadiynyl side chains followed by CuAAC "click labeling" with 9-azidomethylanthracene was performed. Alkynyl DNA was also cross-linked with fluorogenic 9,10-bis-azidomethylanthracene employing the "bis-click" reaction. By this means the fluorescence of the anthracene moiety was imparted to the virtually nonfluorescent DNA. Phosphoramidites of 8-aza-7-deaza-2'-deoxyadenosine with short and long linker arms in a steric nondemanding 7-position were utilized in solid phase oligodeoxynucleotide synthesis. High density alkynylated DNA-without anthracene residues-was found to be of comparable stability with both long and short linker arms. High density anthracene functionalized DNA became less stable with the short linker compared to that with the long linker connectivity. Interstrand cross-linked homodimers constructed from alkynylated oligonucleotides with fluorogenic 9,10-bis-azidomethylanthracene were hybridized with complementary strands to form double helices. They are more stable when the linker was located at a terminus than in a central position. Short linker anthracene adducts were destabilizing compared to long linker adducts. The fluorogenic anthracene residues not only have a significant effect on the duplex stability, but also impart fluorescence to the species. Fluorescence of cross-linked double helices with long linker connectivity was quenched when the cross-link was in a terminal position and was dequenched when the linker was connecting the two double helices at the center of the molecule. The fluorescence of the anthracene cross-linked double helices was strongly increased (dequenched) when the correct base pair was formed, while no change occurred upon mismatch formation.

  20. Determination of the phospholipid precursor of anandamide and other N- acylethanolamine phospholipids before and after sodium azide-induced toxicity in cultured neocortical neurons

    DEFF Research Database (Denmark)

    Hansen, H.H.; Schousboe, A.; Hansen, Harald S.;


    Phospholipase D-mediated hydrolysis of N-acylethanolamine phospholipids (NAPEs) releases anandamide and other N-acylethanolamines, resulting in different actions at cellular targets in the CNS. Recently, we have demonstrated that these N-acyl lipids accumulate in cultured neocortical neurons...

  1. 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.

    The dimeric Eta sup(6)-hexamethylbenzene ruthenium(II) triazole compounds of formulation (((Eta sup(6)-C sub(6)Me Sub(6))Ru(N sub(3)C sub(2)(CO sub(2)R)sub(2)) sub(2) - (mu C sub(2)O sub(4))) have been synthesized by 1,3-diploar cycloadditions...

  2. Metal-Organic Framework Templated Synthesis of Copper Azide as the Primary Explosive with Low Electrostatic Sensitivity and Excellent Initiation Ability. (United States)

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


    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.

  3. Thermodynamic, Dynamic, and Structural Properties of Ionic Liquids Comprised of 1-butyl-3-methylimidazolium Cation and Nitrate, Azide, or Dicyanamide Anions (United States)


    of the symmetric structure of NO3 anion. Cadena and Maginn also analyzed the rotational dynamics of ions in their simulations of [bmim][NO3].xxiii... Cadena and Maginn reported rotational relaxation times of 91 ps at 298 K and about 3ps at 393 K, while our simulations predict 6 and 1.8 ps relaxation...Chem. Soc., 2005, 127, 12192. xxiii Cadena , C.; Maginn, E. J. J. Phys. Chem. B 2006, 110, 18026. xxiv Emel’yanenko, V.N.; Verevkin, S.P.; Heintz

  4. In Vivo Test for Chemical Induction of Micronucleated Polychromatic Erythrocytes in Mouse Bone Marrow Cells. Test Article: Dimethylamine-2-2ethyl azide (DMAZ) (United States)


    Subpart F, Section 798.5395, In Vivo mammalian bone marrow cytogenetics tests : Micronucleus Assay. Revised July 1, 2002, (1). OECD Guideline for Testing ...of Chemicals, No. 474. Mammalian Erythrocyte Micronucleus Test . Adopted July 21, 1997, (2). International Conference on Harmonisation of Technical...Finding Test . Five male and five female mice per dose group per harvest time were used in the Micronucleus Assay. The Range Finding Test was

  5. 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



  6. Test for Chemical Induction of Chromosome Aberrations in Cultured Chinese Hamster Ovary (CHO) Cells With and Without Metabolic Activation. Test Article: Dimethylamine-2-2ethyl azide (DMAZ) (United States)


    chromosomes leading to four-armed configurations. This could be asymmetrical with formation of a dicentric and an acentric chromatid, ifunion is complete...chromatid union. Dicentric - an asymmetrical exchange between two chromosomes resulting in a chromosome with two centromeres with or without sister chromatid union. ’ d - Dicentric - an asymmetrical exchange between two chromosomes resulting, r dm in a chromosome with two centromeres

  7. Attachment of antimicrobial peptides to reverse osmosis membranes by Cu(i)-catalyzed 1,3-dipolar alkyne-azide cycloaddition

    NARCIS (Netherlands)

    Bodner, Elias J.; Kandiyote, Nitzan Shtreimer; Lutskiy, Marina Yamit; Albada, Bauke; Metzler-Nolte, Nils; Uhl, Wolfgang; Kasher, Roni; Arnusch, Christopher J.


    Biofilms are detrimental to many industrial systems that include reverse osmosis (RO) membranes. Accordingly, the development of surfaces with inherently bactericidal properties has attracted much research attention. Antimicrobial peptides (AMPs) have been shown to be potent antimicrobial and ant

  8. New topology in azide-bridged cobalt(II) complexes: the weak ferromagnet [Co(2)(N(3))(4)(Hexamethylenetetramine)(H(2)O)](n). (United States)

    Mautner, Franz A; Ohrström, Lars; Sodin, Beate; Vicente, Ramon


    A new polynuclear azido-bridged Co(II) compound with formula [Co(2)(N(3))(4)(HMTA)(H(2)O)](n) (1) (HMTA = hexamethylenetetramine) has been structurally and magnetically characterized. The compound 1 crystallizes in the monoclinic system C2/m space group, and consist of a complex three-dimensional system in which end-to-end and end-on azido bridging ligands between the Co(II) atoms coexist. The HMTA ligand is also linking three different Co(II) atoms. The network analysis shows for 1 a three- and six-connected network topology not previously reported. The magnetic properties of 1 are also reported, and it was found that the magnetic interactions define another new three- and four-connected net assigned as a (6.8(2))(6(4).10(2))-tfo net. In the high temperature region the chi(M) versus T plot can be fitted by using the Curie-Weiss law, and the best fit theta value is -26.6 K. For 1 magnetic ordering and spontaneous magnetization is achieved below T(c) = 15.6 K.

  9. Microwave synthesis of mono- and bis-tetrazolato complexes via 1,3-dipolar cycloaddition of organonitriles with platinum(II)-bound azides. (United States)

    Mukhopadhyay, Suman; Lasri, Jamal; Charmier, M Adília Januário; da Silva, M Fátima C Guedes; Pombeiro, Armando J L


    [2 + 3] Cycloaddition reactions of the diazidoplatinum(II) complexes cis-[Pt(N3)2(PPh3)2] 1 and cis-[Pt(N3)2(2,2'-bipy)] 4 with organonitriles NCR 2 give the bis(tetrazolato) complexes trans-[Pt(N4CR)2(PPh3)2] 3 [R = Me (3a), Et (3b), Pr (3c), Ph (3d), 4-ClC6H4 (3e)] and cis-[Pt(N4CR)2(2,2'-bipy)] 5 [R = Me (5a), Et (5b), Pr (5c), Ph (5d)]. The reaction of cis-[Pt(N3)2(PPh3)2] I with propionitrile also affords, apart from 3b, the unexpected mixed cyano-tetrazolato complex trans-[Pt(CN)(5-ethyltetrazolato)(PPh3)2] 3b' which is derived from the reaction of the bis(tetrazolato) 3b with propionitrile, with concomitant formation of 5-ethyl-1H-tetrazole, via a suggested unusual oxidative addition of the nitrile to PtII. All these reactions are greatly accelerated by microwave irradiation and this method also shows a higher selectivity in the case of the reaction of propionitrile with 1, leading only to the formation of 3b. All the complexes obtained were characterized by IR, 1H, 13C and 31P[1H] (for complexes 3) NMR spectroscopies, FAB-MS and elemental analyses. Complexes 3b', 3d, 3e and 5d were also characterized by X-ray structural analyses.

  10. Halo- and azidodediazoniation of arenediazonium tetrafluoroborates with trimethylsilyl halides and trimethylsilyl azide and sandmeyer-type bromodediazoniation with Cu(I)Br in [BMIM][PF6] ionic liquid. (United States)

    Hubbard, Abigail; Okazaki, Takao; Laali, Kenneth K


    Reaction of [ArN(2)][BF(4)] salts immobilized in [BMIM][PF(6)] ionic liquid (IL) with TMSX (X = I, Br) and TMSN(3) represents an efficient method for the preparation of iodo-, bromo-, and azido-derivatives via dediazoniation. The reactions can also be effected starting with ArNH(2) by in situ diazotization with [NO][BF(4)] followed by reaction with TMSX or TMSN(3). Depending on the substituents on the benzenediazonium cation, competing fluorodediazoniation (ArF formation) and hydrodediazoniation (ArH formation) were observed. Dediazoniation with TMSN(3) and with TMSI generally gave the highest chemoselectivity toward ArN(3) and ArI formation. The IL was recycled and reused up to 5 times with no appreciable decrease in the conversions. Multinuclear NMR monitoring of the interaction of [ArN(2)][BF(4)]/TMSX, [BMIM][PF6]/TMSX, and [BMIM][PF(6)]/TMSX/[ArN(2)][BF(4)] indicated that TMSF is formed primarily via [ArN(2)][BF(4)]/TMSX, generating [ArN(2)][X] in situ, which gives ArX on dediazoniation. Competing formation of ArF in Sandmeyer-type bromodediazoniation of [ArN(2)][BF(4)] with Cu(I)Br immobilized in the IL points to significant involvement of heterolytic dediazoniation.

  11. 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


    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

  12. 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


    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.

  13. The Calculation of Bond Dissociation Energies for Azide Group in Some Azido Compounds%对一些叠氮化合物的叠氮自由基键离解能的计算

    Institute of Scientific and Technical Information of China (English)

    邵菊香; 程新路; 杨向东; 葛素红



  14. 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.


    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.

  15. 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


    (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.

  16. Underwater-Shock/Bubble Interaction and Its Application to Biology and Medicine (United States)

    Takayama, Kazuyoshi; Yamamoto, H.; Abe, A.

    In 1988 we produced lead azide pellets in house and studied propagation of microunderwater shock wave and its interaction with air bubble. Later we replaced lead azide pellets with silver azide pellets supplied by Chugiku Kayaku Co. Ltd, weighing a few mg to 30 mg [1] and devoted to safely study underwater shock waves and its application to medicine.

  17. Response of Primary Explosives to Gaseous Discharges in an Improved Approaching-Electrode Electrostatic Sensitivity Apparatus (United States)


    basic lead styphnate. RD1333 lead azide, dextrinated lead azide and tetracene all ignited. But, as expected, tetryl, PETN. superfine PETN, RDX, HA.¶X...qualification for this test. The test results shall be reported along with those for normal lead styphnate and dextrinated lead azide obtained using the same

  18. Qualitative Assessment of the Ignition of Highly Flammable Fuels by Primary Explosives, (United States)


    primary explosives used in the investigation are listed below:- basic lead azide lead azide lead styphnate barium styphnate potassium picrate Bakelite Tubes Basic Lead Azide w Lead Styphnate LDNR Barium Styphnate I Flash Composition Potassium Picrate I TABLE 3 IGNITION OF HEXANE SOAKED...Flammability Nichrome Bridgewire in Aluminium Tube Potassium Picrate X LDVR X Barium Styphnate X Tetracene X 200 mq Lead Styphnate X 400 mq Lead

  19. Environmentally Benign Stab Detonators (United States)


    a mixture of lead azide, lead styphnate , barium nitrate, antimony sulfides, and tetracene) mJ millijoule (10–3 J) FINAL REPORT PP...initiating mix (NOL-130) and transfer charge of current stab detonators contain hazardous materials such as lead azide, lead styphnate , and barium nitrate...tetracene) and heavy metal constituents (e.g., lead styphnate , lead azide, barium nitrate, and antimony sulfides) present in the NOL-130 initiating

  20. Synthesis of GAP and PAMMO Homopolymers from Mesylate Polymeric Precursors (United States)

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


    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.

  1. 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


    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.

  2. 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.


    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,

  3. Method of preparation of uranium nitride (United States)

    Kiplinger, Jaqueline Loetsch; Thomson, Robert Kenneth James


    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.

  4. Compilation of Blast Parameters of Selected High Explosives, Propellants, and Pyrotechnics in Surface Burst Configurations. (United States)


    Distance for Dextrinated Lead Azide ............. 212 90. Peak Pressure and Scaled Positive Impulse Versus Scaled Distance for Lead Styphnate...207 41. Summary of Results for Hemispherical Surface Bursts, Peak Pressure, and Scaled Positive Impulse Values for Dextrinated ...these values with standard hemispher- ical TNT data to determine TNT equivalency. MATERIAL Dextrinated lead azide a sensitive primary explosive, was

  5. Stabilization of Parallel Triplexes by Twisted Intercalating Nucleic Acids (TINAs) Incorporating 1,2,3-Triazole Units and Prepared by Microwave-Accelerated Click Chemistry

    DEFF Research Database (Denmark)

    Géci, Imrich; Filitchev, Vyacheslav Viatcheslav; Pedersen, Erik Bjerreg.


    A highly efficient method for postsynthetic modification of unprotected oligonucleotides incorporating internal insertions of (R)-1-O-(4-ethynylbenzyl)glycerol has been developed through the application of click chemistry with water-insoluble pyren-1-yl azide and water-soluble benzyl azide...

  6. Synthesis of telechelic vinyl/allyl functional siloxane copolymers with structural control

    DEFF Research Database (Denmark)

    Madsen, Frederikke Bahrt; Javakhishvili, Irakli; Jensen, Rasmus Egekjær


    groups and high end- group fi delity are obtained in a facile and robust synthetic scheme involving polycondensation, end-group transformation and di ff erent functionalisation reactions such as Cu( I )-mediated azide – alkyne cycloaddition. Pendant alkyl chloride, alkyl azide, bromoisobutyryl, 4...

  7. Pericyclic and related rearrangements for the synthesis of nitrogen heterocyclic ring systems



    The thesis describes synthesis and reactions of allene azides tethered to various functional groups and the application of the discovered cascade transformations towards the synthesis of radianspene J model system. Chapter 1 covers reactions of simple allene azides containing alkyl and cycloalkyl substituents. Thermal rearrangements of these substrates delivered isocyanides and azadienes via the proposed azatrimethylenemethane (ATMM) intermediates. On the other hand, vinylidenecycloprop...

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

    Directory of Open Access Journals (Sweden)

    Hocine Merazig


    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.

  9. Development Program of Dual Mode Impact Delay Module for Artillery Fuzes. (United States)


    istently and unmistakably Dextrinated lead azide was, tent surrogate. On the basis of stab s Id be predicted that any system whi r mated lead azide...of the this last finding, that the mean itiation of the r is at least 430 In tests of Cite subject interface using dextrinated lead azide...ol Rotor of 11)V) tujsc with Miü •up loaded vith dextrinated lend (acceptor) .’)/’. :!•• and covered w: L11 alnr.umii.i

  10. Synthesis of Farnesol Analogues Containing Triazoles in Place of Isoprenes through 'Click Chemistry' (United States)

    Subramanian, Thangaiah; Parkin, Sean; Spielmann, H Peter


    A solid-phase three-component Huisgen reaction has been used to generate polar farnesol and farnesyl diphosphate analogues. The Cu(I)-catalyzed 1,3-cycloadditions of various azides with solid supported (E)-3-methylhept-2-en-6-yn-1-ol provided only the 1,4-disubstituted 1,2,3-triazole regioisomers. The organic azides were generated in situ to minimize handling of potentially explosive azides. We have employed this powerful 'click chemistry' to make farnesol analogues where both β- and γ-isoprenes were replaced by triazole and substituted aromatic rings, respectively.

  11. Synthesis of Farnesol Analogues Containing Triazoles in Place of Isoprenes through ‘Click Chemistry’ (United States)

    Subramanian, Thangaiah; Parkin, Sean


    A solid-phase three-component Huisgen reaction has been used to generate polar farnesol and farnesyl diphosphate analogues. The Cu(I)-catalyzed 1,3-cycloadditions of various azides with solid supported (E)-3-methylhept-2-en-6-yn-1-ol provided only the 1,4-disubstituted 1,2,3-triazole regioisomers. The organic azides were generated in situ to minimize handling of potentially explosive azides. We have employed this powerful ‘click chemistry’ to make farnesol analogues where both β- and γ-isoprenes were replaced by triazole and substituted aromatic rings, respectively. PMID:23125482

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

    Institute of Scientific and Technical Information of China (English)


    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.

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

    DEFF Research Database (Denmark)

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


    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...

  14. Drug: D10275 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D10275 Mixture, Drug Bisoprolol fumarate - hydrochlorothiazide mixt; Ziac (TN) Biso...azides C07BB07 Bisoprolol and thiazides D10275 Bisoprolol fumarate - hydrochlorothiazide mixt PubChem: 163312306 ...

  15. Synthesis, Thermal Processing, and Thin Film Morphology of Poly(3-hexylthiophene)-Poly(styrenesulfonate) Block Copolymers

    NARCIS (Netherlands)

    Erothu, Harikrishna; Kolomanska, Joanna; Johnston, Priscilla; Schumann, Stefan; Deribew, Dargie; Toolan, Daniel T. W.; Gregori, Alberto; Dagron-Lartigau, Christine; Portale, Giuseppe; Bras, Wim; Arnold, Thomas; Distler, Andreas; Hiorns, Roger C.; Mokarian-Tabari, Parvaneh; Collins, Timothy W.; Howse, Jonathan R.; Topham, Paul D.


    A series of novel block copolymers, processable from single organic solvents and subsequently rendered amphiphilic by thermolysis, have been synthesized using Grignard metathesis (GRIM) and reversible addition-fragmentation chain transfer (RAFT) polymerizations and azide-alkyne click chemistry. This

  16. Orientation of llama antibodies strongly increases sensitivity of biosensors. (United States)

    Trilling, Anke K; Hesselink, Thamara; van Houwelingen, Adèle; Cordewener, Jan H G; Jongsma, Maarten A; Schoffelen, Sanne; van Hest, Jan C M; Zuilhof, Han; Beekwilder, Jules


    Sensitivity of biosensors depends on the orientation of bio-receptors on the sensor surface. The objective of this study was to organize bio-receptors on surfaces in a way that their analyte binding site is exposed to the analyte solution. VHH proteins recognizing foot-and-mouth disease virus (FMDV) were used for making biosensors, and azides were introduced in the VHH to function as bioorthogonal reactive groups. The importance of the orientation of bio-receptors was addressed by comparing sensors with randomly oriented VHH (with multiple exposed azide groups) to sensors with uniformly oriented VHH (with only a single azide group). A surface plasmon resonance (SPR) chip exposing cyclooctyne was reacted to azide functionalized VHH domains, using click chemistry. Comparison between randomly and uniformly oriented bio-receptors showed up to 800-fold increase in biosensor sensitivity. This technique may increase the containment of infectious diseases such as FMDV as its strongly enhanced sensitivity may facilitate early diagnostics.

  17. Molecular and Crystal Structures of Three Berberine Derivatives


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


    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.

  18. A ratiometric fluorescent probe for gasotransmitter hydrogen sulfide based on a coumarin-benzopyrylium platform. (United States)

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


    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.

  19. A versatile method for the preparation of conjugates of peptides with DNA/PNA/analog by employing chemo-selective click reaction in water (United States)

    Gogoi, Khirud; Mane, Meenakshi V.; Kunte, Sunita S.; Kumar, Vaijayanti A.


    The specific 1,3 dipolar Hüisgen cycloaddition reaction known as ‘click-reaction’ between azide and alkyne groups is employed for the synthesis of peptide–oligonucleotide conjugates. The peptide nucleic acids (PNA)/DNA and peptides may be appended either by azide or alkyne groups. The cycloaddition reaction between the azide and alkyne appended substrates allows the synthesis of the desired conjugates in high purity and yields irrespective of the sequence and functional groups on either of the two substrates. The versatile approach could also be employed to generate the conjugates of peptides with thioacetamido nucleic acid (TANA) analog. The click reaction is catalyzed by Cu (I) in either water or in organic medium. In water, ∼3-fold excess of the peptide-alkyne/azide drives the reaction to completion in 2 h with no side products. PMID:17981837

  20. Synthesis of α-methylene-δ-oxo-γ-amino esters via Rh(ii)-catalyzed coupling of 1-sulfonyl-1,2,3-triazoles with Morita-Baylis-Hillman adducts. (United States)

    Jeon, Hyun Ji; Kwak, Mi Soo; Jung, Da Jung; Bouffard, Jean; Lee, Sang-Gi


    A rhodium(ii)-catalyzed coupling of 1-sulfonyl-1,2,3-triazoles, prepared from 1-alkynes and sulfonyl azides, with Morita-Baylis-Hillman (MBH) adducts afforded highly functionalized α-methylene-δ-oxo-γ-amino esters in excellent yields with broad functional group tolerance. This transformation can also be successfully accomplished as a multicomponent all-in-one-pot reaction of 1-alkynes, sulfonyl azides and MBH adducts in the presence of Cu(i) and Rh(ii) catalysts.

  1. 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


    @@ 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.

  2. Observation of the controlled assembly of preclick components in the in situ click chemistry generation of a chitinase inhibitor


    Hirose, T.; Maita, N; Gouda, H.; Koseki, J; Yamamoto, T; Sugawara, A; H. Nakano; Hirono, S; Shiomi, K.; Watanabe, T; Taniguchi, H; Sharpless, KB; Omura, S; Sunazuka, T


    Several in situ click chemistry studies have been reported. To date, there is evidence to indicate that proteins act as mold between azide and alkyne fragments by X-ray analysis of protein–ligand complexes. However, only “postclick” structural evidence has been available. We succeeded in obtaining crystal structures of a chitinase complexed with an azide inhibitor and an O-allyl oxime fragment as a mimic of a click partner, revealing a mechanism for accelerating triazole formation in chitinas...

  3. Copper Supported on the SiO2 Nanoparticle in Click Chemistry: An Alternative Catalytic System for Regioselective and One-Pot Synthesis of 1,2,3-Triazoles and β-Hydroxytriazoles%Copper Supported on the SiO2 Nanoparticle in Click Chemistry: An Alternative Catalytic System for Regioselective and One-Pot Synthesis of 1,2,3-Triazoles and β-Hydroxytriazoles

    Institute of Scientific and Technical Information of China (English)

    Ciyabi Hashjin, Maryam; Ciyabi, Roghayeh; Baharloui, Maryam; Hosseini, Ghaffar; Tavakoli, Hamed


    In this work, readily prepared copper supported on the SiO2 nanoparticles has been found to effectively catalyze the 1,3-dipolar cycloaddition of a variety of azides, alkynes, epoxides and sodium azide, furnishing the correspond- ing 1,2,3-triazoles and β-hydroxytriazoles. Click reaction proceeds in short reaction times and under mild reaction conditions, and the resulting products are obtained in good yields at ambient temperature.

  4. "Clickable" LNA/DNA probes for fluorescence sensing of nucleic acids and autoimmune antibodies

    DEFF Research Database (Denmark)

    Jørgensen, Anna S; Gupta, Pankaj; Wengel, Jesper;


    Herein we describe fluorescent oligonucleotides prepared by click chemistry between novel alkyne-modified locked nucleic acid (LNA) strands and a series of fluorescent azides for homogeneous (all-in-solution) detection of nucleic acids and autoimmune antibodies.......Herein we describe fluorescent oligonucleotides prepared by click chemistry between novel alkyne-modified locked nucleic acid (LNA) strands and a series of fluorescent azides for homogeneous (all-in-solution) detection of nucleic acids and autoimmune antibodies....

  5. Microwave Resonant Absorption of Potential Exothermic Compounds (United States)


    exothermic materials: lead azide, lead styphnate , PETN, composition B, black powder, nitrocellulose, boron barium Chromate, and M-30 exhibit sharp...the exothermic materials. Table 1. Compounds Tested Compound Source 1 Lead Azide Broco Inc, Rialto CA 2 Lead Styphnate 3 PETN 4 Comp B 5 Black Powder 6...Nitrocellulose (12.6% Nitration) 7 Boron Barium Chromate ICI America, Valley Forge, PA 8 M30 (Gun Propellent) Radford Army Ammunition Plant, Radford

  6. PEO Ammunition Systems Portfolio Book 2012-2013 (United States)


    consists of an aluminum alloy cup containing an ignition charge of lead styphnate , an intermediate charge of lead azide, and a base charge of RDX. The...51.5 kg SPECIAL FEATURES: • An aluminum alloy cup containing an ignition charge of lead styphnate , an intermediate charge of lead azide, and...49% Barium Nitrate; 16.5% Strontium Nitrate; 5% Binder • Hazard Class/Net Energetic Weight: 1.3G/0.145150 Kg FIELDING: • Fielded PRIME

  7. A Compilation of Hazard and Test Data for Pyrotechnic Compositions (United States)


    Lead thiocynate 33 25 Lead azide 5 29 20 Carborundum 5 Barium nitrate 20 39 Basic lead styphnate 40 Tetrocene 5 2 Lead styphnate (normal) 38 Lead...Basic leas styphnate 53 60 Tetracene 5 5 5 , 3.1 12 4 Barium nitrate 20 25 8.68 31 22 32 Aluminum 10 7 Lead thiocynate 38.18 25 17 Ground glass...4) COMPOSITION: SENSITIVITY: Ingredients Lead Azide Basic Lead Styphnate Tetracene Barium Nitrate Antinomy

  8. Manufacturing Methods and Technology Project Summary Reports. (United States)


    elements as barium , strontium and rare earths were candidates. Preliminary work had shown that the addition of metallic barium to gas tungsten arc...Lead azide, lead styphnate and tetracene chemicals were batch processed as wet explosives in a small number of buildings for conversion into a dry...conducted and the system satisfactorily processed lead azide, lead styphnate and tetracene. Prototype tests on the commercial Car-Trac Conveyor were conducted

  9. Annual Report to Congress, fiscal Year 2003 (United States)


    composed of lead styphnate , lead azide, tetracene, and barium nitrate. All of these compounds contain heavy metals that are either mild toxins or...typically consist of lead azide, lead syphanate, and NOL130 (Naval Ordinance Lab) as well as barium nitrate and antimony sulfide. Although highly...identify, characterize, evaluate, and test environmentally benign candidate materials as potential replacements for the hazardous lead, antimony, and barium

  10. Regioselective azidotrimethylsilylation of carbohydrates and applications thereof. (United States)

    L, Mallikharjuna Rao; Yousuf, Syed Khalid; Mukherjee, Debaraj; Taneja, Subhash Chandra


    Azidotrimethylsilylation of carbohydrates (monosaccharides and disaccharides) has been achieved in high yields under Mitsunobu conditions. The azidation of carbohydrates is effected at 0 °C essentially only at the primary alcoholic position in mono, di- and triols in protected/unprotected glycosides, whereas the remaining secondary hydroxyl groups got silylated. Surprisingly, no azidation of the secondary hydroxyls was observed in all the carbohydrate substrates. Applications of the methodology for the synthesis of amino sugars, triazoles and azasugars are reported.

  11. 2,6-Diazidotoluene

    Directory of Open Access Journals (Sweden)

    Gunnar Spiess


    Full Text Available The structure of the title compound, C7H6N6, consists of almost planar molecules with C—N distances of 1.429 (2 and 1.428 (2 Å. The H atoms of the methyl group are disordered over two sites with occupancy factors of 0.69 and 0.31. The azide groups show typical geometry for covalently bound azides.

  12. Overview of Explosive Initiators (United States)


    Primary Explosives Lead Azide Lead azide came to prominence around the 1920’s, owing largely to its unique blend of performance its basic nature does not encourage lead azide’s tendency UNCLASSIFIED Approved for public release; distribution is unlimited. 5 toward...fig. 4, top). This fuse is usually a long, flexible plastic or rubber tube filled with a pyrotechnic composition such as black powder, allowing

  13. 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


    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.

  14. Liposome functionalization with copper-free "click chemistry". (United States)

    Oude Blenke, Erik; Klaasse, Gruson; Merten, Hannes; Plückthun, Andreas; Mastrobattista, Enrico; Martin, Nathaniel I


    The modification of liposomal surfaces is of interest for many different applications and a variety of chemistries are available that makes this possible. A major disadvantage of commonly used coupling chemistries (e.g. maleimide-thiol coupling) is the limited control over the site of conjugation in cases where multiple reactive functionalities are present, leading to heterogeneous products and in some cases dysfunctional conjugates. Bioorthogonal coupling approaches such as the well-established copper-catalyzed azide-alkyne cycloaddition (CuAAC) "click" reaction are attractive alternatives as the reaction kinetics are favorable and azide-containing reagents are widely available. In the work described here, we prepared lipids containing a reactive cyclooctyne group and, after incorporation into liposomes, demonstrated successful conjugation of both a small molecule dye (5'-TAMRA-azide) as well as a larger azide-containing model protein based upon a designed ankyrin repeat protein (azido-DARPin). By applying the strain-promoted azido-alkyne cycloaddition (SPAAC) the use of Cu(I) as a catalyst is avoided, an important advantage considering the known deleterious effects associated with copper in cell and protein studies. We demonstrate complete control over the number of ligands coupled per liposome when using a small molecule azide with conjugation occurring at a reasonable reaction rate. By comparison, the conjugation of a larger azide-modified protein occurs more slowly, however the number of protein ligands coupled was found to be sufficient for liposome targeting to cells. Importantly, these results provide a strong proof of concept for the site-specific conjugation of protein ligands to liposomal surfaces via SPAAC. Unlike conventional approaches, this strategy provides for the homogeneous coupling of proteins bearing a single site-specific azide modification and eliminates the chance of forming dysfunctional ligands on the liposome. Furthermore, the absence of

  15. Hydrogen bond donation to the heme distal ligand of Staphylococcus aureus IsdG tunes the electronic structure. (United States)

    Lockhart, Cheryl L; Conger, Matthew A; Pittman, Dylanger S; Liptak, Matthew D


    Staphylococcus aureus IsdG catalyzes the final step of staphylococcal iron acquisition from host hemoglobin, whereby host-derived heme is converted to iron and organic products. The Asn7 distal pocket residue is known to be critical for enzyme activity, but the influence of this residue on the substrate electronic structure was unknown prior to this work. Here, an optical spectroscopic and density functional theory characterization of azide- and cyanide-inhibited wild type and N7A IsdG is presented. Magnetic circular dichroism data demonstrate that Asn7 perturbs the electronic structure of azide-inhibited, but not cyanide-inhibited, IsdG. As the iron-ligating α-atom of azide, but not cyanide, can act as a hydrogen bond acceptor, these data indicate that the terminal amide of Asn7 is a hydrogen bond donor to the α-atom of a distal ligand to heme in IsdG. Circular dichroism characterization of azide- and cyanide-inhibited forms of WT and N7A IsdG strongly suggests that the Asn7···N3 hydrogen bond influences the orientation of a distal azide ligand with respect to the heme substrate. Specifically, density functional theory calculations suggest that Asn7···N3 hydrogen bond donation causes the azide ligand to rotate about an axis perpendicular to the porphyrin plane and weakens the π-donor strength of the azide ligand. This lowers the energies of the Fe 3d xz and 3d yz orbitals, mixes Fe 3d xy and porphyrin a 2u character into the singly-occupied molecular orbital, and results in spin delocalization onto the heme meso carbons. These discoveries have important implications for the mechanism of heme oxygenation catalyzed by IsdG.

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

    KAUST Repository

    Kim, Hyeongjun


    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.

  17. Porphyrin Cobalt(III) "Nitrene Radical" Reactivity; Hydrogen Atom Transfer from Ortho-YH Substituents to the Nitrene Moiety of Cobalt-Bound Aryl Nitrene Intermediates (Y = O, NH). (United States)

    Goswami, Monalisa; Rebreyend, Christophe; de Bruin, Bas


    In the field of cobalt(II) porphyrin-catalyzed metallo-radical reactions, organic azides have emerged as successful nitrene transfer reagents. In the pursuit of employing ortho-YH substituted (Y = O, NH) aryl azides in Co(II) porphyrin-catalyzed nitrene transfer reactions, unexpected hydrogen atom transfer (HAT) from the OH or NH₂ group in the ortho-position to the nitrene moiety of the key radical-intermediate was observed. This leads to formation of reactive ortho-iminoquinonoid (Y = O) and phenylene diimine (Y = NH) species. These intermediates convert to subsequent products in non-catalyzed reactions, as is typical for these free organic compounds. As such, the observed reactions prevent the anticipated cobalt-mediated catalytic radical-type coupling of the nitrene radical intermediates to alkynes or alkenes. Nonetheless, the observed reactions provide valuable insights into the reactivity of transition metal nitrene-radical intermediates, and give access to ortho-iminoquinonoid and phenylene diimine intermediates from ortho-YH substituted aryl azides in a catalytic manner. The latter can be employed as intermediates in one-pot catalytic transformations. From the ortho-hydroxy aryl azide substrates both phenoxizinones and benzoxazines could be synthesized in high yields. From the ortho-amino aryl azide substrates azabenzene compounds were obtained as the main products. Computational studies support these observations, and reveal that HAT from the neighboring OH and NH₂ moiety to the nitrene radical moiety has a low energy barrier.

  18. 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


    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.

  19. Conjugating folate on superparamagnetic Fe3O4@Au nanoparticles using click chemistry (United States)

    Shen, Xiaofang; Ge, Zhaoqiang; Pang, Yuehong


    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 Fe3O4@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 Fe3O4@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 Fe3O4@Au-FA nanoparticles.

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

    Institute of Scientific and Technical Information of China (English)


    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.

  1. Nanosecond laser-induced periodic surface structuring of cross-linked azo-polymer films

    Energy Technology Data Exchange (ETDEWEB)

    Berta, Marco, E-mail: [Aix Marseille Université, CNRS, ICR (Institut de Chimie Radicalaire) UMR 7273, 13397 Marseille Cedex 20 (France); Biver, Émeric [Aix Marseille Université, CNRS, LP3 UMR 7341, 13288 Marseille (France); Maria, Sébastien; Phan, Trang N.T. [Aix Marseille Université, CNRS, ICR (Institut de Chimie Radicalaire) UMR 7273, 13397 Marseille Cedex 20 (France); D’Aleo, Anthony; Delaporte, Philippe; Fages, Frederic [Aix Marseille Université, CNRS, CINaM UMR 7325, 13288 Marseille (France); Gigmes, Didier [Aix Marseille Université, CNRS, ICR (Institut de Chimie Radicalaire) UMR 7273, 13397 Marseille Cedex 20 (France)


    In this work we discuss the response to laser ablation of a poly(4-vinylbenzyl azide-random-methyl methacrylate) (p((S-N{sub 3})-r-MMA)) random copolymer. This material is cross-linkable thermally and upon exposure to UV light, and on cross-linked films the irradiation with a 248 nm ns KrF laser induces the formation of laser induced periodical surface structure (LIPSS). The LIPSS morphology is dependent on the amount of 4-vinylbenzyl azide (S-N{sub 3}) groups in the pristine copolymer. We propose a crosslinking mechanism based on the scission of azide with formation of azo groups and we discuss the possible relationship between this chemical modifications and the formation of ripples on the bottom of laser ablation cavities.

  2. Nanosecond laser-induced periodic surface structuring of cross-linked azo-polymer films (United States)

    Berta, Marco; Biver, Émeric; Maria, Sébastien; Phan, Trang N. T.; D'Aleo, Anthony; Delaporte, Philippe; Fages, Frederic; Gigmes, Didier


    In this work we discuss the response to laser ablation of a poly(4-vinylbenzyl azide-random-methyl methacrylate) (p((S-N3)-r-MMA)) random copolymer. This material is cross-linkable thermally and upon exposure to UV light, and on cross-linked films the irradiation with a 248 nm ns KrF laser induces the formation of laser induced periodical surface structure (LIPSS). The LIPSS morphology is dependent on the amount of 4-vinylbenzyl azide (S-N3) groups in the pristine copolymer. We propose a crosslinking mechanism based on the scission of azide with formation of azo groups and we discuss the possible relationship between this chemical modifications and the formation of ripples on the bottom of laser ablation cavities.

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

    Directory of Open Access Journals (Sweden)

    S. P. Panda


    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.

  4. SADARM Environmental Assessment (United States)



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

    Indian Academy of Sciences (India)

    V Jagannadham


    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.

  6. The Pasteur effect and catabolite repression in an oxidative yeast, Kluyveromyces lactis. (United States)

    Royt, P W; MacQuillan, A M


    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.

  7. Triazol-substituted titanocenes by strain-driven 1,3-dipolar cycloadditions

    Directory of Open Access Journals (Sweden)

    Andreas Gansäuer


    Full Text Available An operationally simple, convenient, and mild strategy for the synthesis of triazole-substituted titanocenes via strain-driven 1,3-dipolar cycloadditions between azide-functionalized titanocenes and cyclooctyne has been developed. It features the first synthesis of titanocenes containing azide groups. These compounds constitute ‘second-generation’ functionalized titanocene building blocks for further synthetic elaboration. Our synthesis is modular and large numbers of the complexes can in principle be prepared in short periods of time. Some of the triazole-substituted titanocenes display high cyctotoxic activity against BJAB cells. Comparison of the most active complexes allows the identification of structural features essential for biological activity.

  8. Direct Light-up of cAMP Derivatives in Living Cells by Click Reactions

    Directory of Open Access Journals (Sweden)

    Yan Xu


    Full Text Available 8-Azidoadenosine 3′,5′-cyclic monophosphate (8-azido cAMP was directly detected in living cells, by applying Cu-free azide-alkyne cycloaddition to probe cAMP derivatives by fluorescence light-up. Fluorescence emission was generated by two non-fluorescent molecules, 8-azido cAMP as a model target and difluorinated cyclooctyne (DIFO reagent as a probe. The azide-alkyne cycloaddition reaction between 8-azido cAMP and DIFO induces fluorescence in 8-azido cAMP. The fluorescence emission serves as a way to probe 8-azido cAMP in cells.

  9. Orthogonally bifunctionalised polyacrylamide nanoparticles: a support for the assembly of multifunctional nanodevices (United States)

    Giuntini, F.; Dumoulin, F.; Daly, R.; Ahsen, V.; Scanlan, E. M.; Lavado, A. S. P.; Aylott, J. W.; Rosser, G. A.; Beeby, A.; Boyle, R. W.


    Polyacrylamide nanoparticles bearing two orthogonal reactive functionalities were prepared by reverse microemulsion polymerisation. Water-soluble photosensitisers and peptide or carbohydrate moieties were sequentially attached to the new nanospecies by orthogonal conjugations based on copper-catalysed azide-alkyne cycloaddition and isothiocyanate chemistry.Polyacrylamide nanoparticles bearing two orthogonal reactive functionalities were prepared by reverse microemulsion polymerisation. Water-soluble photosensitisers and peptide or carbohydrate moieties were sequentially attached to the new nanospecies by orthogonal conjugations based on copper-catalysed azide-alkyne cycloaddition and isothiocyanate chemistry. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr11947a

  10. Characterization of Iron-Imido Species Relevant for N-Group Transfer Chemistry


    Iovan, Diana A.; Betley, Theodore A.


    A sterically accessible tert-butyl-substituted dipyrrinato di-iron(II) complex [(tBuL)FeCl]2 possessing two bridging chloride atoms was synthesized from the previously reported solvento adduct. Upon treatment with aryl azides, the formation of high-spin FeIII species was confirmed by 57Fe Mössbauer spectroscopy. Crystallographic characterization revealed two possible oxidation products: (1) a terminal iron iminyl from aryl azides bearing ortho isopropyl substituents, (tBuL)FeCl(•NC6H3-2,6-iPr...

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

    Directory of Open Access Journals (Sweden)

    Paola Bonaccorsi


    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.

  12. Selective posttranslational modification of phage-displayed polypeptides

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  13. Selective posttranslational modification of phage-displayed polypeptides

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  14. A photoinduced, benzyne click reaction. (United States)

    Gann, Adam W; Amoroso, Jon W; Einck, Vincent J; Rice, Walter P; Chambers, James J; Schnarr, Nathan A


    The [3 + 2] cycloaddition of azides and alkynes has proven invaluable across numerous scientific disciplines for imaging, cross-linking, and site-specific labeling among many other applications. We have developed a photoinitiated, benzyne-based [3 + 2] cycloaddition that is tolerant of a variety of functional groups as well as polar, protic solvents. The reaction is complete on the minute time scale using a single equivalent of partner azide, and the benzyne photoprecursor is stable for months under ambient light at room tempurature. Herein we report the optimization and scope of the photoinitiated reaction as well as characterization of the cycloaddition products.

  15. Static Charge Development on Explosives .

    Directory of Open Access Journals (Sweden)

    K. Raha


    Full Text Available Static charge development character of some of the important explosive crystals have been predicted on the basis of their crystal class and symmetry. Among the important mechanism of charge development, the piezoelectric and pyroelectric characters have been considered. Ammonium trinitrate, ammonium nitrate, m-dinitro-benzene, trinitro-toluene, styphnic acid, beeta-lead styphnate, 4,4'dinitro-dipheny1, a-hexamethylenetetranitramine, nitroguanidine, picric acid, dimethylnitramine, a-lead azide and beeta-lead azide are pyroelectric in nature, whereas pentaerythritol tetranitrate, picryliodide, hexamethylenetranitramine, tetranitromethane and trinitroethane are piezoelectric in nature.

  16. Synthesis of enantiopure sugar-decorated six-armed triptycene derivatives (United States)

    Gioia, Maria Luisa Di; Leggio, Antonella; Minuti, Lucio; Papalia, Teresa; Siciliano, Carlo; Temperini, Andrea; Barattucci, Anna


    Summary 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. PMID:24367407

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

    Directory of Open Access Journals (Sweden)

    Sankara Rao Rowthu


    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.

  18. Low-Fouling Antibacterial Reverse Osmosis Membranes via Surface Grafting of Graphene Oxide. (United States)

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


    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.

  19. Ultrasound promoted mild and facile one-pot, three component synthesis of 2H-indazoles by consecutive condensation, CN and NN bond formations catalysed by copper-doped silica cuprous sulphate (CDSCS) as an efficient heterogeneous nano-catalyst. (United States)

    Soltani Rad, Mohammad Navid


    An ultrasonic promoted facile and convenient one-pot three-component procedure for the synthesis of 2H-indazole derivatives using copper-doped silica cuprous sulphate (CDSCS) as a heterogeneous nano-catalyst has been described. In this approach, ultrasonic mediated reaction of different substituted 2-bromobenzaldehydes, structurally diverse primary amines, and tetrabutylammonium azide (TBAA) as an azide source in the presence of CDSCS in DMSO at room temperature furnishes 2H-indazoles in good to excellent yields. Utilizing ultrasonic irradiation techniques provided the dramatic improvements in terms of higher yields and shorter reaction times compared with conventional heating method.

  20. Functionalization of Mechanochemically Passivated Germanium Nanoparticles via "Click" Chemistry (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

  1. Enzymatic production of atranorin: a component of the oak moss absolute by immobilized lichen cells. (United States)

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


    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).

  2. EdU, a new thymidine analogue for labelling proliferating cells in the nervous system. (United States)

    Chehrehasa, Fatemah; Meedeniya, Adrian C B; Dwyer, Patrick; Abrahamsen, Greger; Mackay-Sim, Alan


    Labelling and identifying proliferating cells is central to understanding neurogenesis and neural lineages in vivo and in vitro. We present here a novel thymidine analogue, ethynyl deoxyuridine (EdU) for labelling dividing cells, detected with a fluorescent azide which forms a covalent bond via the "click" chemistry reaction (the Huisgen 1,3-dipolar cycloaddition reaction of an organic azide to a terminal acetylene). Unlike the commonly used BrdU, EdU detection requires no heat or acid treatment. It is quick and easy and compatible with multiple probes for fluorescence immunochemistry, facilitating the characterisation of proliferating cells at high resolution.

  3. A chemical method for fast and sensitive detection of DNA synthesis in vivo


    Salic, Adrian; Mitchison, Timothy J.


    We have developed a method to detect DNA synthesis in proliferating cells, based on the incorporation of 5-ethynyl-2′-deoxyuridine (EdU) and its subsequent detection by a fluorescent azide through a Cu(I)-catalyzed [3 + 2] cycloaddition reaction (“click” chemistry). Detection of the EdU label is highly sensitive and can be accomplished in minutes. The small size of the fluorescent azides used for detection results in a high degree of specimen penetration, allowing the staining of whole-mount ...

  4. Replication Banding Patterns in Human Chromosomes Detected Using 5-ethynyl-2'-deoxyuridine Incorporation


    Hoshi, Osamu; Ushiki, Tatsuo


    A novel technique using the incorporation of 5-ethynyl-2'-deoxyuridine (EdU) into replicating DNA is described for the analysis of replicating banding patterns of human metaphase chromosomes. Human lymphocytes were synchronized with excess thymidine and treated with EdU during the late S phase of the cell cycle. The incorporated EdU was then detected in metaphase chromosomes using Alexa Fluor® 488 azides, through the 1,3-dipolar cycloaddition reaction of organic azides with the terminal acety...

  5. Microbiologically Influenced Corrosion: Global Phenomena, Local Mechanisms (United States)


    addition of catalase and perioxidase, enzymes known to decompose HiCK. Concentrations of 10-30 ppm HiO : were identified in natural biofilms that...of sodium azide to ennobled biofilms containing catalase or peroxidase would inhibit the decomposition of HiOs and result in higher ennobled Ec

  6. Stereo- and regio-selective one-pot synthesis of triazole-based unnatural amino acids and β- amino triazoles (United States)

    Synthesis of triazole based unnatural amino acids and β-amino triazole has been described via stereo and regioselective one-pot multi-component reaction of sulfamidates, sodium azide, and alkynes under MW conditions. The developed method is applicable to a broad substrate scope a...

  7. Synthesis of unnatural amino acids via microwave-assisted regio-selective one-pot multi-component reactions of sulfamidates (United States)

    Synthesis of triazole-based unnatural amino acids, triazole bisaminoacids and β-amino triazole has been described via stereo and regioselective one-pot multi-component reaction of sulfamidates, sodium azide, and alkynes under MW irradiation conditions. The developed method is app...

  8. Expedient Synthesis of N1-Substituted Triazole Peptidomimetics. (United States)

    Coffey, Steven B; Aspnes, Gary; Londregan, Allyn T


    A general procedure for the rapid diversification of peptide scaffolds is described. A one-pot click reaction between a peptide-alkyne and a series of in situ generated aryl/alkyl azides affords novel N1-substituted triazole peptidomimetics. This transformation is of broad scope, operates under mild conditions, and is parallel chemical synthesis compatible.

  9. Expedient synthesis of triazole-linked glycosyl amino acids and peptides.

    NARCIS (Netherlands)

    Kuijpers, B.H.M.; Groothuys, S.; Keereweer, A.R.; Quaedflieg, P.J.; Blaauw, R.H.; Delft, F.L. van; Rutjes, F.P.J.T.


    [structure: see text] An expedient, high-yielding synthesis of two types of triazole-linked glycopeptides is described. These novel and stable glycopeptide mimics were prepared via Cu(I)-catalyzed [3 + 2] cycloaddition of either azide-functionalized glycosides and acetylenic amino acids or acetyleni

  10. 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


    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

  11. “Electro-Click” on Conducting Polymer Films

    DEFF Research Database (Denmark)

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

    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...

  12. Henry’s Law Constants for 2-Azidoethanamine Hypergols: Estimates From a Density Functional Theory/Polarizable Continuum Model (United States)


    of ),298( iG corrg are based on the ideal gas law and the calculation of S via a standard method ( McQuarrie , 1999). 6 An issue in the...Amine Azide-Based Hydrazine Alternative Hypergols; ARL-TR-4516; U.S. Army Research Laboratory: Aberdeen Proving Ground, MD, 2008. McQuarrie , D. A

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

    Directory of Open Access Journals (Sweden)

    Redouan Mahou


    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.

  14. 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...

  15. Consecutive condensation, C-N and N-N bond formations: a copper- catalyzed one-pot three-component synthesis of 2H-indazole. (United States)

    Kumar, Manian Rajesh; Park, Ahbyeol; Park, Namjin; Lee, Sunwoo


    2H-Indazoles are synthesized using copper-catalyzed, one-pot, three-component reactions of 2-bromobenzaldehydes, primary amines, and sodium azide. A copper catalyst plays the key role in the formation of C-N and N-N bonds. This method has a broad substrate scope with a high tolerance for a variety of functional groups.

  16. Observation of the controlled assembly of preclick components in the in situ click chemistry generation of a chitinase inhibitor. (United States)

    Hirose, Tomoyasu; Maita, Nobuo; Gouda, Hiroaki; Koseki, Jun; Yamamoto, Tsuyoshi; Sugawara, Akihiro; Nakano, Hirofumi; Hirono, Shuichi; Shiomi, Kazuro; Watanabe, Takeshi; Taniguchi, Hisaaki; Sharpless, K Barry; Omura, Satoshi; Sunazuka, Toshiaki


    The Huisgen cycloaddition of azides and alkynes, accelerated by target biomolecules, termed "in situ click chemistry," has been successfully exploited to discover highly potent enzyme inhibitors. We have previously reported a specific Serratia marcescens chitinase B (SmChiB)-templated syn-triazole inhibitor generated in situ from an azide-bearing inhibitor and an alkyne fragment. Several in situ click chemistry studies have been reported. Although some mechanistic evidence has been obtained, such as X-ray analysis of [protein]-["click ligand"] complexes, indicating that proteins act as both mold and template between unique pairs of azide and alkyne fragments, to date, observations have been based solely on "postclick" structural information. Here, we describe crystal structures of SmChiB complexed with an azide ligand and an O-allyl oxime fragment as a mimic of a click partner, revealing a mechanism for accelerating syn-triazole formation, which allows generation of its own distinct inhibitor. We have also performed density functional theory calculations based on the X-ray structure to explore the acceleration of the Huisgen cycloaddition by SmChiB. The density functional theory calculations reasonably support that SmChiB plays a role by the cage effect during the pretranslation and posttranslation states of selective syn-triazole click formation.

  17. On-Surface Synthesis by Click Chemistry Investigated by STM and XPS

    DEFF Research Database (Denmark)

    Vadapoo, Sundar Raja


    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...

  18. A facile and regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles using click chemistry (United States)

    The reaction of α-tosyloxy ketones, sodium azide and terminal alkynes in presence of copper(I) in aqueous polyethylene glycol afforded regioselectively 1,4-disubstituted 1,2,3-triazoles in good yield at ambient temperature. The one-pot exclusive formation of 1,4-disubstituted 1,2...

  19. Azidoethoxyphenylalanine as a Vibrational Reporter and Click Chemistry Partner in Proteins. (United States)

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


    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.

  20. Novel cross-linkers for PDMS networks for controlled and well distributed grafting of functionalities by click chemistry

    DEFF Research Database (Denmark)

    Bahrt, Frederikke; Dimitrov, Ivaylo; Daugaard, Anders Egede


    An azide-containing, trifunctional vinyl cross-linker for silicone networks has been synthesized. The cross-linker has through Cu(i) catalyzed 1,3-cycloaddition been reacted with six different alkyne-containing chemical groups which each possess a particular functionality. The functional cross-li...... The Royal Society of Chemistry....

  1. A New Synthetic Route to 12-Oxo-1, 15-pentadecanlactam

    Institute of Scientific and Technical Information of China (English)

    Jia Xing HUANG; Xiao Mei LIANG; Dao Quan WANG


    12-Oxo-1, 15-pentadecanlactam 7 was synthesized from cyclododecanone with a total yield of 36% in a seven-step reaction. The azide 5 to 12-nitro-1, 15-pentadecanlactam 6 is the key step featured by direct ring expansion.

  2. 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


    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.

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

    Institute of Scientific and Technical Information of China (English)



    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.

  4. Covalent deposition of zwitterionic polymer and citric acid by click chemistry-enabled layer-by-layer assembly for improving the blood compatibility of polysulfone membrane. (United States)

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


    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.

  5. An Efficient (2-Aminoarenethiolato)copper(I) Complex for the Copper-Catalysed Huisgen Reaction (CuAAC)

    NARCIS (Netherlands)

    Fabbrizzi, Pierangelo; Cicchi, Stefano; Brandi, Alberto; Sperotto, E.; van Koten, G.


    A (2-aminoarenethiolato)copper(I) complex has been used as an efficient catalyst (1 mol-%) for the copper-catalysedHuisgen reaction (CuAAC) of azides and terminal alkynes in an organic solvent. The reaction was also extremely effective in CH2Cl2 allowing the complete decoration of dendrimeric scaffo

  6. Synthesis of Photoactivatable Phospholipidic Probes

    Institute of Scientific and Technical Information of China (English)

    Qing PENG; Fan Qi QU; Yi XIA; Jie Hua ZHOU; Qiong You WU; Ling PENG


    We synthesized and characterized photoactivatable phospholipidic probes 1-3. These probes have the perfluorinated aryl azide function at the polar head of phospholipid. They are stable in dark and become highly reactive upon photoirradiation. The preliminary results suggest that they are promising tools to study the topology of membrane proteins and protein-lipid interactions using photolabeling approach.

  7. Synthesis and application of water-soluble, photoswitchable cyanine dyes for bioorthogonal labeling of cell-surface carbohydrates. (United States)

    Mertsch, Alexander; Letschert, Sebastian; Memmel, Elisabeth; Sauer, Markus; Seibel, Jürgen


    The synthesis of cyanine dyes addressing absorption wavelengths at 550 and 648 nm is reported. Alkyne functionalized dyes were used for bioorthogonal click reactions by labeling of metabolically incorporated sugar-azides on the surface of living neuroblastoma cells, which were applied to direct stochastic optical reconstruction microscopy (dSTORM) for the visualization of cell-surface glycans in the nm-range.

  8. FeCl2-promoted cleavage of the unactivated C-C bond of alkylarenes and polystyrene: direct synthesis of arylamines. (United States)

    Qin, Chong; Shen, Tao; Tang, Conghui; Jiao, Ning


    Ironing it out: an efficient and convenient nitrogenation strategy involving C-C bond cleavage for the straightforward synthesis of versatile arylamines is presented. Various alkyl azides and alkylarenes, including the common industrial by-product cumene, react using this protocol. Moreover, this method provides a potential strategy for the degradation of polystyrene.

  9. Santa Margarita Lagoon Water Quality Monitoring Data (United States)


    using a standard Winkler titration method (APHA, AWWA , and WPCF, 1989) to compare to instrument measurements. Calibration tables and field data logs...samples was done following the azide modification to the Winkler titration (APHA, AWWA , and WPCF, 1989). This modification is used for most wastewater

  10. New 1,2,3-Triazole Iminosugars Derivatives Using Click Chemistry

    Directory of Open Access Journals (Sweden)

    Chahrazed Benhaoua


    Full Text Available The click concept refers ease, efficient, and the selective chemicals transformations. In this study, a novel regiospecific copper (I-catalyzed 1, 3-dipolar of terminal alkynes to azide provided a practicable synthetic pathway of triazole iminosugars derivatives. A series of new triazole-pyrrolidinols are reported in good yield.

  11. Carbon-rich "Click" 1,2,3-triazoles: hexaphenylbenzene and hexa-peri-hexabenzocoronene-based ligands for Suzuki-Miyaura catalysts. (United States)

    Wright, James R; Crowley, James D; Lucas, Nigel T


    Hexaphenylbenzene (HPB) and hexa-peri-hexabenzocoronene-(HBC) functionalised 1,2,3-triazoles have been synthesised using an optimised copper(i)-catalysed azide-alkyne cycloaddition (CuAAC) reaction. The coordination chemistry of these ligands was explored through the synthesis of the respective palladium(ii) complexes and their activity as catalysts in the Suzuki-Miyaura reaction assessed.

  12. Effects of Particle Beams on Explosives (United States)


    the primary explosives do not demonstrate an ignition energy dependance on confinement. The threshold energies are: Lead azide, 24 cal/gm; Lead...This result demonstrates the strong dependance of ignition threshold on confinement. The chemical and physical changes resulting from irradiation can

  13. An Efficient Passerini Tetrazole Reaction (PT-3CR)

    NARCIS (Netherlands)

    Chandgude, Ajay L; Dömling, Alexander


    A sonication accelerated, catalyst free, simple, high yielding and efficient method for the Passerini-type three component reaction (PT-3CR) has been developed. It comprises reaction of an aldehyde/ketone, a isocyanide and a TMS-azide in methanol:water (1:1) as the solvent system. Use of sonication

  14. Structure Property Correlations in Primary Explosives (United States)


    is to the elements; therefore, the heat of detonation (an indicator of sensitivity) is simply the heat of formation for the metal azides, AgN - of compounds. Furthermore, the heat of detonation is not the sole criterion for usefulness as a primary. TNT has a higher heat of detonation than

  15. Synthesis and Application of Prenyl-Derived Photoaffinity Probes

    Institute of Scientific and Technical Information of China (English)

    LI, Lingdong; TANG, wei; ZHAO, Zongbao


    Three photoaffinity probes containing isoprenoid chains and an azide group were synthesized using one-pot coupling reaction as the key step. The capability of these probes as labeling agents for isoprenoid chain-interacting proteins from Saccharomyces cerevisiae proteome was validated by photoaffinity reaction and "click" conjunction with the biotin reporter followed by streptavidin blot analysis.

  16. 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

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

    DEFF Research Database (Denmark)

    Johannessen, Christian; Abdali, Salim


    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....

  18. Services Textbook of Explosives (United States)


    barium styphnates ...... ..... ......... 34 Lead styphnate , RD 1303 ..... ...... ...... ..... 34 Basic lead stYphnates ............. 39 Barium styphnate ...conditions may cause deterioration of the lead azide. Lead and barium styphnates Lead styphnate , RD 1303 34. Lead styphnate is the normal lead salt of...tribasic lead styphnate . They are used in fuzeheads and igniters. Barium styphnate 42. In the search for materials having properties

  19. Remediation Technologies Screening Matrix and Reference Guide, Second Edition (United States)


    Metals - Aluminum - Antimony - Arsenic* - Barium - Beryllium - Bismuth - Boron - Cadmium - Calcium - Chromium - Cobalt - Copper - Iron...include lead azide and lead styphnate , are highly susceptible to initiation. Primary explosives often are referred to as initiating explosives because...Illuminating flares contain sodium nitrate, magnesium, and a binder. Signaling flares contain barium , strontium, or other metal nitrates

  20. Installation Restoration General Environmental Technology Development. Task 3. Guidelines for In-Place Closure of Dry Lagoons. Volume 2. Evaluation of In-Place Closure Technologies. (United States)


    Nitroqlycerine Tr itonal Ammonia picrate PETN U DMH Am Ito I An ilin e Nitt ouenzene barium nitrate Lead azide Lead styphnate Acid s Ammronium nitrate Lead * Zinc...temperature for RDX, 1MX, lead styphnate , and lead azilde thermal decomposition 305 65 Time versus temperature for NG, NC, NQ, and NH 4NO 3 thermal

  1. Defense Environmental Restoration Program Annual Report to Congress for Fiscal Year 1988 (United States)


    styphnate . Mission-support operations have generated hazardous wastes such as TNT, oils, spent halogenated and nonhalogenated solvents, tetracene...asbestos, tranzite, VOCs, trichloroethylene, sodium orthosilicate, heavy metals ( barium , cadmium, chromium, lead, mercury, silver, beryllium), sul- furic...tetrazine, lead styphnate , lead azide, tetryl, octal, hexavalent chromium, copper, cadmium, lead, mercury, arsenic, nitrobodies, sulfates, and chlorides

  2. 50th Annual Fuze Conference Sessions 3 and 4 Held in Norfolk, Virginia on May 9-11, 2006 (United States)


    NOL-130 Lead-based components replaced Initiator Mix Composition Antimony TrisulfideAntimony Trisulfide Barium NitrateBarium Nitrate TetraceneTetracene...Cyanuric Triazide Lead Styphnate Lead Azide NOL-130GNOL-130 Transfer Charge Replacements Replacing the transfer charge will eliminate rest of the

  3. Overview of On-Site Analytical Methods for Explosives in Soil. (United States)


    develop associated secondary explosives include Amatol a sampling and analytical approach that achieves (ammonium nitrate/TNT), Baratol ( barium ni...azide, lead tions: for TNT, immediate freezing and 233 days styphnate , and mercury fulminate. As a conser- at 20’C; for DNT, 107 days at 4°C; for RDX

  4. Friction Sensitivity of Primary Explosives (United States)


    potassium dinitrobenzofuroxan none tetrazene 407913 tetrazene 7902454 The mixes which were tested are: NOL 130 (basic lead styphnate , barium nitrate, lead...azide, tetrazene, and antimony sulfide); PA 100 (normal lead styphnate , barium nitrate, tetrazene, lead dioxide, calcium silicide, and antimony...styuhnate, basic lead styphnate , potassium dinitrobenzofuroxan, and tetrazene were tested to determine the- 10% and 50% probability of friction

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

    Indian Academy of Sciences (India)

    Siavash Bahari; Mehdi Ahmadi Sabegh


    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.

  6. Regioselective oxidation of unprotected 1,4 linked glucans

    NARCIS (Netherlands)

    Eisink, Niek N.H.M.; Lohse, Jonas; Witte, Martin D.; Minnaard, Adriaan J.


    Palladium-catalyzed alcohol oxidation allows the chemo- and regioselective modification of unprotected 1,4 linked glucans. This is demonstrated in the two-step bisfunctionalization of 1,4 linked glucans up to the 7-mer. Introduction of an anomeric azide is followed by a highly regioselective mono-ox

  7. Synthesis of pentafluorosulfanylpyrazole and pentafluorosulfanyl-1,2,3-triazole and their derivatives as energetic materials by click chemistry. (United States)

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


    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.

  8. Versatile procedure for site-specific grafting of polymer brushes on patchy particles via atom transfer radical polymerization (ATRP)

    NARCIS (Netherlands)

    Van Ravensteijn, Bas G P; Kegel, Willem K.


    We report the preparation of chemically anisotropic colloidal dumbbells of which one lobe is functionalized with chemical handles in the form of chlorine groups. The chlorines are easily converted to azides and subsequently to active initiators for Atom Transfer Radical Polymerization (ATRP) by Clic

  9. A new synthetic approach to phosphatidylethanolamine

    Institute of Scientific and Technical Information of China (English)

    Yang Song; Wei Yuan; Yu Luo; Wei Lu


    A new synthetic method for phosphatidylethanolamine head group was developed via ring-opening of cyclic dioxaphospholane 2 with sodium azide and subsequent hydrogenation.The advantage of this strategy included short reaction steps,readily available materials and good yields.

  10. Effective click construction of bridged- and spiro-multicyclic polymer topologies with tailored cyclic prepolymers (kyklo-telechelics). (United States)

    Sugai, Naoto; Heguri, Hiroyuki; Ohta, Kengo; Meng, Qingyuan; Yamamoto, Takuya; Tezuka, Yasuyuki


    An alkyne-azide addition, i.e., click, reaction in conjunction with an electrostatic self-assembly and covalent fixation (ESA-CF) process has been demonstrated to effectively construct a variety of unprecedented multicyclic polymer topologies. A series of single cyclic poly(tetrahydrofuran), poly(THF), precursors having an alkyne group (Ia), an azide group (Ib), two alkyne groups at the opposite positions (Ic), and an alkyne group and an azide group at the opposite positions (Id) have been prepared by the ESA-CF process. Moreover, a bicyclic 8-shaped precursor having two alkyne groups at the opposite positions (Ie) was synthesized. The subsequent click reaction of Ia with linear (IIa) and three-armed star (IIb) telechelic precursors having azide groups has been performed to construct bridged-type two-way (IIIa) and three-way (IIIb) paddle-shaped polymer topologies, respectively. Likewise, spiro-type tandem tricyclic (IVa) and tetracyclic (IVb) topologies resulted from Ib/Ic and Ib/Ie, respectively. Furthermore, three types of multicyclic topologies that are composed of repeating ring (Va), alternating ring/linear (Vb), and alternating ring/star (Vc) units have been synthesized from Id, Ic/IIa, and Ic/IIb, respectively.

  11. 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.


    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

  12. Two consecutive click reactions as a general route to functional cyclic polyesters. (United States)

    Yuan, You-Yong; Du, Jin-Zhi; Wang, Jun


    A simple and universal route to functional cyclic polyesters has been demonstrated, combining two consecutive click reactions of azide-alkyne cycloaddition of linear hetero-bifunctional precursors and thiol-ene coupling for post cyclization functionalizations. Functional cationic and thermo-responsive cyclic polyphosphoesters have been synthesized to demonstrate the efficiency of the procedures.

  13. Glucose selective bis-boronic acid click-fluor. (United States)

    Zhai, Wenlei; Male, Louise; Fossey, John S


    Four novel bis-boronic acid compounds were synthesised via copper catalysed azide-alkyne cycloaddition (CuAAC) reactions. Glucose selectivity was observed for a particular structural motif. Moreover, a new glucose selective fluorescent sensor was designed and synthesised as a result.

  14. Covalent protein-oligonucleotide conjugates by copper-free click reaction. (United States)

    Khatwani, Santoshkumar L; Kang, Jun Sung; Mullen, Daniel G; Hast, Michael A; Beese, Lorena S; Distefano, Mark D; Taton, T Andrew


    Covalent protein-oligodeoxynucleotide (protein-ODN) conjugates are useful in a number of biological applications, but synthesizing discrete conjugates-where the connection between the two components is at a defined location in both the protein and the ODN-under mild conditions with significant yield can be a challenge. In this article, we demonstrate a strategy for synthesizing discrete protein-ODN conjugates using strain-promoted azide-alkyne [3+2] cycloaddition (SPAAC, a copper-free 'click' reaction). Azide-functionalized proteins, prepared by enzymatic prenylation of C-terminal CVIA tags with synthetic azidoprenyl diphosphates, were 'clicked' to ODNs that had been modified with a strained dibenzocyclooctyne (DIBO-ODN). The resulting protein-ODN conjugates were purified and characterized by size-exclusion chromatography and gel electrophoresis. We find that the yields and reaction times of the SPAAC bioconjugation reactions are comparable to those previously reported for copper-catalyzed azide-alkyne [3+2] cycloaddition (CuAAC) bioconjugation, but require no catalyst. The same SPAAC chemistry was used to immobilize azide-modified proteins onto surfaces, using surface-bound DIBO-ODN as a heterobifunctional linker. Cu-free click bioconjugation of proteins to ODNs is a simple and versatile alternative to Cu-catalyzed click methods.

  15. 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


    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.

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

    DEFF Research Database (Denmark)

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


    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...

  17. 29 CFR 1910.109 - Explosives and blasting agents. (United States)


    .... Explosive—any chemical compound, mixture, or device, the primary or common purpose of which is to function by explosion, i.e., with substantially instantaneous release of gas and heat, unless such compound..., nitroglycerin, picric acid, lead azide, fulminate of mercury, black powder, blasting caps, and...

  18. Laser Induced Breakdown Spectroscopy (LIBS) (United States)


    depositors favored large denominations causing the smaller denominations to become essentially worthless and obsolete. With the Coinage Act of February...Thallium 201 Hydrogen cyanide (AC) FUNGI Thorium 232 Cyanogen chloride (CK) Aflatoxin Lead 210 Arsine (SA) Bacillus Sodium 22...fuel oil ]. Bromazepam (PIM 281) Aromatic nitro-compound explosive mixtures. Brotizolam (PIM 919) Azide explosives. Bupivacaine (PIM

  19. Nanomolar cholera toxin inhibitors based on symmetrical pentavalent ganglioside GM1os-sym-corannulenes

    NARCIS (Netherlands)

    Mattarella, M.; Garcia-Hartjes, J.; Wennekes, T.; Zuilhof, H.; Siegel, J.S.


    Eight symmetric and pentavalent corannulene derivatives were functionalized with galactose and the ganglioside GM1-oligosaccharide (GM1os) via copper-catalyzed alkyne-azide cycloaddition (CuAAC) reactions. The compounds were evaluated for their ability to inhibit the binding of the pentavalent chole

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

    Directory of Open Access Journals (Sweden)

    Mehrak Faraji


    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.

  1. Undergraduate Electron-Spin-Resonance Experiment. (United States)

    Willis, James S.


    Describes the basic procedures for use of an electron-spin resonance spectrometer and potassium azide (KN3) in an experiment which extends from the phase of sample preparation (crystal growth, sample mounting, and orientation) through data taking to the stages of calculation and theoretical explanation. (Author/DS)

  2. Oxidative Hemolysis of Erythrocytes (United States)

    Wlodek, Lidia; Kusior, Dorota


    This exercise for students will allow them to simultaneously observe lipid peroxidation and consequent hemolysis of rat erythrocytes and the effect of sodium azide, a catalase inhibitor, on these processes. It will also demonstrate a protective action of antioxidants, the therapeutically used N-acetylcysteine and albumins present in plasma.

  3. Towards copper-free nanocapsules obtained by orthogonal interfacial "click" polymerization in miniemulsion. (United States)

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


    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.

  4. Comparative study of chemical and physical methods for distinguishing between passive and metabolically active mechanisms of water contaminant removal by biofilms. (United States)

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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Xiaofang, E-mail:; Ge, Zhaoqiang; Pang, Yuehong


    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.

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

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


    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).

  7. Using click chemistry to modify block copolymers and their morphologies (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

  8. Ruthenium-catalyzed synthesis of 5-amino-1,2,3-triazole-4-carboxylates for triazole-based scaffolds: beyond the dimroth rearrangement. (United States)

    Ferrini, Serena; Chandanshive, Jay Zumbar; Lena, Stefano; Comes Franchini, Mauro; Giannini, Giuseppe; Tafi, Andrea; Taddei, Maurizio


    The 5-amino-1,2,3-triazole-4-carboxylic acid is a suitable molecule for the preparation of collections of peptidomimetics or biologically active compounds based on the triazole scaffold. However, its chemistry may be influenced by the possibility of undergoing the Dimroth rearrangement. To overcome this problem, a protocol based on the ruthenium-catalyzed cycloaddition of N-Boc ynamides with azides has been developed to give a protected version of this triazole amino acid. When aryl or alkyl azides are reacted with N-Boc-aminopropiolates or arylynamides, the cycloaddition occurs with complete regiocontrol, while N-Boc-alkyl ynamides yield a mixture of regioisomers. The prepared amino acids were employed for the preparation of triazole-containing dipeptides having the structural motives typical of turn inducers. In addition, triazoles active as HSP90 inhibitors (as compound 41, IC50 = 29 nM) were synthesized.

  9. General method for labeling siRNA by click chemistry with fluorine-18 for the purpose of PET imaging. (United States)

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


    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.

  10. 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.


    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.

  11. Instantaneous Click Chemistry by a Copper-Containing Polymeric-Membrane-Installed Microflow Catalytic Reactor. (United States)

    Yamada, Yoichi M A; Ohno, Aya; Sato, Takuma; Uozumi, Yasuhiro


    The copper(I)-catalyzed Huisgen cycloaddition (azide-alkyne cycloaddition) is an important reaction in click chemistry that ideally proceeds instantaneously. An instantaneous Huisgen cycloaddition has been developed that uses a novel catalytic dinuclear copper complex-containing polymeric membrane-installed microflow device. A polymeric membranous copper catalyst was prepared from poly(4-vinylpyridine), copper(II) sulfate, sodium chloride, and sodium ascorbate at the interface of two laminar flows inside microchannels. Elucidation of the structure by XANES, EXAFS, and elemental analysis, as well as second-order Møller-Plesset perturbation theory (MP2) calculations and density functional theory (DFT) calculations assigned the local structure near Cu as a μ-chloro dinuclear Cu(I) complex. The microflow device promotes the instantaneous click reaction of a variety of alkynes and organic azides to afford the corresponding triazoles in quantitative yield.

  12. The growing impact of bioorthogonal click chemistry on the development of radiopharmaceuticals. (United States)

    Zeng, Dexing; Zeglis, Brian M; Lewis, Jason S; Anderson, Carolyn J


    Click chemistry has become a ubiquitous chemical tool with applications in nearly all areas of modern chemistry, including drug discovery, bioconjugation, and nanoscience. Radiochemistry is no exception, as the canonical Cu(I)-catalyzed azide-alkyne cycloaddition, strain-promoted azide-alkyne cycloaddition, inverse electron demand Diels-Alder reaction, and other types of bioorthogonal click ligations have had a significant impact on the synthesis and development of radiopharmaceuticals. This review will focus on recent applications of click chemistry ligations in the preparation of imaging agents for SPECT and PET, including small molecules, peptides, and proteins labeled with radionuclides such as (18)F, (64)Cu, (111)In, and (99m)Tc.

  13. Click-to-Chelate: Development of Technetium and Rhenium-Tricarbonyl Labeled Radiopharmaceuticals

    Directory of Open Access Journals (Sweden)

    Thomas L. Mindt


    Full Text Available The Click-to-Chelate approach is a highly efficient strategy for the radiolabeling of molecules of medicinal interest with technetium and rhenium-tricarbonyl cores. Reaction of azide-functionalized molecules with alkyne prochelators by the Cu(I-catalyzed azide-alkyne cycloaddition (CuAAC; click reaction enables the simultaneous synthesis and conjugation of tridentate chelating systems for the stable complexation of the radiometals. In many cases, the functionalization of (biomolecules with the ligand system and radiolabeling can be achieved by convenient one-pot procedures. Since its first report in 2006, Click-to-Chelate has been applied to the development of numerous novel radiotracers with promising potential for translation into the clinic. This review summarizes the use of the Click-to-Chelate approach in radiopharmaceutical sciences and provides a perspective for future applications.

  14. Chemical Architecture and Applications of Nucleic Acid Derivatives Containing 1,2,3-Triazole Functionalities Synthesized via Click Chemistry

    Directory of Open Access Journals (Sweden)

    Wei Gong


    Full Text Available There is considerable attention directed at chemically modifying nucleic acids with robust functional groups in order to alter their properties. Since the breakthrough of copper-assisted azide-alkyne cycloadditions (CuAAC, there have been several reports describing the synthesis and properties of novel triazole-modified nucleic acid derivatives for potential downstream DNA- and RNA-based applications. This review will focus on highlighting representative novel nucleic acid molecular structures that have been synthesized via the “click” azide-alkyne cycloaddition. Many of these derivatives show compatibility for various applications that involve enzymatic transformation, nucleic acid hybridization, molecular tagging and purification, and gene silencing. The details of these applications are discussed. In conclusion, the future of nucleic acid analogues functionalized with triazoles is promising.

  15. Click chemistry for rapid labeling and ligation of RNA. (United States)

    Paredes, Eduardo; Das, Subha R


    The copper(I)-promoted azide-alkyne cycloaddition reaction (click chemistry) is shown to be compatible with RNA (with free 2'-hydroxyl groups) in spite of the intrinsic lability of RNA. RNA degradation is minimized through stabilization of the Cu(I) in aqueous buffer with acetonitrile as cosolvent and no other ligand; this suggests the general possibility of "ligandless" click chemistry. With the viability of click chemistry validated on synthetic RNA bearing "click"-reactive alkynes, the scope of the reaction is extended to in-vitro-transcribed or, indeed, any RNA, as a click-reactive azide is incorporated enzymatically. Once clickable groups are installed on RNA, they can be rapidly click labeled or conjugated together in click ligations, which may be either templated or nontemplated. In click ligations the resultant unnatural triazole-linked RNA backbone is not detrimental to RNA function, thus suggesting a broad applicability of click chemistry in RNA biological studies.

  16. Diversity-Oriented Peptide Stapling

    DEFF Research Database (Denmark)

    Tran, Thu Phuong; Larsen, Christian Ørnbøl; Røndbjerg, Tobias


    The introduction of macrocyclic constraints in peptides (peptide stapling) is an important tool within peptide medicinal chemistry for stabilising and pre-organising peptides in a desired conformation. In recent years, the copper-catalysed azide-alkyne cycloaddition (CuAAC) has emerged...... as a powerful method for peptide stapling. However, to date CuAAC stapling has not provided a simple method for obtaining peptides that are easily diversified further. In the present study, we report a new diversity-oriented peptide stapling (DOPS) methodology based on CuAAC chemistry. Stapling of peptides...... incorporating two azide-modified amino acids with 1,3,5-triethynylbenzene efficiently provides (i, i+7)- and (i, i+9)-stapled peptides with a single free alkyne positioned on the staple, that can be further conjugated or dimerised. A unique feature of the present method is that it provides easy access...

  17. Synthesis and anticonvulsant activity of 1-substituted benzyl-N-substituted-1, 2, 3-triazole-4-for-mamides

    Institute of Scientific and Technical Information of China (English)

    WANG Junmin; JUN Changsoo; CHAI Kyuyun; KWAK Kyungchell; QUAN Zheshan


    Substituted benzyl azids were synthesized through the reaction of substituted benzyl chloride and sodium azid, which subsequently underwent cyclization with ethyl propiolate and amidation to give thirteen 1-substituted benzyl-N-substituted-1, 2, 3-triazole-4-formamide derivatives (3a-3m). The structure of the synthesized compounds was confirmed by IR, 1H-NMR, MS and elemental analysis. Their anticonvulsant activity against maximal electrolshock (MES) induced seizure was tested and the result showed that all these compounds possess anticonvulsant activity in different degrees. Among those, the compounds containing chloro atoms on the phenyl ring were less potent in anticonvulsant activity, while introducing one or two fluorin atoms on benzyl system increased its activity. Furthermore, their activity decreased when there was substituent on the nitrogen atom of carboxamide, and the larger the substituent, the lower the activity.

  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


    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. Synthesis improvement of zidovudine%齐多夫定合成工艺改进

    Institute of Scientific and Technical Information of China (English)

    余勇; 刘骞峰; 杨永忠; 徐云侠; 吴生秀


    β-Thymidine was used as the starting material. Oxygen bridge compound was formed via mitsuobureaction from 5' -primary hydroxyl protected by p-methoxy benzoic acid in DEAD/PPh3 system. The zidovu-dine was obtained via azide reaction between oxygen bridge compound and sodium azide. The total yield was62%.%以β-胸苷为起始原料,5’-伯羟基采用对甲氧基苯甲酸保护,并在DEAD/PPh3体系中经过mitsuobu反应形成氧桥化合物,再与叠氮化钠发生叠氮化反应,最后脱对甲氧基苯甲酸保护基后获得目标产物齐多夫定,总收率62%.

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

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


    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.

  1. A versatile pathway to end-functionalized cellulose ethers for click chemistry applications. (United States)

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


    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.

  2. Study of monopropellants for electrothermal thrusters. Evaluation test program task summary report (United States)

    Kuenzly, J. D.


    An electrothermal thruster designed for operation with MIL-grade hydrazine is suitable for operation with propellants having lower freezing points. These propellants are 76% hydrazine - 24% hydrazine azide, Aerozine-50, 50% hydrazine - 50% monomethylydrazine, and a TRW-formulated mixture of 35% hydrazine - 50% monomethylhydrane - 15% ammonia. A steady-state specific impulse of 200 sec was exceeded by all propellants. A pulse-mode value of 175 sec specific impulse was exceeded by the azide blend for pulse widths greater than 50 ms and was met by the carbonaceous propellants for pulse widths greater than 100 ms. Longer residence times were required for the carbonaceous propellants; the original thruster design was modified by increasing the characteristic chamber length and density of screen packing. A substantial amount of thermal energy must be supplied to initiate decomposition of propellants containing unsymmetrical-dimethylhydrazine and monomethylhydrazine. The rate controlling factor appeared to be the endothermic removal of methyl radicals.

  3. Patterned porous silicon photonic crystals with modular surface chemistry for spatial control of neural stem cell differentiation (United States)

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


    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

  4. Convenient Synthesis and Antimicrobial Activity of Some Novel Amino Acid Coupled Triazoles

    Directory of Open Access Journals (Sweden)

    S. M. El Rayes


    Full Text Available This study describes a promising one-pot synthesis of [2-(5-benzyl-4-phenyl-4H-[1,2,4]triazol-3-thio-acetyl]-amino acid methyl esters 6a-h and dipeptides 10a-e, which were successfully synthesized starting from amino acid esters 5a-h, 9a-e and azides 4, 8a,b, respectively. On the other hand, azide 4 underwent Curtius rearrangement to the corresponding isocyanate, which subsequently reacted with selected aliphatic amine and/or aniline derivatives to give the corresponding urea derivatives 11 and 12a,b. Reactions of the isocyanate with secondary amines gave amide derivatives 13a,b. The structural elucidation of products is reported and some of the products were also screened for their antimicrobial activity.

  5. The localization of vanadium- and nitrate-sensitive ATPases in Cucumis sativus L. root cells

    Directory of Open Access Journals (Sweden)

    Grażyna Kłobus


    Full Text Available Distinct separation of plasma membrane and tonoplast membranes was attained by centrifugation of cucumber root microsomes in a sucrose density gradient. The fractions enriched in plasma membranes, identified on the basis of the sensitivity of ATPases to VO43- sedimented at a specific density of 1. 1463-1. 1513 g x cm-3. They did not exhibit cytochrome oxidase activity and there was only trace activity of the azide-sensitive ATPase in these fractions. The fractions enriched in tonoplast membranes, having peak activity of nitrate-sensitive ATPase, were found in the region of specific densities of 1. 1082-1.1175. The presence of vanadium-sensitive and azide-sensitive ATPases was not found in these fractions. The ATPase inhibitors, DCCD, DES and EDAC, inhibited the activity of both vanadium-sensitive and nitrate-sensitive ATPases.

  6. Effects and mechanisms of eugenol, isoeugenol, coniferylaldehyde and dihydroeugenol on the riboflavin-sensitized photooxidation of α-terpinene in methanol. (United States)

    Lee, Ju Yeon; Jung, Mun Yhung


    The effects of eugenol, isoeugenol, coniferylaldehyde, and dihydroeugenol on the riboflavin-sensitized photooxidation of α-terpinene in methanol were studied. Riboflavin greatly accelerated α-terpinene oxidation in methanol during light illumination, resulting in two major oxidation products (p-cymene and ascaridole). The results clearly showed the involvement of Type I and II mechanisms. All the eugenols exerted strong protective activity on riboflavin sensitized photooxidation of α-terpinene. Dihydroeugenol showed the highest protective activity, followed by isoeugenol, coniferylaldehyde, and eugenol, in a decreasing order. Dihydroeugenol greatly inhibited the production of ascaridole, but showed relatively low inhibitory activity on the formation of p-cymene. The protective activity of dihydroeugenol was higher than those of BHA, BHT and sodium azide. Sodium azide, a specific singlet oxygen quencher, showed strong inhibitory activity on the formation of ascaridole, but very low inhibitory activity on the formation of p-cymene, verifying the feasibility of mechanism study with the present model system.

  7. Tunable Surface Properties of a Conductive PEDOT/EVAL blend

    DEFF Research Database (Denmark)

    Pizzi, Elisa; Martinelli, Andrea; D'Ilario, Lucio;

    Conductive polymers have been studied extensively during recent years. Especially,poly(3,4-ethylenedioxythiophene) (PEDOT) have found many application areas and arebroadly considered one of the most promising conductive polymers. In order to broadenthe application field of PEDOT we have developed...... an azide functional poly(3,4-ethylenedioxythiophene) (PEDOT-N3)1. The azide functional conductive polymer canbe postpolymerization functionalized to introduce a large range of molecules onto theconductive backbone through click chemistry2.Here we present a study of the incorporation of poly......(ethylene-co-vinyl alcohol) (EVAL)into a copolymer of EDOT and EDOT-N3 (poly(EDOT-co-EDOT-N3)). Poly(ethyleneco-vinyl alcohol) (EVAL) is known to swell in polar solvents, which was exploited inthis study to permit a good blending of the two polymers. Since both polymers haveresidual functional groups the polymer blend...

  8. Two-step functionalization of oligosaccharides using glycosyl iodide and trimethylene oxide and its applications to multivalent glycoconjugates. (United States)

    Hsieh, Hsiao-Wu; Davis, Ryan A; Hoch, Jessica A; Gervay-Hague, Jacquelyn


    Oligosaccharide conjugates, such as glycoproteins and glycolipids, are potential chemotherapeutics and also serve as useful tools for understanding the biological roles of carbohydrates. With many modern isolation and synthetic technologies providing access to a wide variety of free sugars, there is increasing need for general methodologies for carbohydrate functionalization. Herein, we report a two-step methodology for the conjugation of per-O-acetylated oligosaccharides to functionalized linkers that can be used for various displays. Oligosaccharides obtained from both synthetic and commercial sources were converted to glycosyl iodides and activated with I2 to form reactive donors that were subsequently trapped with trimethylene oxide to form iodopropyl conjugates in a single step. The terminal iodide served as a chemical handle for further modification. Conversion into the corresponding azide followed by copper-catalyzed azide-alkyne cycloaddition afforded multivalent glycoconjugates of Gb3 for further investigation as anti-cancer therapeutics.

  9. Reactivity mapping with electrochemical gradients for monitoring reactivity at surfaces in space and time. (United States)

    Krabbenborg, Sven O; Nicosia, Carlo; Chen, Pengkun; Huskens, Jurriaan


    Studying and controlling reactions at surfaces is of great fundamental and applied interest in, among others, biology, electronics and catalysis. Because reaction kinetics is different at surfaces compared with solution, frequently, solution-characterization techniques cannot be used. Here we report solution gradients, prepared by electrochemical means, for controlling and monitoring reactivity at surfaces in space and time. As a proof of principle, electrochemically derived gradients of a reaction parameter (pH) and of a catalyst (Cu(I)) have been employed to make surface gradients on the micron scale and to study the kinetics of the (surface-confined) imine hydrolysis and the copper(I)-catalysed azide-alkyne 1,3-dipolar cycloaddition, respectively. For both systems, the kinetic data were spatially visualized in a two-dimensional reactivity map. In the case of the copper(I)-catalysed azide-alkyne 1,3-dipolar cycloaddition, the reaction order (2) was deduced from it.

  10. Light effect on Click reaction: Role of photonic quantum dot catalyst (United States)

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


    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.

  11. Syntheses of Sulfo-Glycodendrimers Using Click Chemistry and Their Biological Evaluation

    Directory of Open Access Journals (Sweden)

    Tomohiro Fukuda


    Full Text Available A series of novel glycol-clusters containing sulfonated N-acetyl-D-glucosamine (GlcNAc have been synthesized using click chemistry. Three dendrimers with aromatic dendrons were synthesized using chlorination, azidation and click chemistries. The resulting dendrimers were modified with azide-terminated sulfonated GlcNAc using click chemistry. The sulfonated dendrimers showed affinity for proteins, including the lectin wheat germ agglutinin and amyloid beta peptide (1-42. The dendrimers of G1 and G2 in particular showed the largest affinity for the proteins. The addition of the sulfonated GlcNAc dendrimers of G1 and G2 exhibited an inhibition effect on the aggregation of the amyloid beta peptide, reduced the b-sheet conformation, and led to a reduction in the level of nanofiber formation.

  12. 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


    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.

  13. On-demand electrochemical activation of the click reaction on self-assembled monolayers on gold presenting masked acetylene groups. (United States)

    Choi, Inseong; Kim, Young-Kwan; Min, Dal-Hee; Lee, SangWook; Yeo, Woon-Seok


    We report on a new surface modification method for grafting a "dynamic" property for on-demand activation of the click reaction. Our approach utilizes the acetylene group masked with dicobalt hexacarbonyl, Co(2)(CO)(6), which is not reactive toward the click reaction. Electrochemical treatment reveals the acetylene group on the selected region, which is then used as a chemical handle for surface functionalization via the click reaction with an azide-containing molecule. Electrochemical and chemical conversions on the surface were verified by cyclic voltammetry, X-ray photoelectron spectroscopy, and fluorescence spectroscopy. We have demonstrated immobilization of an azide-modified RGD peptide and promotion of cell adhesion/migration to the region of electrochemical induction.

  14. Construction of Biofunctional and Biomedical Polymers by Use of “Click" Chemistry

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    The lecture will address recent research activities aiming at developing novel biomacromolecular materials with unsurpassed properties by use of the proper synthetic tools where various “click” chemistry approaches play a key prominent role. Two entirely different themes will be elaborated...... with first application of orthogonal “clicking” employing both the copper catalyzed alkyne azide 1,3- cycloaddition (CuAAC) and thiol-ene “click” and lastly “electroclicking” onto a conducting polymer surface. In the first part the classical medical material workhorse, poly(-caprolactone) (PCL), has been...... that comprises rod-like, coil-like, and dendritic fragments. The facile route to linear-dendritic cholesteryl-b-PCL-b-(L-lysine)G2 by azide-alkyne and thiol-ene “click” reactions will be elucidated.2 Here the driving motivation was to contrive a robust, facile, and effective synthetic strategy. Thirdly...

  15. Tetrakis(azido-κN(di-2-pyridylamine-κ2N2,N2′platinum(IV

    Directory of Open Access Journals (Sweden)

    Kwang Ha


    Full Text Available In the title complex, [Pt(N34(C10H9N3], the PtIV ion is six-coordinated in a slightly distorted octahedral environment by the two pyridine N atoms of the chelating di-2-pyridylamine (dpa ligand and four N atoms from four azide anions. The dpa ligand is not planar, the dihedral angle between the pyridine rings being 20.0 (3°. The azide ligands are slightly bent [N—N—N = 173.5 (8–175.1 (8°]. In the crystal, the complex molecules are connected by N—H...N hydrogen bonds, forming a chain along the b axis. An intermolecular π–π interaction between the chains is also present, the ring centroid–centroid distance being 3.713 (4 Å.

  16. A chemical method for fast and sensitive detection of DNA synthesis in vivo. (United States)

    Salic, Adrian; Mitchison, Timothy J


    We have developed a method to detect DNA synthesis in proliferating cells, based on the incorporation of 5-ethynyl-2'-deoxyuridine (EdU) and its subsequent detection by a fluorescent azide through a Cu(I)-catalyzed [3 + 2] cycloaddition reaction ("click" chemistry). Detection of the EdU label is highly sensitive and can be accomplished in minutes. The small size of the fluorescent azides used for detection results in a high degree of specimen penetration, allowing the staining of whole-mount preparations of large tissue and organ explants. In contrast to BrdU, the method does not require sample fixation or DNA denaturation and permits good structural preservation. We demonstrate the use of the method in cultured cells and in the intestine and brain of whole animals.

  17. 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


    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.

  18. Guidance Document: Surface Soils Sampling for Munitions Residues in Military Live Fire Training Ranges: Canadian Protocol (United States)


    room temperature. To avoid the loss of volatiles, the digestion process has to be conducted in a closed vessel, using a microwave apparatus...1996), Microwave assisted acid digestion of siliceous and organically based matrices, EPA SW-846 Method 3052, Revision 0, U.S. Environmental...styphnate/ lead azide Antimony Antimony Sulfide Arsenic Copper • • • Bismuth Tin Zinc Iron Tungsten Nickel Cobalt and Chromium 2.3 Fate

  19. A versatile and an efficient synthesis of 5-substituted-1-tetrazoles

    Indian Academy of Sciences (India)

    Madhusudana Reddy Muthukur Bhoje Gowd; Mohamed Afzal Pasha


    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.

  20. Heat release mechanism of energetics

    Energy Technology Data Exchange (ETDEWEB)

    Kubota, N. [Third Research Center, Technical Research and development Institute (Japan)


    Determination of the heat release mechanism of energetic materials is a major subject of combustion study. In order to elucidate the combustion process of various types of energetic materials a generalized combustion wave structure was proposed and the heat release process was discussed. The heat release process was significantly different between the physical structures of the materials: homogeneous and heterogeneous materials. The thermal structure of an azide polymer was evaluated to demonstrate the heat release mechanism. (author) 6 refs.

  1. An efficient synthesis of novel bis-triazole glycoconjugates via a three-component condensation as a key reaction. (United States)

    Cheng, Jie; Gu, Zhenlong; He, Caiyu; Jin, Jie; Wang, Lijun; Li, Guojun; Sun, Bei; Wang, Hui; Bai, Jun


    Novel bis-triazole glycoconjugates were designed and prepared successfully via 5 steps from propargyl per-O-acetyl-β-d-glucoside or xyloside (total yield of 48-53%), after utilizing a three-component condensation of propargyl per-O-acetyl-β-d-glycoside, formaldehyde, and sodium azide as a key step to synthesize 2-hydroxymethyl-2H-1,2,3-triazole glycoconjugates. The developed bis-triazole glycoconjugates would be crucial in antivirus pharmacology and chemical biology.

  2. 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


    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.

  3. Diversity-oriented synthesis of dihydrobenzoxazepinones by coupling the Ugi multicomponent reaction with a Mitsunobu cyclization

    Directory of Open Access Journals (Sweden)

    Lisa Moni


    Full Text Available An operationally simple protocol for the synthesis of 2,3-dihydrobenzo[f][1,4]oxazepin-3-ones, based on an Ugi reaction of an ortho-(benzyloxybenzylamine, glycolic acid, an isocyanide and an aldehyde, followed by an intramolecular Mitsunobu substitution was developed. The required ortho-(benzyloxybenzylamines have been in situ generated from the corresponding azides, in turn prepared in high yields from salicylic derivatives.

  4. Hypergolic Ignition of Ionic Liquids (Preprint) (United States)


    imidazolium dicyanamide/WFNA; ID = 15 ms. Figure 3. IR product spectrum of 1-butyl-3-methyl-imidazolium ( BMIM ) azide reacting with WFNA. Figure...4. IR product spectrum of BMIM dicyanamide reacting with WFNA. Figure 5. IR product spectrum of BMIM dicyanamide reacting with WFNA. The...evolution of CO2, N2O and HNCO is shown here. Figure 6. Difference product spectrum of BMIM dicyanamide reacting with WFNA. The dark line is the

  5. Perchlorate Remediation Using New Nanoscale Polymer Technology (United States)


    conditions to give a total of 101 g product. Reduce Amount of Reagents The propargyl tosylate initiated PEOX was analyzed for acetylene content. There...the copper(I) catalyzed reaction between azide functional groups (-N3) and propargyl or acetylenic functional groups (-C≡C-), has become a major...available at an affordable price . This potential perchlorate binding site was reacted with PEOX DP= 100 as a model compound in methanol. 1H-NMR and SEC

  6. Convenient Approach to Access Octa-Glycosylated Porphyrins via “Click Chemistry”

    Directory of Open Access Journals (Sweden)

    Misako Okada


    Full Text Available Easy, quantitative, and one-pot introduction of eight β-lactoside-modules onto a porphyrin-core was achieved through Cu+-catalyzed chemoselective coupling (click chemistry between a porphyrin carrying eight alkyne-terminals and β-lactosyl azides. The obtained porphyrin-based glycocluster shows not only good water-solubility but also strong/specific lectin-affinity.

  7. Click chemistry with DNA


    El-Sagheer, Afaf H.; Brown, Tom


    The advent of click chemistry has led to an influx of new ideas in the nucleic acids field. The copper catalysed alkyne–azide cycloaddition (CuAAC) reaction is the method of choice for DNA click chemistry due to its remarkable efficiency. It has been used to label oligonucleotides with fluorescent dyes, sugars, peptides and other reporter groups, to cyclise DNA, to synthesise DNA catenanes, to join oligonucleotides to PNA, and to produce analogues of DNA with modified nucleobases and backbone...

  8. Copper iodide nanoparticles on poly(4-vinyl pyridine) as new and green catalyst for multicomponent click synthesis of 1,4-disubstituted-1,2,3-triazoles in water

    Institute of Scientific and Technical Information of China (English)

    Jalal Albadi; Mosadegh Keshavarz; Masoumeh Abedini; Masoumeh Vafaie-nezhad


    Poly(4-vinyl pyridine) supported nanoparticle of copper(Ⅰ) iodide is reported as a green and recyclable catalyst for the regioselective synthesis of 1,4-disubstituted-1H-1,2,3-triazoles from benzyl halides,sodium azide and terminal alkynes in water.This catalyst can be recovered by simple filtration and recycled up to 8 consecutive runs without any loss of its efficiency.

  9. Unique tetrameric and hexameric mannoside clusters prepared by click chemistry. (United States)

    Al-Mughaid, Hussein; Al-Zoubi, Raed M; Paul, Nawal K; Grindley, T Bruce


    The synthesis of novel tetrameric and hexameric mannoside clusters bearing 1,2,3-trizole linkages via Cu(I)-catalyzed azide-alkyne cycloaddition reaction ("click chemistry") is described. An attractive feature of these multiarmed mannoside clusters as potential inhibitors of uropathogenic Escherichia coli is the use of an aglycone whose length is designed to fit in the tyrosine gate. The acetylated mannosides were deprotected and the corresponding de-O-acetylated mannosides were found to exhibit good water solubility.


    Institute of Scientific and Technical Information of China (English)

    Devamani; Srividhya; Sundaram; Manjunathan; Sivashankaran; Nithyanandan; Subramanan; Balamurugan; Sengodan; Senthil


    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...

  11. In situ assembly of porous Au-paper electrode and functionalization of magnetic silica nanoparticles with HRP via click chemistry for Microcystin-LR immunoassay. (United States)

    Ge, Shenguang; Liu, Weiyan; Ge, Lei; Yan, Mei; Yan, Jixian; Huang, Jiadong; Yu, Jinghua


    A simple, low-cost and sensitive origami electrochemical immunoassay-device was developed based on a novel gold nanoparticle modified porous paper working electrode (Au-PWE) for point-of-care testing. Azide-functionalized Au-PWE was prepared by the functionalization of Au-PWE with 1-azidoundecan-11-thiol. Alkyne end-terminated antibody was prepared with 4-pentynoic acid and antibody by the 1-ethyl-3-(3-(dimethylamino) propyl) carbodiimide hydrochloride and N-hydroxysuccinimide activation reaction. Alkyne-antibody was coupled to azido-Au-PWE by click reaction as a recognition element. Nearly monodispersed sphere-like silica-coated ferroferric oxide (Fe3O4@SiO2) nanoparticles were prepared via the reverse microemulsion method. Azide-functionalized Fe3O4@SiO2 was prepared by the functionalization of silica shell with 3-bromopropyltrichlorosilane followed by substitution with sodium azide. Alkyne-functionalized antibody and horse radish peroxidase were coupled to azide-functionalized Fe3O4@SiO2 by click reaction as signal label. Horse radish peroxidase and ferroferric oxide could catalyze the oxidation of thionine in the presence of hydrogen peroxide. After the sandwich immunoreaction, the current was proportional to the logarithm of the Microcystin-LR. The linear regression equation was i(μA)=119.89+46.27 log cMC-LR (μg/mL) in the range from 0.01 to 200 μg/mL. The limit of detection was 0.004 μg/mL. This immunoassay would provide a universal immunoassay method in environmental monitoring and public health.

  12. Lattice dynamics and electronic structure of energetic solids LiN3 and NaN3: A first principles study


    Babu, K Ramesh; Vaitheeswaran, G.


    We report density functional theory calculations on the crystal structure, elastic, lattice dynamics and electronic properties of iso-structural layered monoclinic alkali azides, LiN3 and NaN3. The effect of van der Waals interactions on the ground- state structural properties is studied by using various dispersion corrected density functionals. Based on the equilibrium crystal structure, the elastic constants, phonon dispersion and phonon density of states of the compounds are calculated. Th...

  13. Tulane/Xavier Vaccine Peptide Program (United States)


    resin bound peptide -PEG conjugate to remove copper and uncoupled PEG. After removal from the resin, MALDI-TOF MS analysis of the product...synthesized) was used to further modify the peptide with a singly modified PEG chain bearing a terminal alkyne functionality through a copper -catalyzed azide...COVERED (From - To) 1 July 2010 – 30 June 201 4. TITLE AND SUBTITLE Tulane/Xavier Vaccine Peptide Program 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c

  14. Cryptophane-Folate Biosensor for 129Xe NMR (United States)


    2005) Head- to-tail peptide cyclodimerization by copper -catalyzed azide-alkyne cycloaddition. Angew. Chem., Int. Ed. Engl. 44, 2215−2220. (55...cryptophane biosensor was synthesized in 20 nonlinear steps, which included functionalization with folate recognition moiety, solubilizing peptide , and...carbonic anhydrases I or II.36 Another example included a peptide - labeled 129Xe biosensor by Schlundt et al. that produced a 1 ppm downfield shift upon

  15. 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


    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.

  16. Isolation and characterization of mutants defective in the cyanide-insensitive respiratory pathway of Pseudomonas aeruginosa.


    Cunningham, L.; Williams, H D


    The branched respiratory chain of Pseudomonas aeruginosa contains at least two terminal oxidases which are active under normal physiological conditions. One of these, cytochrome co, is a cytochrome c oxidase which is completely inhibited by concentrations of the respiratory inhibitor potassium cyanide as low as 100 microM. The second oxidase, the cyanide-insensitive oxidase, is resistant to cyanide concentrations in excess of 1 mM as well as to sodium azide. In this work, we describe the isol...

  17. 2-C-branched glycosides from 2'-carbonylalkyl 2-O-Ms(Ts)-C-glycosides. A tandem SN2-SN2 reaction via 1,2-cyclopropanated sugars. (United States)

    Shao, Huawu; Ekthawatchai, Sanchai; Wu, Shih-Hsiung; Zou, Wei


    [reaction: see text] Under basic conditions, 2'-aldehydo (acetonyl) 2-O-Ms(Ts)-alpha-C-glycosides undergo an intramolecular S(N)2 reaction to form 1,2-cyclopropanated sugars, which react with nucleophiles (alcohols, thiols, and azide) at the anomeric carbon to give 2-C-branched glycosides. By way of contrast, the 1,2-cyclopropanes derived from 2'-ketones only react with thiols to give 2-C-branched thioglycosides.

  18. One pot Click chemistry: A three component reaction for the synthesis of 2-mercaptobenzimidazole linked coumarinyl triazoles as anti-tubercular agents. (United States)

    Anand, Ashish; Kulkarni, Manohar V; Joshi, Shrinivas D; Dixit, Sheshagiri R


    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.

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

    DEFF Research Database (Denmark)

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


    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...... itself. These findings support the experimentally determined rate law and shed light on the origin of high reactivity of the in situ generated copper acetylides....

  20. Aspartic acid-96 is the internal proton donor in the reprotonation of the Schiff base of bacteriorhodopsin. (United States)

    Otto, H; Marti, T; Holz, M; Mogi, T; Lindau, M; Khorana, H G; Heyn, M P


    Above pH 8 the decay of the photocycle intermediate M of bacteriorhodopsin splits into two components: the usual millisecond pH-independent component and an additional slower component with a rate constant proportional to the molar concentration of H+, [H+]. In parallel, the charge translocation signal associated with the reprotonation of the Schiff base develops a similar slow component. These observations are explained by a two-step reprotonation mechanism. An internal donor first reprotonates the Schiff base in the decay of M to N and is then reprotonated from the cytoplasm in the N----O transition. The decay rate of N is proportional to [H+]. By postulating a back reaction from N to M, the M decay splits up into two components, with the slower one having the same pH dependence as the decay of N. Photocycle, photovoltage, and pH-indicator experiments with mutants in which aspartic acid-96 is replaced by asparagine or alanine, which we call D96N and D96A, suggest that Asp-96 is the internal proton donor involved in the re-uptake pathway. In both mutants the stoichiometry of proton pumping is the same as in wild type. However, the M decay is monophasic, with the logarithm of the decay time [log (tau)] linearly dependent on pH, suggesting that the internal donor is absent and that the Schiff base is directly reprotonated from the cytoplasm. Like H+, azide increases the M decay rate in D96N. The rate constant is proportional to the azide concentration and can become greater than 100 times greater than in wild type. Thus, azide functions as a mobile proton donor directly reprotonating the Schiff base in a bimolecular reaction. Both the proton and azide effects, which are absent in wild type, indicate that the internal donor is removed and that the reprotonation pathway is different from wild type in these mutants. PMID:2556706

  1. 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


    <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

  2. Direct Nucleophilic Substitution of Free Allylic Alcohols in Water Catalyzed by FeCl3⋅6 H2O: Which is the Real Catalyst?


    Trillo Alarcón, María Paz; Baeza, Alejandro; Nájera Domingo, Carmen


    The allylic substitution reaction, and particularly the direct allylic amination reaction, of free allylic alcohols in water catalyzed by FeCl3⋅6 H2O is described. This novel environmentally-friendly methodology allows the use of a wide variety of nitrogenated nucleophiles such as sulfonamides, carbamates, benzamides, anilines, benzotriazoles, and azides, generally giving good yields of the corresponding substitution products. The synthetic applicability of the process is also demonstrated be...



    Jennifer Fernandes; Pankaj Kumar; Abhishek Kumar


    Phenyl oxazolidinones were prepared from R-glycidyl butarate and Para bromo aniline, further (3-(4-bromophenyl) methylene oxazolidine-5yl) and substituted benzothiazinen was refluxed resulted in oxazolidinones benzothiazinen moieties. Treatment of these oxazolidinones benzo thiazinen moieties with methane sulfonyl gives its sulphonates on further treatment with sodium azide and tri phenyl phosphine in acetic anhydride gives acetamide derivatives. Further synthesized compounds were characteriz...

  4. Design, synthesis and in vitro antimalarial evaluation of triazole-linked chalcone and dienone hybrid compounds. (United States)

    Guantai, Eric M; Ncokazi, Kanyile; Egan, Timothy J; Gut, Jiri; Rosenthal, Philip J; Smith, Peter J; Chibale, Kelly


    A targeted series of chalcone and dienone hybrid compounds containing aminoquinoline and nucleoside templates was synthesized and evaluated for in vitro antimalarial activity. The Cu(I)-catalyzed cycloaddition of azides and terminal alkynes was applied as the hybridization strategy. Several chalcone-chloroquinoline hybrid compounds were found to be notably active, with compound 8b the most active, exhibiting submicromolar IC(50) values against the D10, Dd2 and W2 strains of Plasmodium falciparum.

  5. Dissecting the Roles of Brain Injury and Combat-Related Stress in Post-Traumatic Headache (United States)


    slice was placed in block (4% goat serum, 0.1% Triton-X, 0.5% sodium azide in PBS) for 1 h. Immunoglobulin G (IgG) extravasation was used to detect...plastic changes in sensory cortical function that might serve as mechanisms entraining PTH. We use two-photon microscopy and electrophysiology...changes in neural network processing and provides potential network level mechanisms that underlie the changes in sensory perception seen in PTH. 8

  6. 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: [Universidade Federal Rural de Pernambuco (UFRPE), Recife, PE (Brazil). Dept. de Ciencias Moleculares


    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)

  7. Exploring architectures displaying multimeric presentations of a trihydroxypiperidine iminosugar

    Directory of Open Access Journals (Sweden)

    Camilla Matassini


    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.

  8. Assessment of Nanobiotechnology-Targeted siRNA Designed to Inhibit NF-kappaB Classical And Alternative Signaling in Breast Tumor Macrophages (United States)


    including mannose, fucose , and galactose via ‘click’ chemistry. In this work, we show that the incorporation of contrast agents into the...following blocks: (1) an azide-displaying block for the attachment of alkyne-functionalized mannose, fucose , or galactose via ‘click’ chemistry, (2) a...immunohistochemistry). Biodistribution studies involving the fucose - and galactose-targeted nanoparticles are ongoing. Conclusions: The materials developed

  9. 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


    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.

  10. Involvement of superoxide and myeloperoxidase in oxygen-dependent killing of Staphylococcus aureus by neutrophils.


    Hampton, M B; A. J. Kettle; Winterbourn, C C


    We have used a quantitative assay that measures independent rate constants for phagocytosis and killing of Staphylococcus aureus to investigate the involvement of superoxide and myeloperoxidase in bacterial killing by human neutrophils. To inhibit superoxide-dependent processes, superoxide dismutase was cross-linked to immunoglobulin G and the conjugate was attached to the surface of S. aureus via protein A in its cell wall. Myeloperoxidase was inhibited with azide, and myeloperoxidase-defici...

  11. Sampling for Explosives Residues at Fort Greely, Alaska. Reconnaissance Visit July 2000 (United States)


    and stearic acid (1.5%) 55 g Primer perc #K90 Aluminum powder (5%), antimony sulfide (16%), barium nitrate (30%), lead styphnate (40%), tetracene...nitrate (0.75%) 4.64 g Primer M55 perc Fuse Primer mix NOL #130*9 Antimony sulfide (15%), barium nitrate (20%), lead azide (20%), lead styphnate (40... Barium (Ba), lead (Pb), chromium (Cr), cadmium (Cd), zinc (Zn), and antimony (Sb) are metals used in various primers. Unlike the organic explosives

  12. Site Characterization and Analysis Penetrometer System (SCAPS) Heavy Metal Sensors (United States)


    bleaches, hydrochloric acid, sulfuric acid, nitric acid, explosive compounds (e.g., lead azide and lead styphnate ), phosphate cleaners, petroleum and...products of these chemicals. Previous investigations have indicated that heavy metals, including arsenic (As), barium (Ba), beryllium (Be), cadmium (Cd...Lake City. It was used by the LCAAP fire department from 1951 to 1967 to burn wooden boxes. Antimony, barium , cadmium, copper, lead, mercury, silver

  13. FY97 Environmental Technology Division Annual Report. (United States)


    Leachate Procedure (TCLP) test due to the high barium , lead or chromium content), or military munitions for which there are no documented...batteries used in various missiles that contain lead, silver, cadmium, barium and chromium, as well as nickel and lithium, which are all toxic and/or...maintenance, storage, disposal, and demilitarization. Some of these sites contain primary explosives, such as lead azide, lead styphnate , and nitroglycerin (NG

  14. Methods for the Preparation of Initiating and Delay Compositions (United States)


    invustigatod include lead azide, lead styphnate , barium styphnatc, lead 2:4 dinitrorcsorcinatc, lead 4:6 dinitrorosorcinatc. Examples arc given from...method (a) Granulated barium styphnatc (R.D. 1320B). By adding a mixture of magnesium styphnate and sodium carboxy methyl cellulose solutions to a solution...increase in proportion of colloid the number of constituent crystals greatly increases. Granulated barium styphnate is a very stable substance and its method

  15. Hydrogen peroxide release and hydroxyl radical formation in mixtures containing mineral fibres and human neutrophils.


    Leanderson, P; Tagesson, C


    The ability of different mineral fibres (rock wool, glass wool, ceramic fibres, chrysotile A, chrysotile B, amosite, crocidolite, antophyllite, erionite, and wollastonite) to stimulate hydrogen peroxide (H2O2) and hydroxyl radical (OH.) formation in mixtures containing human polymorphonuclear leucocytes (PMNLs) was investigated. In the presence of azide, all the fibres caused considerable H2O2 formation, and about twice as much H2O2 was found in mixtures with the natural fibres (asbestos, eri...

  16. Impact of bacterial and fungal processes on {sup 14}C-hexadecane mineralisation in weathered hydrocarbon contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Adetutu, Eric M.; Ball, Andy S. [School of Biological Sciences, Flinders University, Adelaide, South Australia, 5001 (Australia); Weber, John; Aleer, Samuel; Dandie, Catherine E. [Centre for Environmental Risk Assessment and Remediation (CERAR), University of South Australia, Mawson Lakes Campus, Adelaide, South Australia, 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of the Environment (CRC CARE), Mawson Lakes, Adelaide, South Australia, 5095 (Australia); Juhasz, Albert L., E-mail: [Centre for Environmental Risk Assessment and Remediation (CERAR), University of South Australia, Mawson Lakes Campus, Adelaide, South Australia, 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of the Environment (CRC CARE), Mawson Lakes, Adelaide, South Australia, 5095 (Australia)


    In this study, the impact of bacterial and fungal processes on {sup 14}C-hexadecane mineralisation was investigated in weathered hydrocarbon contaminated soil. The extent of {sup 14}C-hexadecane mineralisation varied depending on the bioremediation strategy employed. Under enhanced natural attenuation conditions, {sup 14}C-hexadecane mineralisation after 98 days was 8.5 {+-} 3.7% compared to < 1.2% without nitrogen and phosphorus additions. {sup 14}C-hexadecane mineralisation was further enhanced through Tween 80 amendments (28.9 {+-} 2.4%) which also promoted the growth of a Phanerochaete chyrsosporium fungal mat. Although fungal growth in weathered hydrocarbon contaminated soil could be promoted through supplementing additional carbon sources (Tween 80, sawdust, compost, pea straw), fungal {sup 14}C-hexadecane mineralisation was negligible when sodium azide was added to soil microcosms to inhibit bacterial activity. In contrast, when fungal activity was inhibited through nystatin additions, {sup 14}C-hexadecane mineralisation ranged from 6.5 {+-} 0.2 to 35.8 {+-} 3.8% after 98 days depending on the supplied amendment. Bacteria inhibition with sodium azide resulted in a reduction in bacterial diversity (33-37%) compared to microcosms supplemented with nystatin or microcosms without inhibitory supplements. However, alkB bacterial groups were undetected in sodium azide supplemented microcosms, highlighting the important role of this bacterial group in {sup 14}C-hexadecane mineralisation. - Highlights: Black-Right-Pointing-Pointer The roles of different microbial groups in hydrocarbon mineralisation was assessed. Black-Right-Pointing-Pointer Inhibiting fungal growth did not affect {sup 14}C-hexadecane mineralisation. Black-Right-Pointing-Pointer Inhibiting bacterial growth resulted in negligible {sup 14}C-hexadecane mineralisation. Black-Right-Pointing-Pointer alkB bacterial groups were undetected in sodium azide supplemented microcosms. Black

  17. Staudinger Ligation of Peptides at Non-Glycyl Residues


    Soellner, Matthew B.; Tam, Annie; Raines, Ronald T.


    The Staudinger ligation provides a means to form an amide bond between a phosphinothioester and azide. This reaction holds promise for the ligation of peptides en route to the total chemical synthesis of proteins. (Diphenylphosphino)methanethiol is the most efficacious of known reagents for mediating the Staudinger ligation of peptides, providing high (>90%) isolated yields for equimolar couplings in which a glycine residue is at the nascent junction. Surprisingly, the yields are lower (80%) ...

  18. 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


    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


    Institute of Scientific and Technical Information of China (English)

    WU Jinhuang; SUN Yanhui; FENG Xinde


    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.

  20. Generation and characterization of alkali metal clusters in Y-FAU zeolites. An ESR and MAS NMR spectroscopic study (United States)

    Hannus, István; Béres, Attila; Nagy, János B.; Halász, János; Kiricsi, Imre


    Charged and neutral metal clusters of various compositions and sizes can be prepared by controlling the alkali metal content by the decomposition of alkali azides and the composition of the host zeolite by ion-exchange. ESR signals show that electron transfer from alkali metal atoms to alkali metal cations does occur, but in a direction opposite to that predicted by the gas-phase thermochemistry. Alkali metal clusters proved to be very active basic catalytic centers.

  1. Proceedings of the High Energy Density Matter (HEDM) Conference Held in Rosslyn, Virginia on 12-13 May 1987, (United States)


    laser initiated decomposition, IR, UV-Vis, ultraviolet, visible, spectroscopy, H 30, N 202, dinitrogen dioxide , CO, carbon monoxide, CH, high spin...asymmetric dinitrogen dioxide (a-N202), is an analogue of fluorine azide (FN3) and is predicted to be a cryogenic solid. Benard reported that FN3 can be...DETECTION OF H4 * PHOTODISSOCIATION TO FORM H2(B) - A 500 nm - DETECT H2 (B) EMISSION WITH PMT - FLASHLAMP PHOTOLYSIS, X = 200 TO 800 nm - LASER

  2. 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: [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


    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)

  3. A new fluorescent probe for gasotransmitter H₂S: high sensitivity, excellent selectivity, and a significant fluorescence off-on response. (United States)

    Zhang, Jingyu; Guo, Wei


    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.

  4. Polysulfone Functionalized With Phosphonated Poly(pentafluorostyrene) Grafts for Potential Fuel Cell Applications

    DEFF Research Database (Denmark)

    Dimitrov, Ivaylo; Takamuku, Shogo; Jankova Atanasova, Katja


    A multi‐step synthetic strategy to polysulfone (PSU) grafted with phosphonated poly(pentafluorostyrene) (PFS) is developed. It involves controlled radical polymerization resulting in alkyne‐end functional PFS. The next step is the modification of PSU with a number of azide side groups. The grafting....... The proposed synthetic route opens the possibility to tune copolymers’ hydrophilic–hydrophobic balance to obtain membranes with an optimal balance between proton conductivity and mechanical properties....

  5. Phase-vanishing method with acetylene evolution and its utilization in several organic syntheses. (United States)

    Matake, Ryosuke; Niwa, Yuki; Matsubara, Hiroshi


    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.

  6. The Reactivity of 2-Ethoxy-4-Chloroquinazoline and Its Use in Synthesis of Novel Quinazoline Derivatives


    El-Hashash, M. A.; Darwish, K. M.; Rizk, S. A.; EL-BASSIOUNY, F.A.


    The behavior of 2-ethoxy-4-chloroquinazoline 2 towards various nitrogen nucleophiles, namely: thiosemicarbazide, sodium azide, glucosamine, ethanol, and hydrazine hydrate has been discussed. Also, the behavior of 4-(2-ethoxyquinazolin-4-yl)thiosemicarbazide towards one-carbon, for example, ethyl chloroformate, and two-carbon donors, for example, ethyl chloroacetate and diethyl oxalate has been investigated. On the other hand, new 5-ethoxy-2-substituted[1,2,4]-triazolo-[1,5-c]quinazoline deriv...

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

    DEFF Research Database (Denmark)

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


    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...... active ligands including cell binding peptides are patterned in gradients by this method without losing their biological function or the conductivity of the polymer....

  8. Bis{bis(azido-κNbis[bis(pyridin-2-yl-κNamine]cobalt(III} sulfate dihydrate

    Directory of Open Access Journals (Sweden)

    Fatima Setifi


    Full Text Available The search for new molecular materials with interesting magnetic properties, using the pseudohalide azide ion and di-2-pyridylamine (dpa, C10H9N3 as a chelating ligand, led to the synthesis and structure determination of the title compound, [Co(N32(dpa2]2SO4·2H2O. The crystal structure comprises discrete [Co(dpa2(N32]+ cations, sulfate anions, as well as H2O solvent molecules. The CoIII cations display a slightly distorted octahedral coordination sphere defined by two N atoms from azide anions and four N atoms from the pyridyl rings of two dpa ligands. In the crystal, extensive C—H...O, N—H...O, and O—H...O interactions result in supramolecular sheets that lie parallel to the ab plane. The sheets are further linked through O—H...N interactions between the water molecules of one sheet and azide anions of another sheet, forming a supramolecular framework.

  9. Coupling of Ligands to the Liposome Surface by Click Chemistry. (United States)

    Spanedda, Maria Vittoria; De Giorgi, Marcella; Hassane, Fatouma Saïd; Schuber, Francis; Bourel-Bonnet, Line; Frisch, Benoît


    Click chemistry represents a new bioconjugation strategy that can be used to conveniently attach various ligands to the surface of preformed liposomes. This efficient and chemoselective reaction involves a Cu(I)-catalyzed azide-alkyne cycloaddition which can be performed under mild experimental conditions in aqueous media. Here we describe the application of a model click reaction to the conjugation, in a single step, of unprotected α-1-thiomannosyl ligands, functionalized with an azide group, to liposomes containing a terminal alkyne-functionalized lipid anchor. Excellent coupling yields have been obtained in the presence of bathophenanthroline disulfonate, a water soluble copper-ion chelator, acting as a catalyst. No vesicle leakage is triggered by this conjugation reaction and the coupled mannose ligands are exposed at the surface of the liposomes. The major limitation of Cu(I)-catalyzed click reactions is that this conjugation is restricted to liposomes made of saturated (phospho)lipids. To circumvent that constraint, an example of alternative copper-free azide-alkyne click reaction has been developed. Molecular tools and results are presented here.

  10. Synthesis and biological evaluation of indole-2-carboxamides bearing photoactivatable functionalities as novel allosteric modulators for the cannabinoid CB1 receptor. (United States)

    Qiao, Chang-Jiang; Ali, Hamed I; Ahn, Kwang H; Kolluru, Srikanth; Kendall, Debra A; Lu, Dai


    5-Chloro-3-ethyl-N-(4-(piperidin-1-yl)phenethyl)-1H-indole-2-carboxamide (ORG27569, 1) is a prototypical allosteric modulator for the cannabinoid CB1 receptor. Based on this indole-2-carboxamide scaffold, we designed and synthesized novel CB1 allosteric modulators that possess photoactivatable functionalities, which include benzophenone, phenyl azide, aliphatic azide and phenyltrifluoromethyldiazrine. To assess their allosteric effects, the dissociation constant (KB) and allosteric binding cooperativity factor (α) were determined and compared to their parent compounds. Within this series, benzophenone-containing compounds 26 and 27, phenylazide-containing compound 28, and the aliphatic azide containing compound 36b showed allosteric binding parameters (KB and α) comparable to their parent compound 1, 7, 8, and 9, respectively. We further assessed these modulators for their impact on G-protein coupling activity. Interestingly, these compounds exhibited negative allosteric modulator properties in a manner similar to their parent compounds, which antagonize agonist-induced G-protein coupling. These novel CB1 allosteric modulators, possessing photoactivatable functionalities, provide valuable tools for future photo-affinity labeling and mapping the CB1 allosteric binding site(s).

  11. Synthesis and in Vitro Antiproliferative Evaluation of C-13 Epimers of Triazolyl-d-Secoestrone Alcohols: The First Potent 13α-d-Secoestrone Derivative

    Directory of Open Access Journals (Sweden)

    Johanna Szabó


    Full Text Available The syntheses of C-13 epimeric 3-[(1-benzyl-1,2,3-triazol-4-ylmethoxy]-d-secoestrones are reported. Triazoles were prepared from 3-(prop-2-inyloxy-d-secoalcohols and p-substituted benzyl azides via Cu(I-catalyzed azide-alkyne cycloaddition (CuAAC. The antiproliferative activities of the products and their precursors were determined in vitro against a panel of human adherent cervical (HeLa, SiHa and C33A, breast (MCF-7, MDA-MB-231, MDA-MB-361 and T47D and ovarian (A2780 cell lines by means of MTT assays. The orientation of the angular methyl group and the substitution pattern of the benzyl group of the azide greatly influenced the cell growth-inhibitory potential of the compounds. The 13β derivatives generally proved to be more potent than their 13α counterparts. Introduction of a benzyltriazolylmethyl group onto the 3-OH position seemed to be advantageous. One 13α compound containing an unsubstituted benzyltriazolyl function displayed outstanding antiproliferative activities against three cell lines.

  12. Synthesis, antimicrobial activity, and membrane permeabilizing properties of C-terminally modified nisin conjugates accessed by CuAAC. (United States)

    Slootweg, Jack C; van der Wal, Steffen; Quarles van Ufford, H C; Breukink, Eefjan; Liskamp, Rob M J; Rijkers, Dirk T S


    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.

  13. "Click" and Olefin Metathesis Chemistry in Water at Room Temperature Enabled by Biodegradable Micelles. (United States)

    Lipshutz, Bruce H; Bošković, Zarko; Crowe, Christopher S; Davis, Victoria K; Whittemore, Hannah C; Vosburg, David A; Wenzel, Anna G


    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).

  14. Lifetimes of -halo and -azidobenzyl carbocations in aqueous solution

    Indian Academy of Sciences (India)

    R Sanjeev; V Jagannadham


    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.

  15. One-Step Electrochemical Preparation of Multilayer Graphene Functionalized with Nitrogen (United States)

    Ustavytska, Olena; Kurys, Yaroslav; Koshechko, Vyacheslav; Pokhodenko, Vitaly


    A new environmentally friendly one-step method for producing multilayer (preferably 7-9 layers) nitrogen-doped graphene (N-MLG) with a slight amount of oxygen-containing defects was developed. The approach is based on the electrochemical exfoliation of graphite electrode in the presence of azide ions under the conditions of electrolysis with pulse changing of the electrode polarization potential. It was found that usage of azide anions lead not only to the exfoliation of graphite but also to the simultaneous functionalization of graphene sheets by nitrogen atoms (as a result of electrochemical decomposition of azide anions with ammonia evolution). Composition, morphology, structure, and electrochemical properties of N-MLG were characterized by C,H,N analysis, transmission electron microscopy, atomic force microscopy, FTIR, UV-Vis, and Raman spectroscopy, as well as cyclic voltammetry. The perspective of using N-MLG as oxygen reduction reaction electrocatalyst and for the electrochemical analysis of biomarkers (dopamine, ascorbic acid, and uric acid) in their mixtures was shown.

  16. Bridging the phenotypic gap: Real-time assessment of mitochondrial function and metabolism of the nematode Caenorhabditis elegans

    Directory of Open Access Journals (Sweden)

    Flett Aileen


    Full Text Available Abstract Background The ATP levels of an organism are an important physiological parameter that is affected by genetic make up, ageing, stress and disease. Results We have generated luminescent C. elegans through ubiquitous, constitutive expression of firefly luciferase, widely used for in vitro ATP determination. We hypothesise that whole animal luminescence reflects its intracellular ATP levels in vivo. To test this, we characterised the bioluminescence response of C. elegans during sublethal exposure to, and recovery from azide, a treatment that inhibits mitochondrial respiration reversibly, and causes ATP depletion. Consistent with our expectations, in vivo luminescence decreased with increasing sublethal azide levels, and recovered fully when worms were removed from azide. Firefly luciferase expression levels, stability and activity did not influence the final luminescence. Bioluminescence also reflected the lowered activity of the electron transport chain achieved with RNA interference (RNAi of genes encoding respiratory chain components. Conclusion Results indicated that C. elegans luminescence reports on ATP levels in real-time. For the first time, we are able to directly assess the metabolism of a whole, living, multicellular organism by determination of the relative ATP levels. This will enable genetic analysis based on a readily quantifiable metabolic phenotype and will provide novel insights into mechanisms of fitness and disease that are likely to be of relevance for other organisms, as well as the worm.

  17. Effects of film mulch and soil pesticides on nematodes, weeds, and yields of vegetable crops. (United States)

    Johnson, A W; Jaworski, C A; Glaze, N C; Sumner, D R; Chalfant, R B


    Field plots in Tifton loamy sand were treated with various soil pesticides in 1973 and 1974 and either left exposed or covered with biodegradable flint mulch. Test crops were cantaloup, slicing and pickling cucumber, squash, and sweet corn. Overhead sprinkler irrigation was used in 1973, and trickle irrigation under the film mulch was used on sweet corn in 1974. Soil was assayed for nematodes, and roots of plants were evaluated for damage by root-knot nematodes. Nematode populations were reduced by soil treatment with an organic phosphate or carbamate nematicide-herbicide-fungicide combination (NHF), DD-MENCS, methyl bromide-chloropicrin (MBR-CP), ethoprop, carbofuran, and sodium azide + ethoprop or carbofuran. Sodium azide, sodium azide + ethoprop or carbofuran, ethoprop, and carbofuran were less effective than DD-MENCS, MBR-CP, attd the NHF combination. The NHF combination controlled grasses and broadteaf weeds as effectively as the herbicide alone. Growth and yield were greatest when nematodes and weeds were controlled. Yields of marketable vegetables were highest from plants in plots treated with DD-MENCS with a film mulch.

  18. Surface Modification Using Photo-Crosslinkable Random Copolymers (United States)

    Bae, Joonwon; Bang, Joona; Lowenhielm, Peter; Spiessberger, Christian; Russell, Thomas P.; Hawker, Craig J.


    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.

  19. 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: [Tulane University, Department of Chemistry (United States)


    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.

  20. Involvement of superoxide and myeloperoxidase in oxygen-dependent killing of Staphylococcus aureus by neutrophils. (United States)

    Hampton, M B; Kettle, A J; Winterbourn, C C


    We have used a quantitative assay that measures independent rate constants for phagocytosis and killing of Staphylococcus aureus to investigate the involvement of superoxide and myeloperoxidase in bacterial killing by human neutrophils. To inhibit superoxide-dependent processes, superoxide dismutase was cross-linked to immunoglobulin G and the conjugate was attached to the surface of S. aureus via protein A in its cell wall. Myeloperoxidase was inhibited with azide, and myeloperoxidase-deficient neutrophils were used. Adding the NADPH oxidase inhibitor diphenyleneiodonium, to prevent superoxide production, decreased the killing rate to 25%, indicating that oxidative killing mechanisms predominate in this system. The rate constant for killing of S. aureus with superoxide dismutase attached was 70% of that for control bacteria linked to inactivated enzyme. Superoxide dismutase had no effect in the presence of diphenyleneiodonium. The rate of killing was decreased to 33% in the presence of azide and to 40% with myeloperoxidase-deficient neutrophils. Superoxide dismutase had no effect in the presence of azide. On the assumption that the oxidative and nonoxidative components of killing can be considered separately, the oxidative rate was decreased by almost half by superoxide dismutase and was about six times lower when myeloperoxidase was inactive. We conclude that myeloperoxidase-dependent processes are strongly favored by human neutrophils as their prime mechanism of oxidative killing of S. aureus and that superoxide makes a direct contribution to killing. Our results also suggest that superoxide acts in conjunction with a myeloperoxidase-dependent pathway.

  1. Orthogonal spin labeling using click chemistry for in vitro and in vivo applications (United States)

    Kucher, Svetlana; Korneev, Sergei; Tyagi, Swati; Apfelbaum, Ronja; Grohmann, Dina; Lemke, Edward A.; Klare, Johann P.; Steinhoff, Heinz-Jürgen; Klose, Daniel


    Site-directed spin labeling for EPR- and NMR spectroscopy has mainly been achieved exploiting the specific reactivity of cysteines. For proteins with native cysteines or for in vivo applications, an alternative coupling strategy is required. In these cases click chemistry offers major benefits by providing a fast and highly selective, biocompatible reaction between azide and alkyne groups. Here, we establish click chemistry as a tool to target unnatural amino acids in vitro and in vivo using azide- and alkyne-functionalized spin labels. The approach is compatible with a variety of labels including reduction-sensitive nitroxides. Comparing spin labeling efficiencies from the copper-free with the strongly reducing copper(I)-catalyzed azide-alkyne click reaction, we find that the faster kinetics for the catalyzed reaction outrun reduction of the labile nitroxide spin labels and allow quantitative labeling yields within short reaction times. Inter-spin distance measurements demonstrate that the novel side chain is suitable for paramagnetic NMR- or EPR-based conformational studies of macromolecular complexes.

  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. (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


    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. In vitro antioxidant capacity of tea of Echinodorus grandiforus, “leather hat,” in Wistar rat liver

    Directory of Open Access Journals (Sweden)



    Full Text Available Oxidative stress has been considered as one of the factors responsible for hepatic diseases, which sometimes require new ways of treatment. The present study aimed to evaluate the in vitro antioxidant capacity of the tea of Echinodorus grandiforus (“leather hat” plant in rat liver. Different preparations of tea were evaluated for phenolic composition, antioxidant activity by DPPH assay and ability to inhibit lipid peroxidation induced by copper sulfate. The antioxidant activity was assessed in liver tissue treated with sodium azide in the presence or absence of tea by assays for lipid peroxidation (TBARS, protein oxidation (carbonyl and the antioxidant enzymes catalase (CAT and superoxide dismutase (SOD. The results show that different preparations of tea are important sources of polyphenols and contain theobromine, catechin and vitexin. Furthermore, the results indicate that this tea exhibits an antioxidant activity by its ability to scavenge DPPH radical. Different preparations of tea prevented damage to lipids and proteins induced by sodium azide, as well as assisting in restoring CAT and SOD activities. Thus, it can be seen that E. grandiforus tea had antioxidant activity in serum and liver being able to prevent oxidative damages generated by sodium azide.

  4. {μ-2-[(3-Amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1:2κ(5)O(1),O(6):N,N',O(1)}{2-[(3-amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1κ(3)N,N',O(1)}-μ-azido-1:2κ(2)N:N-azido-2κN-methanol-2κO-dinickel(II). (United States)

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


    Two distinct coordination geometries are found in the binuclear title complex, [Ni(2)(C(13)H(19)N(2)O(2))(2)(N(3))(2)(CH(3)OH)], as one Schiff base ligand is penta-dentate, coordinating via the anti-cipated oxide O, imine N and amine N atoms (as for the second, tridentate, ligand) but the oxide O is bridging and coordination also occurs through the meth-oxy O atom. The Ni(II) atoms are linked by a μ(2)-oxide atom and one end of a μ(2)-azide ligand, forming an Ni(2)ON core. The coordination geometry for the Ni(II) atom coordinated by the tridentate ligand is completed by the meth-oxy O atom derived from the penta-dentate ligand, with the resulting N(3)O(3) donor set defining a fac octa-hedron. The second Ni(II) atom has its cis-octa-hedral N(4)O(2) coordination geometry completed by the imine N and amine N atoms of the penta-dentate Schiff base ligand, a terminally coordinated azide N and a methanol O atom. The arrangement is stabilized by an intra-molecular hydrogen bond between the methanol H and the oxide O atom. Linear supra-molecular chains along the a axis are formed in the crystal packing whereby two amine H atoms from different amine atoms hydrogen bond to the terminal N atom of the monodentate azide ligand.

  5. 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


    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...

  6. Biodegradabilite et proprietes energetiques d'elastomeres azotures (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

  7. I. Synthesis, characterization, and base catalysis of novel zeolite supported super-basic materials II. Oxidative dehydrogenation of ethane over reduced heteropolyanion catalysts (United States)

    Galownia, Jonathan M.

    This thesis is composed of two separate and unrelated projects. The first part of this thesis outlines an investigation into the synthesis and characterization of a novel zeolite supported super-base capable of carbon-carbon olefin addition to alkyl aromatics. A zeolite supported basic material capable of such reactions would benefit many fine chemical syntheses, as well as vastly improve the economics associated with production of the high performance thermoplastic polyester polyethylene naphthalate. The thermal decomposition of alkali---metal azides impregnated in zeolite X is investigated as a novel route to the synthesis of a zeolite supported super-base. Impregnation of the alkali---metal azide precursor is shown to result in azide species occluded within the pores of the zeolite support by using high speed, solid-state 23Na MAS and 2D MQMAS NMR, FTIR, and TGA characterization methods. Addition of alkali---metal azides to the zeolite results in redistribution of the extra-lattice cations in the zeolite framework. Thermal decomposition of impregnated azide species produces further cation redistribution, but no neutral metallic clusters are detected by high speed, solid-state 23Na MAS NMR following thermal activation of the materials. Instead, it is possible that inactive ionic clusters are formed. The thermally activated materials do not promote base catalysis for the isomerization of 1-butene, the ethylation of toluene and o-xylene, and the alkenylation of o-xylene with 1,3-butadiene to produce 5-ortho-tolyl-pent-2-ene (5-OTP). The lack of catalytic activity in the materials is attributed to failure of the materials to form neutral metallic clusters during thermal treatment, possibly due to preferential formation of NMR silent ionic clusters. The formation of neutral metallic clusters is found to be insensitive to synthesis technique and activation procedure. It is concluded that the impregnation of alkali---metal azides in zeolite X does not provide a


    Institute of Scientific and Technical Information of China (English)

    Kan Yue; Jinlin He; Chang Liu; Mingjun Huang; Xue-Hui Dong; Kai Guo; Peihong Ni


    "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.

  9. Synthesis, QSAR and anticandidal evaluation of 1,2,3-triazoles derived from naturally bioactive scaffolds. (United States)

    Irfan, Mohammad; Aneja, Babita; Yadava, Umesh; Khan, Shabana I; Manzoor, Nikhat; Daniliuc, Constantin G; Abid, Mohammad


    In the present study, we used eight natural precursors (1a-h) with most of them having promising antimicrobial activities and synthesised their novel 1,2,3-triazole derivatives (3a-h). In the reaction sequences, the precursor compounds (1a-h) were converted to their respective alkyne (2a-h) followed by addition of benzyl azide freshly prepared by the reaction of benzyl bromide with sodium azide using [3 + 2] azide-alkyne cycloaddition strategy. Structural elucidation of all the triazole derivatives was done using FT-IR, (1)H, (13)C NMR, mass and elemental analysis techniques. The single crystal X-ray diffraction for 3d was also recorded. The result of in vitro anticandidal activity performed against three different strains of Candida showed that compound 3e was found superior/comparable to fluconazole (FLC) with IC50 values of 0.044 μg/mL against Candida albicans (ATCC 90028), 12.022 μg/mL against Candida glabrata (ATCC 90030), and 3.60 μg/mL against Candida tropicalis (ATCC 750). Moreover, at their IC50 values, compounds 3e and 3h showed <5% hemolysis which indicates the non-toxic behaviour of these inhibitors. Cytotoxicity assay was also performed on VERO cell line and all the derivatives were found non-toxic up to the concentration of 10.0 μg/mL. The in silico technique of 3D-QSAR was applied to establish structure activity relationship of the synthesized compounds. The results reveal the molecular fragments that play an essential role in improving the anticandidal activity.

  10. A comparison of conventional and click labeling approaches to the synthesis of F-18 labeled glucopyranosyl triazole

    Energy Technology Data Exchange (ETDEWEB)

    Kim, D. H.; Choi, Y. S.; Lee, K. H.; Choi, J. Y.; Choi, Y.; Kim, B. T. [Samsung Medical Center, Seoul (Korea, Republic of)


    Radiolabeled glucose analogs are attractive targets for in vivo imaging of glucose metabolism. In the present study, F-18 labeled glucopyranosyl triazole was synthesized using conventional and click labeling approaches, and their results were compared in terms of radiochemical yield, specific activity, and synthesis time. 4-[(2-Fluoroethyl)-1-(-D-glucopyranosyl)]-1H-1, 2, 3-triazole (1) was synthesized by the Cu(I)-catalyzed 1, 3-cycloaddition of tetraacetyl glucopyranosyl azide and 3-butyn-1-ol, hydroxy group fluorination, tetraacetyl group deprotection, and subsequent neutralization. [F-18]1 was synthesized using two conventional radiofluorination of tetraacetyl triazole tosylate precursor, followed by tetraacetyl group deprotection and Cu(I)-catalyzed 1, 3-cycloaddition of F-18 labeled butyne and glucopyranosyl azide. The radiotracer was purified by reverse phase HPLC and co-injected with 1 into a HPLC system to confirm its identity. Non-radiolabeled standard 1 was synthesized in overall 33% yield. In the synthesis of [F-18]1, the click labeling approach was superior to the conventional approach, due to a higher decay-corrected radiochemical yield (30% vs. 21%), higher specific activity (59.9 GBq/mol vs. 23.5 GBq/mol), and shorter synthesis time (75-80 min vs. 95-100 min). In addition, protection of the hydroxy groups of glucopyranosyl azide was not required in the former method. The radiotracer was identified by co-elution with 1 on HPLC. These results demonstrate that click labeling approach is a rapid and efficient method which does not require the protection of functional groups, and that it can readily be applied to the preparation of other radiotracers.

  11. Controlling noncovalent interactions between a lysine-rich α-helical peptide and self-assembled monolayers of alkanethiols on Au through functional group diversity (United States)

    Raigoza, Annette F.; Onyirioha, Kristeen; Webb, Lauren J.


    Reliably attaching a structured biomolecule to an inorganic substrate would enable the preparation of surfaces that incorporate both biological and inorganic functions and structures. To this end, we have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to well-ordered alkanethiol self-assembled monolayers (SAM) on a Au(111) surface, in which the SAM is composed of a mixture of methyl and azide termination. Proteins, however, are composed of many diverse functional groups, and this composition directly effects protein structure, interactions, and reactivity. Here, we explore the utility of mixed SAMs with alternative terminating functional groups to tune and direct the reactivity of the surface through noncovalent peptide-surface interactions. We study both polar surfaces (OH-terminated) and charged surfaces (COOH- and NH3-terminated, which are negatively and positively charged, respectively, under our reaction conditions). Surfaces were functionalized with a bipolar peptide composed of Lys and Leu residues that could express different interactions through either hydrophilic and/or charge (Lys) or hydrophobic (Leu) influences. X-ray photoelectron spectroscopy (XPS) and surface infrared spectroscopy were used to characterize surfaces at all stages of the peptide functionalization procedure. This strategy resulted in a high density of surface-bound α-helices without aggregation. Mixed SAMs that included a positively charged alkanethiol along with the azide-terminated thiol resulted in a more efficient reaction and better alignment of the peptide with the azide on the surface. Negatively charged surfaces increased physisorption of the peptide, which was then removed during sample rinsing. This work demonstrates that varying easily controlled chemical inputs during the functionalization steps allows the reaction conditions to be balanced for the chemical needs of a

  12. Layer-by-layer assembly of graphene oxide on polypropylene macroporous membranes via click chemistry to improve antibacterial and antifouling performance

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhen-Bei, E-mail: [The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecular-Based Materials, College of Chemistry and Materials Science, Anhui Normal University, East Beijing Rd. 1, Wuhu, Anhui 241000 (China); Wu, Jing-Jing, E-mail: [The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecular-Based Materials, College of Chemistry and Materials Science, Anhui Normal University, East Beijing Rd. 1, Wuhu, Anhui 241000 (China); Su, Yu, E-mail: [The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecular-Based Materials, College of Chemistry and Materials Science, Anhui Normal University, East Beijing Rd. 1, Wuhu, Anhui 241000 (China); Zhou, Jin, E-mail: [Department of Materials and Chemical Engineering, Chizhou University, Muzhi Rd. 199, Chizhou, Anhui 247000 (China); Gao, Yong, E-mail: [School of Chemistry and Environmental Engineering, Jiangsu University of Technology, Changzhou 213001 (China); Yu, Hai-Yin, E-mail: [The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecular-Based Materials, College of Chemistry and Materials Science, Anhui Normal University, East Beijing Rd. 1, Wuhu, Anhui 241000 (China); Gu, Jia-Shan, E-mail: [The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecular-Based Materials, College of Chemistry and Materials Science, Anhui Normal University, East Beijing Rd. 1, Wuhu, Anhui 241000 (China)


    Graphical abstract: - Highlights: • Clickable membrane prepared by photo bromination and S{sub N}2 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.

  13. The fermentation of lignocellulose hydrolysates with xylose isomerases and yeasts

    Energy Technology Data Exchange (ETDEWEB)

    Linden, T.


    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

  14. The fermentation of lignocellulose hydrolysates with xylose isomerases and yeasts

    Energy Technology Data Exchange (ETDEWEB)

    Linden, T.


    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.

  15. In-frame amber stop codon replacement mutagenesis for the directed evolution of proteins containing non-canonical amino acids: identification of residues open to bio-orthogonal modification.

    Directory of Open Access Journals (Sweden)

    James A J Arpino

    Full Text Available Expanded genetic code approaches are a powerful means to add new and useful chemistry to proteins at defined residues positions. One such use is the introduction of non-biological reactive chemical handles for site-specific biocompatible orthogonal conjugation of proteins. Due to our currently limited information on the impact of non-canonical amino acids (nAAs on the protein structure-function relationship, rational protein engineering is a "hit and miss" approach to selecting suitable sites. Furthermore, dogma suggests surface exposed native residues should be the primary focus for introducing new conjugation chemistry. Here we describe a directed evolution approach to introduce and select for in-frame codon replacement to facilitate engineering proteins with nAAs. To demonstrate the approach, the commonly reprogrammed amber stop codon (TAG was randomly introduced in-frame in two different proteins: the bionanotechnologically important cyt b(562 and therapeutic protein KGF. The target protein is linked at the gene level to sfGFP via a TEV protease site. In absence of a nAA, an in-frame TAG will terminate translation resulting in a non-fluorescent cell phenotype. In the presence of a nAA, TAG will encode for nAA incorporation so instilling a green fluorescence phenotype on E. coli. The presence of endogenously expressed TEV proteases separates in vivo target protein from its fusion to sfGFP if expressed as a soluble fusion product. Using this approach, we incorporated an azide reactive handle and identified residue positions amenable to conjugation with a fluorescence dye via strain-promoted azide-alkyne cycloaddition (SPAAC. Interestingly, best positions for efficient conjugation via SPAAC were residues whose native side chain were buried through analysis of their determined 3D structures and thus may not have been chosen through rational protein engineering. Molecular modeling suggests these buried native residues could become partially

  16. 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


    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.

  17. Proton conducting sulphonated fluorinated poly(styrene) crosslinked electrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Soules, A.; Ameduri, B.; Boutevin, B.; David, G. [Institut Charles Gerhardt UMR CNRS 5253 Equipe, Ingenierie et Architectures Macromoleculaires,' ' Ecole Nationale Superieure de Chimie de Montpellier, 8 rue de l' Ecole Normale, 34296 Montpellier, Cedex 05 (France); Perrin, R. [CEA Le Ripault Departement des Materiaux, DMAT/SCMF/LSTP, BP16 - 37260 Monts (France); Gebel, G. [Structure et Proprietes des Architectures Moleculaires UMR 5819 (CEA-CNRS-UJF), INAC, SPrAM, CEA Grenoble, 17 Rue des Martyrs, 38054 Grenoble, Cedex 9 (France)


    Potential membranes for polymer electrolyte membrane fuel cell based on crosslinked sulphonated fluorinated polystyrenes (PS) were synthesised in two steps. First, azide-telechelic polystyrene was obtained by iodine transfer polymerisation of styrene in the presence of 1,6-diiodoperfluorohexane followed by azido chain-end functionalisation. Then azide-telechelic polystyrene was efficiently crosslinked with 1,10-diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane under UV irradiation. After 45 min only, almost completion of azide crosslinking could be achieved, resulting in crosslinked membranes with insoluble fractions higher than 95%. The sulphonation of the crosslinked membranes afforded ionic exchange capacities (IECs) ranging from 2.2 to 3.2 meq g{sup -1}. The hydration number was shown to be very high (from 30 to 75), depending on both the content of perfluorodecane and of sulphonic acid groups. The morphology of the membranes, assessed by small-angle X-ray scattering, was found to be a lamellar-type structure with two types of ionic domains. For the membrane that exhibited an IEC value of 2.2 meq.g{sup -1}, proton conductivity was in the same range as that of Nafion {sup registered} (120-135{sup -1}), whereas the membrane IEC value of 3.2 meq.g{sup -1} showed a proton conductivity higher than that of Nafion {sup registered} in liquid water from 25 to 80 C, though a high water uptake. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Facile chemical functionalization of proteins through intein-linked yeast display. (United States)

    Marshall, Carrie J; Agarwal, Nitin; Kalia, Jeet; Grosskopf, Vanessa A; McGrath, Nicholas A; Abbott, Nicholas L; Raines, Ronald T; Shusta, Eric V


    Intein-mediated expressed protein ligation (EPL) permits the site-specific chemical customization of proteins. While traditional techniques have used purified, soluble proteins, we have extended these methods to release and modify intein fusion proteins expressed on the yeast surface, thereby eliminating the need for soluble protein expression and purification. To this end, we sought to simultaneously release yeast surface-displayed proteins and selectively conjugate with chemical functionalities compatible with EPL and click chemistry. Single-chain antibodies (scFv) and green fluorescent protein (GFP) were displayed on the yeast surface as fusions to the N-terminus of the Mxe GyrA intein. ScFv and GFP were released from the yeast surface with either a sulfur nucleophile (MESNA) or a nitrogen nucleophile (hydrazine) linked to an azido group. The hydrazine azide permitted the simultaneous release and azido functionalization of displayed proteins, but nonspecific reactions with other yeast proteins were detected, and cleavage efficiency was limited. In contrast, MESNA released significantly more protein from the yeast surface while also generating a unique thioester at the carboxy-terminus of the released protein. These protein thioesters were subsequently reacted with a cysteine alkyne in an EPL reaction and then employed in an azide-alkyne cycloaddition to immobilize the scFv and GFP on an azide-decorated surface with >90% site-specificity. Importantly, the immobilized proteins retained their activity. Since yeast surface display is also a protein engineering platform, these approaches provide a particularly powerful tool for the rapid assessment of engineered proteins.

  19. Synthesis of heteroglycoclusters by using orthogonal chemoselective ligations

    Directory of Open Access Journals (Sweden)

    Baptiste Thomas


    Full Text Available Synthetic heteroglycoclusters are being subjected to increasing interest due to their potential to serve as selective ligands for carbohydrate-binding proteins. In this paper, we describe an expedient strategy to prepare cyclopeptides displaying well-defined distributions and combinations of carbohydrates. By using both oxime ligation and copper(I-catalyzed alkyne–azide cycloaddition, two series of compounds bearing binary combinations of αMan, αFuc or βLac in an overall tetravalent presentation, and either 2:2 or 3:1 relative proportions, have been prepared.

  20. A generic strategy for co-presentation of heparin-binding growth factors based on CVD polymerization. (United States)

    Deng, Xiaopei; Lahann, Joerg


    A multifunctional copolymer with both aldehyde and alkyne groups is synthesized by chemical vapor deposition (CVD) for orthogonal co-immobilization of biomolecules. Surface analytical methods including FTIR and XPS are used to confirm the surface modification. Heparin-binding growth factors [basic fibroblast growth factor (bFGF) in this study] can be immobilized through interaction with heparin, which was covalently attached to the CVD surface through an aldehyde-hydrazide reaction. In parallel, an alkyne-azide reaction is used to orthogonally co-immobilize an adhesion peptide as the second biomolecule.