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Sample records for liquid azide salts

  1. Synthesis of radiolabelled aryl azides from diazonium salts: experimental and computational results permit the identification of the preferred mechanism.

    Science.gov (United States)

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

    2015-05-28

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

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

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    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. Reaction-based azide gas sensing with tailored ionic liquids measured by quartz crystal microbalance.

    Science.gov (United States)

    Tseng, Ming-Chung; Chu, Yen-Ho

    2014-02-18

    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.

  4. Copper catalysed azide-alkyne cycloaddition (CuAAC) in liquid ammonia.

    Science.gov (United States)

    Ji, Pengju; Atherton, John H; Page, Michael I

    2012-10-21

    Copper(I) catalysed azide-alkyne cycloaddition reactions (CuAAC) occur smoothly in liquid ammonia (LNH(3)) at room temperature to give exclusively 1,4-substituted 1,2,3-triazoles with excellent yields (up to 99%). The CuAAC reactions in liquid ammonia require relatively small amounts of copper(I) catalyst (0.5 mole%) compared with that in conventional solvents. The product can be obtained conveniently by simply evaporation of ammonia, indicating its potential application in industry. The rate of the CuAAC reaction in liquid ammonia shows a second order dependence on the copper(I) concentration and the reaction occurs only with terminal alkynes. Deuterium exchange experiments with phenyl acetylene-d(1) show that the acidity of the alkyne is increased at least 1000-fold with catalytic amounts of copper(I) in liquid ammonia. The mechanism of the CuAAC reaction in liquid ammonia is discussed.

  5. Ionic liquids/[bmim][N3] mixtures: promising media for the synthesis of aryl azides by SNAr.

    Science.gov (United States)

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

    2008-08-15

    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.

  6. Ionic Liquids: Just Molten Salts After All?

    Directory of Open Access Journals (Sweden)

    Anna K. Croft

    2009-07-01

    Full Text Available While there has been much effort in recent years to characterise ionic liquids in terms of parameters that are well described for molecular solvents, using these to explain reaction outcomes remains problematic. Herein we propose that many reaction outcomes in ionic liquids may be explained by considering the electrostatic interactions present in the solution; that is, by recognising that ionic liquids are salts. This is supported by evidence in the literature, along with studies presented here.

  7. Liquid salt environment stress-rupture testing

    Science.gov (United States)

    Ren, Weiju; Holcomb, David E.; Muralidharan, Govindarajan; Wilson, Dane F.

    2016-03-22

    Disclosed herein are systems, devices and methods for stress-rupture testing selected materials within a high-temperature liquid salt environment. Exemplary testing systems include a load train for holding a test specimen within a heated inert gas vessel. A thermal break included in the load train can thermally insulate a load cell positioned along the load train within the inert gas vessel. The test specimen can include a cylindrical gage portion having an internal void filled with a molten salt during stress-rupture testing. The gage portion can have an inner surface area to volume ratio of greater than 20 to maximize the corrosive effect of the molten salt on the specimen material during testing. Also disclosed are methods of making a salt ingot for placement within the test specimen.

  8. A perspective on liquid salts for energy and materials.

    Science.gov (United States)

    Irvine, J T S

    2016-08-15

    Liquid salts comprising molten salts and ionic liquids offer important media to address both energy and materials challenges. Here we review topics presented in this Faraday Discussion volume related to improved electrowinning of metals, optimisation of processes, new electrochemical device concepts, chemistry in ionic liquids, conversion of biomass, carbon chemistry and nuclear applications. The underlying phenomenology is then reviewed and commentary given. Some future applications are then discussed, further exemplifying the high potential rewards achievable from these chemistries.

  9. 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)

    2004-01-01

    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.

  10. Liquid Fluoride Salt Experimentation Using a Small Natural Circulation Cell

    Energy Technology Data Exchange (ETDEWEB)

    Yoder Jr, Graydon L [ORNL; Heatherly, Dennis Wayne [ORNL; Williams, David F [ORNL; Elkassabgi, Yousri M. [Texas A& M University, Kingsville; Caja, Joseph [Electrochemical Systems, Inc.; Caja, Mario [ORNL; Jordan, John [Texas A& M University, Kingsville; Salinas, Roberto [Texas A& M University, Kingsville

    2014-04-01

    A small molten fluoride salt experiment has been constructed and tested to develop experimental techniques for application in liquid fluoride salt systems. There were five major objectives in developing this test apparatus: Allow visual observation of the salt during testing (how can lighting be introduced, how can pictures be taken, what can be seen) Determine if IR photography can be used to examine components submerged in the salt Determine if the experimental configuration provides salt velocity sufficient for collection of corrosion data for future experimentation Determine if a laser Doppler velocimeter can be used to quantify salt velocities. Acquire natural circulation heat transfer data in fluoride salt at temperatures up to 700oC All of these objectives were successfully achieved during testing with the exception of the fourth: acquiring velocity data using the laser Doppler velocimeter. This paper describes the experiment and experimental techniques used, and presents data taken during natural circulation testing.

  11. An Overview of Liquid Fluoride Salt Heat Transport Systems

    Energy Technology Data Exchange (ETDEWEB)

    Holcomb, David Eugene [ORNL; Cetiner, Sacit M [ORNL

    2010-09-01

    Heat transport is central to all thermal-based forms of electricity generation. The ever increasing demand for higher thermal efficiency necessitates power generation cycles transitioning to progressively higher temperatures. Similarly, the desire to provide direct thermal coupling between heat sources and higher temperature chemical processes provides the underlying incentive to move toward higher temperature heat transfer loops. As the system temperature rises, the available materials and technology choices become progressively more limited. Superficially, fluoride salts at {approx}700 C resemble water at room temperature being optically transparent and having similar heat capacity, roughly three times the viscosity, and about twice the density. Fluoride salts are a leading candidate heat-transport material at high temperatures. Fluoride salts have been extensively used in specialized industrial processes for decades, yet they have not entered widespread deployment for general heat transport purposes. This report does not provide an exhaustive screening of potential heat transfer media and other high temperature liquids such as alkali metal carbonate eutectics or chloride salts may have economic or technological advantages. A particular advantage of fluoride salts is that the technology for their use is relatively mature as they were extensively studied during the 1940s-1970s as part of the U.S. Atomic Energy Commission's program to develop molten salt reactors (MSRs). However, the instrumentation, components, and practices for use of fluoride salts are not yet developed sufficiently for commercial implementation. This report provides an overview of the current understanding of the technologies involved in liquid salt heat transport (LSHT) along with providing references to the more detailed primary information resources. Much of the information presented here derives from the earlier MSR program. However, technology has evolved over the intervening years

  12. An Overview of Liquid Fluoride Salt Heat Transport Systems

    Energy Technology Data Exchange (ETDEWEB)

    Holcomb, David Eugene [ORNL; Cetiner, Sacit M [ORNL

    2010-09-01

    Heat transport is central to all thermal-based forms of electricity generation. The ever increasing demand for higher thermal efficiency necessitates power generation cycles transitioning to progressively higher temperatures. Similarly, the desire to provide direct thermal coupling between heat sources and higher temperature chemical processes provides the underlying incentive to move toward higher temperature heat transfer loops. As the system temperature rises, the available materials and technology choices become progressively more limited. Superficially, fluoride salts at {approx}700 C resemble water at room temperature being optically transparent and having similar heat capacity, roughly three times the viscosity, and about twice the density. Fluoride salts are a leading candidate heat-transport material at high temperatures. Fluoride salts have been extensively used in specialized industrial processes for decades, yet they have not entered widespread deployment for general heat transport purposes. This report does not provide an exhaustive screening of potential heat transfer media and other high temperature liquids such as alkali metal carbonate eutectics or chloride salts may have economic or technological advantages. A particular advantage of fluoride salts is that the technology for their use is relatively mature as they were extensively studied during the 1940s-1970s as part of the U.S. Atomic Energy Commission's program to develop molten salt reactors (MSRs). However, the instrumentation, components, and practices for use of fluoride salts are not yet developed sufficiently for commercial implementation. This report provides an overview of the current understanding of the technologies involved in liquid salt heat transport (LSHT) along with providing references to the more detailed primary information resources. Much of the information presented here derives from the earlier MSR program. However, technology has evolved over the intervening years

  13. Liquid Salt Heat Exchanger Technology for VHTR Based Applications

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Mark; Sridhara, Kumar; Allen, Todd; Peterson, Per

    2012-10-11

    The objective of this research is to evaluate performance of liquid salt fluids for use as a heat carrier for transferring high-temperature process heat from the very high-temperature reactor (VHTR) to chemical process plants. Currently, helium is being considered as the heat transfer fluid; however, the tube size requirements and the power associated with pumping helium may not be economical. Recent work on liquid salts has shown tremendous potential to transport high-temperature heat efficiently at low pressures over long distances. This project has two broad objectives: To investigate the compatibility of Incoloy 617 and coated and uncoated SiC ceramic composite with MgCl2-KCl molten salt to determine component lifetimes and aid in the design of heat exchangers and piping; and, To conduct the necessary research on the development of metallic and ceramic heat exchangers, which are needed for both the helium-to-salt side and salt-to-process side, with the goal of making these heat exchangers technologically viable. The research will consist of three separate tasks. The first task deals with material compatibility issues with liquid salt and the development of techniques for on-line measurement of corrosion products, which can be used to measure material loss in heat exchangers. Researchers will examine static corrosion of candidate materials in specific high-temperature heat transfer salt systems and develop an in situ electrochemical probe to measure metallic species concentrations dissolved in the liquid salt. The second task deals with the design of both the intermediate and process side heat exchanger systems. Researchers will optimize heat exchanger design and study issues related to corrosion, fabrication, and thermal stresses using commercial and in-house codes. The third task focuses integral testing of flowing liquid salts in a heat transfer/materials loop to determine potential issues of using the salts and to capture realistic behavior of the salts in a

  14. Lithium conducting ionic liquids based on lithium borate salts

    Energy Technology Data Exchange (ETDEWEB)

    Zygadlo-Monikowska, E.; Florjanczyk, Z.; Sluzewska, K.; Ostrowska, J.; Langwald, N.; Tomaszewska, A. [Warsaw University of Technology, Faculty of Chemistry, ul. Noakowskiego 3, 00-664 Warsaw (Poland)

    2010-09-15

    The simple reaction of trialkoxyborates with butyllithium resulted in the obtaining of new lithium borate salts: Li{l_brace}[CH{sub 3}(OCH{sub 2}CH{sub 2}){sub n}O]{sub 3}BC{sub 4}H{sub 9}{r_brace}, containing oxyethylene substituents (EO) of n=1, 2, 3 and 7. Salts of n {>=} 2 show properties of room temperature ionic liquid (RTIL) of low glass transition temperature, T{sub g} of the order from -70 to -80 C. The ionic conductivity of the salts depends on the number of EO units, the highest conductivity is shown by the salt with n = 3; in bulk its ambient temperature conductivity is 2 x 10{sup -5} S cm{sup -1} and in solution in cyclic propylene sulfite or EC/PC mixture, conductivity increases by an order of magnitude. Solid polymer electrolytes with borate salts over a wide concentration range, from 10 to 90 mol.% were obtained and characterized. Three types of polymeric matrices: poly(ethylene oxide) (PEO), poly(trimethylene carbonate) (PTMC) and two copolymers of acrylonitrile and butyl acrylate p(AN-BuA) were used in them as polymer matrices. It has been found that for systems of low salt concentration (10 mol.%) the best conducting properties were shown by solid polymer electrolytes with PEO, whereas for systems of high salt concentration, of the polymer-in-salt type, good results were achieved for PTMC as polymer matrix. (author)

  15. Renewing Liquid Fueled Molten Salt Reactor Research and Development

    Science.gov (United States)

    Towell, Rusty; NEXT Lab Team

    2016-09-01

    Globally there is a desperate need for affordable, safe, and clean energy on demand. More than anything else, this would raise the living conditions of those in poverty around the world. An advanced reactor that utilizes liquid fuel and molten salts is capable of meeting these needs. Although, this technology was demonstrated in the Molten Salt Reactor Experiment (MSRE) at ORNL in the 60's, little progress has been made since the program was cancelled over 40 years ago. A new research effort has been initiated to advance the technical readiness level of key reactor components. This presentation will explain the motivation and initial steps for this new research initiative.

  16. Membrane Treatment of Liquid Salt Bearing Radioactive Wastes

    Energy Technology Data Exchange (ETDEWEB)

    Dmitriev, S. A.; Adamovich, D. V.; Demkin, V. I.; Timofeev, E. M.

    2003-02-25

    The main fields of introduction and application of membrane methods for preliminary treatment and processing salt liquid radioactive waste (SLRW) can be nuclear power stations (NPP) and enterprises on atomic submarines (AS) utilization. Unlike the earlier developed technology for the liquid salt bearing radioactive waste decontamination and concentrating this report presents the new enhanced membrane technology for the liquid salt bearing radioactive waste processing based on the state-of-the-art membrane unit design, namely, the filtering units equipped with the metal-ceramic membranes of ''TruMem'' brand, as well as the electrodialysis and electroosmosis concentrators. Application of the above mentioned units in conjunction with the pulse pole changer will allow the marked increase of the radioactive waste concentrating factor and the significant reduction of the waste volume intended for conversion into monolith and disposal. Besides, the application of the electrodialysis units loaded with an ion exchange material at the end polishing stage of the radioactive waste decontamination process will allow the reagent-free radioactive waste treatment that meets the standards set for the release of the decontaminated liquid radioactive waste effluents into the natural reservoirs of fish-farming value.

  17. Functionalization of glassy carbon with diazonium salts in ionic liquids.

    Science.gov (United States)

    Actis, Paolo; Caulliez, Guilain; Shul, Galyna; Opallo, Marcin; Mermoux, Michel; Marcus, Bernadette; Boukherroub, Rabah; Szunerits, Sabine

    2008-06-17

    The paper reports on the chemical functionalization of glassy carbon electrodes with 4-bromobenzene (4-BBDT) and 4-(4'-nitrophenylazo)benzene diazonium tetrafluoroborate (4-NAB) salts in ionic liquids. The reaction was carried out at room temperature in air without any external electrical bias in either hydrophobic (1-butyl-3-methylimidazolium hexafluorophosphate) or hydrophilic (1-butyl-3-methylimidazolium methyl sulfate) ionic liquids. The resulting surfaces were characterized using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and electrochemical measurements. Electrochemical reduction of the terminal nitro groups allowed the determination of surface coverage and formation of an amine-terminated carbon surfaces. The results were compared to glassy carbon chemically modified in an aqueous solution in the presence of 1% sodium dodecyl sulfate (SDS) with the same diazonium salt. Furthermore, Raman spectroscopy coupled with electrochemical measurements allowed to distinguish between the reduction of -NO2 to -NH2 group and the -N=N- to -NH-NH- bond.

  18. Li(+) solvation in glyme-Li salt solvate ionic liquids.

    Science.gov (United States)

    Ueno, Kazuhide; Tatara, Ryoichi; Tsuzuki, Seiji; Saito, Soshi; Doi, Hiroyuki; Yoshida, Kazuki; Mandai, Toshihiko; Matsugami, Masaru; Umebayashi, Yasuhiro; Dokko, Kaoru; Watanabe, Masayoshi

    2015-03-28

    Certain molten complexes of Li salts and solvents can be regarded as ionic liquids. In this study, the local structure of Li(+) ions in equimolar mixtures ([Li(glyme)]X) of glymes (G3: triglyme and G4: tetraglyme) and Li salts (LiX: lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]), lithium bis(pentafluoroethanesulfonyl)amide (Li[BETI]), lithium trifluoromethanesulfonate (Li[OTf]), LiBF4, LiClO4, LiNO3, and lithium trifluoroacetate (Li[TFA])) was investigated to discriminate between solvate ionic liquids and concentrated solutions. Raman spectra and ab initio molecular orbital calculations have shown that the glyme molecules adopt a crown-ether like conformation to form a monomeric [Li(glyme)](+) in the molten state. Further, Raman spectroscopic analysis allowed us to estimate the fraction of the free glyme in [Li(glyme)]X. The amount of free glyme was estimated to be a few percent in [Li(glyme)]X with perfluorosulfonylamide type anions, and thereby could be regarded as solvate ionic liquids. Other equimolar mixtures of [Li(glyme)]X were found to contain a considerable amount of free glyme, and they were categorized as traditional concentrated solutions. The activity of Li(+) in the glyme-Li salt mixtures was also evaluated by measuring the electrode potential of Li/Li(+) as a function of concentration, by using concentration cells against a reference electrode. At a higher concentration of Li salt, the amount of free glyme diminishes and affects the electrode reaction, leading to a drastic increase in the electrode potential. Unlike conventional electrolytes (dilute and concentrated solutions), the significantly high electrode potential found in the solvate ILs indicates that the solvation of Li(+) by the glyme forms stable and discrete solvate ions ([Li(glyme)](+)) in the molten state. This anomalous Li(+) solvation may have a great impact on the electrode reactions in Li batteries.

  19. Liquid electrolytes based on new lithium conductive imidazole salts

    Energy Technology Data Exchange (ETDEWEB)

    Niedzicki, L.; Kasprzyk, M.; Kuziak, K.; Zukowska, G.Z.; Marcinek, M.; Wieczorek, W. [Department of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland); Armand, M. [LRCS, University de Picardie Jules Verne, UMR 6007 CNRS, 33 rue de Saint-Leu, 80039 Amiens (France)

    2011-02-01

    In the present paper new generation of imidazole-derived lithium salts (LiTDI - lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide, LiPDI - lithium 4,5-dicyano-2-(pentafluoroethyl)imidazolide and LiHDI - lithium 4,5-dicyano-2-(n-heptafluoropropyl)imidazolide) applied in a model liquid electrolyte, with propylene carbonate used as a solvent, is described. Room temperature ionic conductivities measured by Impedance Spectroscopy are as high as 10{sup -2} to 10{sup -3} S cm{sup -1} for the 0.1-1 mol dm{sup -3} salt concentration range. Lithium cation transference numbers calculated using the Bruce-Vincent method exceed 0.4 at salt concentration equal to 1 mol dm{sup -3}. Interface resistance measurements showed good stability at high - 0.5 mol dm{sup -3} or low - 0.01 mol dm{sup -3} salt concentrations. Ionic associations were estimated using Fuoss-Kraus semiempirical method revealing relatively low association rates. The effect of anion structure on ionic interactions and electrochemical characteristics of the studied electrolytes is discussed. (author)

  20. Acrylate Functionalized Tetraalkylammonium Salts with Ionic Liquid Properties

    Directory of Open Access Journals (Sweden)

    Silvia Janietz

    2012-05-01

    Full Text Available Acrylate functionalized ionic liquids based on tetraalkylammonium salts with terminal acrylates- and methylacrylates were synthesized. Melting points and ionic conductivity of twenty compounds in six groups were determined. Within one group the effect of three different counterions was investigated and discussed. The groups differ in cationic structure elements because of their functional groups such as acrylate and methacrylate, alkyl residues at the nitrogen and number of quaternary ammonium atoms within the organic cation. The effect of these cationic structure elements has been examined concerning the compiled parameters with a view to qualifying them as components for solid state electrolytes. The newly synthesized ionic liquids were characterized by NMR and FTIR analysis. The exchange of halide ions like bromide as counter ions to weakly coordinating [PF6], [OTf] or [TFSI] reduces the melting points significantly and leads to an ion conductivity of about 10−4 S/cm at room temperature. In the case of the dicationic ionic liquid, an ion conductivity of about 10−3 S/cm was observed.

  1. Liquid-Liquid Extraction-Chromogenic Systems Containing Iron(III), 4-Nitrocatechol and Tetrazolium Salts

    OpenAIRE

    Galya K. Toncheva; Teodora S. Stefanova; Gavazov, Kiril B.

    2015-01-01

    Complex formation and liquid-liquid extraction were studied in systems containing iron(III), 4-nitrocatechol (4NC),tetrazolium salt (TZS), water and organic solvent. Three different TZS were used: 3-(4,5-dimethyl-2-thiazol)-2,5-diphenyl-2H-tetrazolium bromide (MTT), 3-(2-naphtyl)-2,5-diphenyl-2H-tetrazolium chloride (Tetrazolium violet, TV) and 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (INT).The cations of the first two TZSs (TZ+: MTT+ and TV+) form intensively color...

  2. Liquid-Liquid Extraction-Chromogenic Systems Containing Iron(III, 4-Nitrocatechol and Tetrazolium Salts

    Directory of Open Access Journals (Sweden)

    Galya K. Toncheva

    2015-03-01

    Full Text Available Complex formation and liquid-liquid extraction were studied in systems containing iron(III, 4-nitrocatechol (4NC,tetrazolium salt (TZS, water and organic solvent. Three different TZS were used: 3-(4,5-dimethyl-2-thiazol-2,5-diphenyl-2H-tetrazolium bromide (MTT, 3-(2-naphtyl-2,5-diphenyl-2H-tetrazolium chloride (Tetrazolium violet, TV and 2-(4-iodophenyl-3-(4-nitrophenyl-5-phenyl-2H-tetrazolium chloride (INT.The cations of the first two TZSs (TZ+: MTT+ and TV+ form intensively colored (molar absorptivity of 4.6´104 L mol–1 cm–1 and 4.4´104 L mol–1 cm–1, respectively chloroform extractable ion-associates with the FeIII-4NC anionic chelate. These ternary complexes can be represented with the following general formula: (TZ+3[FeIII(4NC3]3−.

  3. Mesocarbon microbead based graphite for spherical fuel element to inhibit the infiltration of liquid fluoride salt in molten salt reactor

    Science.gov (United States)

    Zhong, Yajuan; Zhang, Junpeng; Lin, Jun; Xu, Liujun; Zhang, Feng; Xu, Hongxia; Chen, Yu; Jiang, Haitao; Li, Ziwei; Zhu, Zhiyong; Guo, Quangui

    2017-07-01

    Mesocarbon microbeads (MCMB) and quasi-isostatic pressing method were used to prepare MCMB based graphite (MG) for spherical fuel element to inhibit the infiltration of liquid fluoride salt in molten salt reactor (MSR). Characteristics of mercury infiltration and molten salt infiltration in MG were investigated and compared with A3-3 (graphite for spherical fuel element in high temperature gas cooled reactor) to identify the infiltration behaviors. The results indicated that MG had a low porosity about 14%, and an average pore diameter of 96 nm. Fluoride salt occupation of A3-3 (average pore diameter was 760 nm) was 10 wt% under 6.5 atm, whereas salt gain did not infiltrate in MG even up to 6.5 atm. It demonstrated that MG could inhibit the infiltration of liquid fluoride salt effectively. Coefficient of thermal expansion (CTE) of MG lies in 6.01 × 10-6 K-1 (α∥) and 6.15 × 10-6 K-1 (α⊥) at the temperature range of 25-700 °C. The anisotropy factor of MG calculated by CTE maintained below 1.02, which could meet the requirement of the spherical fuel element (below 1.30). The constant isotropic property of MG is beneficial for the integrity and safety of the graphite used in the spherical fuel element for a MSR.

  4. Salting-out assisted liquid-liquid extraction coupled to dispersive liquid-liquid microextraction for the determination of chlorophenols in wine by high-performance liquid chromatography.

    Science.gov (United States)

    Fan, Yingying; Hu, Shibin; Liu, Shuhui

    2014-12-01

    A novel procedure of sample preparation combined with high-performance liquid chromatography with diode array detection is introduced for the analysis of highly chlorinated phenols (trichlorophenols, tetrachlorophenols, and pentachlorophenol) in wine. The main features of the proposed method are (i) low-toxicity diethyl carbonate as extraction solvent to selectively extract the analytes without matrix effect, (ii) the combination of salting-out assisted liquid-liquid extraction and dispersive liquid-liquid microextraction to achieve an enrichment factor of 334-361, and (iii) the extract is analyzed by high-performance liquid chromatography to avoid derivatization. Under the optimum conditions, correlation coefficients (r) were >0.997 for calibration curves in the range 1-80 ng/mL, detection limits and quantification limits ranged from 0.19 to 0.67 and 0.63 to 2.23 ng/mL, respectively, and relative standard deviation was wines, with recovery rates in the range 82-104%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement

    Science.gov (United States)

    Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.

    2016-10-01

    We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation-glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids.

  6. Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement

    Science.gov (United States)

    Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.

    2016-01-01

    We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids. PMID:27767069

  7. Study on the release of chlorhexidine base and salts from different liquid crystalline structures.

    Science.gov (United States)

    Farkas, Edit; Kiss, Dorottya; Zelkó, Romána

    2007-08-01

    The aim of this study was to investigate the influence of two types of chlorhexidine species, chlorhexidine base and its salts, on the physico-chemical features of liquid crystalline systems and on drug transport through lipophilic membranes. A non-ionic surfactant, Synperonic A7 (PEG7-C13-15) was selected for the preparation of the liquid crystalline systems. Mixtures of different ratios of Synperonic A7 and water were prepared. The liquid crystalline systems were characterized using polarizing microscopy and dynamic oscillatory test. Membrane transport was also examined. The addition of chlorhexidine species to the liquid crystalline system modified the structure of the liquid crystalline system. As a result of the changes of liquid crystalline structures, the drug release of various types of chlorhexidine could be also modified. The combination of the base and salt forms of the drug in one dosage form could eliminate the drug release changes from liquid crystalline systems of dynamically changeable structures.

  8. Salting-out effect of ionic liquids on isobaric vapor-liquid equilibrium of acetonitrile-water system☆

    Institute of Scientific and Technical Information of China (English)

    Jing Fang; Rui Zhao; Hui Wang; Chunli Li; Jing Liu

    2015-01-01

    This paper presents the vapor–liquid equilibrium (VLE) data of acetonitrile–water system containing ionic liquids (ILs) at atmospheric pressure (101.3 kPa). Since ionic liquids dissociate into anions and cations, the VLE data for the acetonitrile+water+ILs systems are correlated by salt effect models, Furter model and improved Furter model. The overall average relative deviation of Furter model and improved Furter model is 5.43%and 4.68%, respectively. Thus the salt effect models are applicable for the correlation of IL containing systems. The salting-out effect theory can be used to explain the change of relative volatility of acetonitrile–water system.

  9. Solution, thermal and optical properties of bis(pyridinium salt)s as ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Jo, Tae Soo; Koh, Jung Jae; Han, Haesook [Department of Chemistry, University of Nevada at Las Vegas, 4505 Maryland Parkway, Box 454003, Las Vegas, NV 89154 (United States); Bhowmik, Pradip K., E-mail: pradip.bhowmik@unlv.edu [Department of Chemistry, University of Nevada at Las Vegas, 4505 Maryland Parkway, Box 454003, Las Vegas, NV 89154 (United States)

    2013-05-15

    Bis(pyridinium salt)s containing different alkyl chain lengths and various organic counterions were prepared by the ring-transmutation reaction of bis(pyrylium tosylate) with aliphatic amines in dimethyl sulfoxide at 130–135 °C for 18 h and their tosylate counterions were exchanged to other anions such as triflimide, methyl orange, and dioctyl sulfosuccinate by the metathesis reaction in a common organic solvent. Their chemical structures were established by using {sup 1}H, {sup 19}F, and {sup 13}C NMR spectra. The thermal properties of bis(pyridinium salt)s were studied by DSC and TGA measurements. Some of the dicationic salts provided low melting points below 100 °C and some of them displayed amorphous properties. Polarized optical microscopy studies revealed the crystal structures prior to melting temperatures in some cases. Their optical properties were examined by using UV–Vis and photoluminescent spectrometers; and they emitted blue light both in the solution and solid states regardless of their microstructures, counterions, and the polarity of organic solvents. However, most of these salts exhibited hypsochromic shifts in their emission peaks in the solid state when compared with those of their solution spectra. Due to unique properties of methyl orange anion as a pH indicator, two of the salts showed different color change in varying concentrations of triflic acid in common organic solvents, demonstrating their potential use as an acid sensor in methanol, acetonitrile and acetone. Highlights: ► Luminescent dicationic salts were synthesized by ring-transmutation and metathesis reactions. ► Thermal and optical properties of dicationic salts are affected by the size of anion structures. ► Due to the methyl orange counterions, some dicationic salts showed pH- sensing property.

  10. Observation of Charge Inversion of an Ionic Liquid at the Solid Salt-Liquid Interface by Sum Frequency Generation Spectroscopy.

    Science.gov (United States)

    Peñalber, Chariz Y; Baldelli, Steven

    2012-04-05

    Sum frequency generation (SFG) vibrational spectroscopy of the ionic liquid, 1-butyl-3-methylimidazolium dicyanamide [BMIM][DCA], in contact with two different solid salt surfaces, BaF2(111) single crystal and solid NaCl{100}, are discussed in this Letter. This investigation describes the nature of an ionic liquid-(solid) salt interface using SFG, contributing a new understanding to the molecular-level interactions involved in salts, which are conceptually similar compounds (of purely ionic character) but of different physical properties (liquid versus solid at room temperature). Results show the presence of [BMIM](+) at the NaCl{100} surface and [DCA](-) at the BaF2(111) surface. [BMIM](+) cations adhere closely via Coulombic interactions to the negatively charged NaCl{100} surface, while [DCA](-) anions subsequently have a strong electrostatic affinity to the positively charged BaF2(111) surface. Ions of the ionic liquid adsorb to the solid salt surface to form a Helmholtz-like electric double layer.

  11. Aluminium sensitized spectrofluorimetric determination of fluoroquinolones in milk samples coupled with salting-out assisted liquid-liquid ultrasonic extraction

    Science.gov (United States)

    Xia, Qinghai; Yang, Yaling; Liu, Mousheng

    2012-10-01

    An aluminium sensitized spectrofluorimetric method coupled with salting-out assisted liquid-liquid ultrasonic extraction for the determination of four widely used fluoroquinolones (FQs) namely norfloxacin (NOR), ofloxacin (OFL), ciprofloxacin (CIP) and gatifloxacin (GAT) in bovine raw milk was described. The analytical procedure involves the fluorescence sensitization of aluminium (Al3+) by complexation with FQs, salting-out assisted liquid-liquid ultrasonic extraction (SALLUE), followed by spectrofluorometry. The influence of several parameters on the extraction (the salt species, the amount of salt, pH, temperature and phase volume ratio) was investigated. Under optimized experimental conditions, the detection limits of the method in milk varied from 0.009 μg/mL for NOR to 0.016 μg/mL for GAT (signal-to-noise ratio (S/N) = 3). The relative standard deviations (RSD) values were found to be relatively low (0.54-2.48% for four compounds). The calibration graph was linear from 0.015 to 2.25 μg/mL with coefficient of determinations not less than 0.9974. The methodology developed was applied to the determination of FQs in bovine raw milk samples. The main advantage of this method is simple, accurate and green. The method showed promising applications for analyzing polar analytes especially polar drugs in various sample matrices.

  12. High-throughput salting-out-assisted homogeneous liquid-liquid extraction with acetonitrile for determination of baicalin in rat plasma with high-performance liquid chromatography.

    Science.gov (United States)

    Li, Tingting; Zhang, Lei; Tong, Ling; Liao, Qiongfeng

    2014-05-01

    Baicalin is the main indicator for qualitative and quantitative analysis of Scutellaria baicalensis Georgi and its prescription in vivo and in vitro. Owing to its insolubility and instability, the analysis of baicalin in biological samples is analytically challenging. Although there have been many pharmacokinetic or metabolism studies on baicalin, the current reported sample pretreatment methods are not the optimal choice with regard to absolute recovery and operation procedure. Here we report a high-throughput salting-out-assisted homogeneous liquid-liquid extraction method with acetonitrile and ammonium sulfate. Eight kinds of commonly used salts, preferred salt concentration and auxiliary solvents were investigated. The extraction efficiency in the presence of ammonium salt and auxiliary solvent (methanol) in comparison to that from the salt-free aqueous increased to above 90%. The performance of the developed pretreatment method was further evaluated through testing specificity, linearity, precision, accuracy, extraction recovery and stability. In particular, the stability investigation results proved that the operation at low temperature would no longer necessary be for salting-out-assisted homogeneous liquid-liquid extraction compared with protein precipitation, and the pretreatment method would be valuable if the compounds were unstable within matrices.

  13. AN EXPERIMENT TO STUDY PEBBLE BED LIQUID-FLUORIDE-SALT HEAT TRANSFER

    Energy Technology Data Exchange (ETDEWEB)

    Yoder Jr, Graydon L [ORNL; Aaron, Adam M [ORNL; Heatherly, Dennis Wayne [ORNL; Holcomb, David Eugene [ORNL; Kisner, Roger A [ORNL; McCarthy, Mike [ORNL; Peretz, Fred J [ORNL; Wilgen, John B [ORNL; Wilson, Dane F [ORNL

    2011-01-01

    A forced-convection liquid-fluoride-salt loop is being constructed at Oak Ridge National Laboratory (ORNL). This loop was designed as a versatile experimental facility capable of supporting general thermal/fluid/corrosion testing of liquid fluoride salts. The initial test configuration is designed to support the Pebble Bed Advanced High-Temperature Reactor and incorporates a test section designed to examine the heat transfer behavior of FLiNaK salt in a heated pebble bed. The loop is constructed of Inconel 600 and is capable of operating at up to 700oC. It contains a total of 72 kg of FLiNaK salt and uses an overhung impeller centrifugal sump pump that can provide FLiNaK flow at 4.5 kg/s with a head of 0.125 MPa. The test section is made of silicon carbide (SiC) and contains approximately 600 graphite spheres, 3 cm in diameter. The pebble bed is heated using a unique inductive technique. A forced induction air cooler removes the heat added to the pebble bed. The salt level within the loop is maintained by controlling an argon cover gas pressure. Salt purification is performed in batch mode by transferring the salt from the loop into a specially made nickel crucible system designed to remove oxygen, moisture and other salt impurities. Materials selection for the loop and test section material was informed by 3 months of Inconel 600 and SiC corrosion testing as well as tests examining subcomponent performance in the salt. Several SiC-to-Inconel 600 mechanical joint designs were considered before final salt and gas seals were chosen. Structural calculations of the SiC test section were performed to arrive at a satisfactory test section configuration. Several pump vendors provided potential loop pump designs; however, because of cost, the pump was designed and fabricated in-house. The pump includes a commercial rotating dry gas shaft seal to maintain loop cover gas inventory. The primary instrumentation on the loop includes temperature, pressure, and loop flow rate

  14. Thiophene-2-carbonyl azide

    Directory of Open Access Journals (Sweden)

    Michael Findlater

    2013-08-01

    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.

  15. Lead-Salt Quantum-Dot Ionic Liquids

    KAUST Repository

    Sun, Liangfeng

    2010-03-08

    PbS quantum dots (QDs) are functionalized using ionic liquids with thiol moieties as capping ligands. The resulting amphiphilic QD ionic liquids exhibit fluidlike behavior at room temperature, even in the absence of solvents. The photostability of the QDs is dramatically improved compared to the as-synthesized oleic acid-capped QDs dispersed in toluene. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Engineering Database of Liquid Salt Thermophysical and Thermochemical Properties

    Energy Technology Data Exchange (ETDEWEB)

    Manohar S. Sohal; Matthias A. Ebner; Piyush Sabharwall; Phil Sharpe

    2010-03-01

    The purpose of this report is to provide a review of thermodynamic and thermophysical properties of candidate molten salt coolants, which may be used as a primary coolant within a nuclear reactor or heat transport medium from the Next Generation Nuclear Plant (NGNP) to a processing plant, for example, a hydrogen-production plant. Thermodynamic properties of four types of molten salts, including LiF-BeF2 (67 and 33 mol%, respectively; also known as FLiBe), LiF-NaF-KF (46.5, 11.5, and 52 mol%, also known as FLiNaK), and KCl-MgCl2 (67 and 33 mol%), and sodium nitrate-sodium nitrite-potassium nitrate (NaNO3–NaNO2–KNO3, (7-49-44 or 7-40-53 mol%) have been investigated. Limitations of existing correlations to predict density, viscosity, specific heat capacity, surface tension, and thermal conductivity, were identified. The impact of thermodynamic properties on the heat transfer, especially Nusselt number was also discussed. Stability of the molten salts with structural alloys and their compatibility with the structural alloys was studied. Nickel and alloys with dense Ni coatings are effectively inert to corrosion in fluorides but not so in chlorides. Of the chromium containing alloys, Hastelloy N appears to have the best corrosion resistance in fluorides, while Haynes 230 was most resistant in chloride. In general, alloys with increasing carbon and chromium content are increasingly subject to corrosion by the fluoride salts FLiBe and FLiNaK, due to attack and dissolution of the intergranular chromium carbide. Future research to obtain needed information was identified.

  17. Nanostructure of mixtures of protic ionic liquids and lithium salts: effect of alkyl chain length.

    Science.gov (United States)

    Méndez-Morales, Trinidad; Carrete, Jesús; Rodríguez, Julio R; Cabeza, Óscar; Gallego, Luis J; Russina, Olga; Varela, Luis M

    2015-02-21

    The bulk structure of mixtures of two protic ionic liquids, propylammonium nitrate and butylammonium nitrate, with a salt with a common anion, is analyzed at room temperature by means of small angle X-ray scattering and classical molecular dynamics simulations. The study of several structural properties, such as density, radial distribution functions, spatial distribution functions, hydrogen bonds, coordination numbers and velocity autocorrelation functions, demonstrates that increasing the alkyl chain length of the alkylammonium cation results in more segregated, better defined polar and apolar domains, the latter having a larger size. This increase, ascribed to the erosion of the H-bond network in the ionic liquid polar regions as salt is added, is confirmed by means of small angle X-ray scattering measurements, which show a clear linear increase of the characteristic spatial sizes of the studied protic ionic liquids with salt concentration, similar to that previously reported for ethylammonium nitrate (J. Phys. Chem. B, 2014, 118, 761-770). In addition, larger ionic liquid cations lead to a lower degree of hydrogen bonding and to more sparsely packed three-dimensional structures, which are more easily perturbed by the addition of lithium salts.

  18. Development of a Forced-Convection Liquid-Fluoride-Salt Test Loop

    Energy Technology Data Exchange (ETDEWEB)

    Yoder Jr, Graydon L [ORNL; Wilson, Dane F [ORNL; Peretz, Fred J [ORNL; Wilgen, John B [ORNL; Romanoski, Glenn R [ORNL; Kisner, Roger A [ORNL; Holcomb, David Eugene [ORNL; Heatherly, Dennis Wayne [ORNL; Aaron, Adam M [ORNL

    2010-01-01

    A small forced-convection molten-fluoride-salt loop is being constructed at Oak Ridge National Laboratory to examine the heat transfer behavior of FLiNaK salt in a heated pebble bed. Objectives of the experiment include reestablishing infrastructure needed for fluoride-salt loop testing, developing a unique inductive heating technique for performing heat transfer (or other) experiments, measuring heat transfer characteristics in a liquid-fluoride-salt-cooled pebble bed, and demonstrating the use of silicon carbide (SiC) as a structural component for salt systems. The salt loop will consist of an Inconel 600 piping system, a sump-type pump, a SiC test section, and an air-cooled heat exchanger, as well as auxiliary systems needed to pre-heat the loop, transport salt into and out of the loop, and maintain an inert cover gas over the salt. A 30,000 Hz inductive heating system will be used to provide up to 250 kW of power to a 15 cm diameter SiC test section containing a packed bed of 3 cm graphite spheres. A SiC-to-Inconel 600 joint will use a conventional nickel/grafoil spiral wound gasket sandwiched between SiC and Inconel flanges. The loop system can provide up to 4.5 kg/s of salt flow at a head of 0.125 MPa and operate at a pressure just above atmospheric. Pebble Reynolds numbers of up to 2600 are possible with this configuration. A sump system is provided to drain and store the salt when not in use. Instrumentation on the loop will include pressure, temperature, and flow measurements, while the test section will be instrumented to provide pebble and FLiNaK temperatures.

  19. Bio-based ionic liquid crystalline quaternary ammonium salts: properties and applications.

    Science.gov (United States)

    Sasi, Renjith; Rao, Talasila P; Devaki, Sudha J

    2014-03-26

    In the present work, we describe the preparation, properties, and applications of novel ionic liquid crystalline quaternary ammonium salts (QSs) of 3-pentadecylphenol, a bio-based low-cost material derived from cashew nut shell liquid. Amphotropic liquid crystalline phase formation in QSs was characterized using a combination of techniques, such as DSC, PLM, XRD, SEM, and rheology, which revealed the formation of one, two, and three dimensionally ordered mesophases in different length scales. On the basis of these results, a plausible mechanism for the formation of specific modes of packing in various mesophases was proposed. Observation of anisotropic ionic conductivity and electrochemical stability suggests their application as a solid electrolyte.

  20. Combination of counter current salting-out homogenous liquid-liquid extraction and dispersive liquid-liquid microextraction as a novel microextraction of drugs in urine samples.

    Science.gov (United States)

    Akramipour, Reza; Fattahi, Nazir; Pirsaheb, Meghdad; Gheini, Simin

    2016-02-15

    The counter current salting-out homogenous liquid-liquid extraction (CCSHLLE) joined with the dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) has been developed as a high preconcentration technique for the determination of different drugs in urine samples. Amphetamines were employed as model compounds to assess the extraction procedure and were determined by high performance liquid chromatography-ultraviolet detection (HPLC-UV). In this method, initially, NaCl as a separation reagent is filled into a small column and a mixture of urine and acetonitrile is passed through the column. By passing the mixture, NaCl is dissolved and the fine droplets of acetonitrile are formed due to salting-out effect. The produced droplets go up through the remained mixture and collect as a separated layer. Then, the collected acetonitrile is removed with a syringe and mixed with 30.0μL 1-undecanol (extraction solvent). In the second step, the 5.00mLK2CO3 solution (2% w/v) is rapidly injected into the above mixture placed in a test tube for further DLLME-SFO. Under the optimum conditions, calibration curves are linear in the range of 1-3000μgL(-1) and limit of detections (LODs) are in the range of 0.5-2μgL(-1). The extraction recoveries and enrichment factors ranged from 78 to 84% and 157 to 168, respectively. Repeatability (intra-day) and reproducibility (inter-day) of method based on seven replicate measurements of 100μgL(-1) of amphetamines were in the range of 3.5-4.5% and 4-5%, respectively. The method was successfully applied for the determination of amphetamines in the actual urine samples. The relative recoveries of urine samples spiked with amphetamine and methamphetamine are 90-108%.

  1. Can the Transport Properties of Molten Salts and Ionic Liquids Be Used To Determine Ion Association?

    Science.gov (United States)

    Harris, Kenneth R

    2016-12-01

    There have long been arguments supporting the concept of ion association in molten salts and ionic liquids, largely based on differences between the conductivity and that predicted from self-diffusion coefficients by the Nernst-Einstein equation for noninteracting ions. It is known from molecular dynamics simulations that even simple models based on charged hard spheres show such a difference due to the (anti)-correlation of ion motions. Formally this is expressed as a difference between the velocity cross-correlation coefficient of the oppositely charged ions and the mean of those for the two like-charged ions. This article examines molten salt and ionic liquid transport property data, comparing simple and model associated salts (ZnCl2, PbCl2, and TlCl) including weakly dissociated molecular liquids (H2O, HCOOH, H2SO4). Analysis employing Laity resistance coefficients (rij) shows that the common ion-association rationalization is flawed, consistent with recent direct measurements of the degree of ionicity in ionic liquid chlorides and with theoretical studies. However, the protic ionic liquids [PyrOMe][BF4] and [DBUH][CH3SO3] have larger than usual NE deviation parameters (>0.5), and large negative like-ion rii, analogous to those of ZnCl2. Structural, spectroscopic, and theoretical studies are suggested to determine whether these are indeed genuine examples of association.

  2. Double-salting out assisted liquid-liquid extraction (SALLE) HPLC method for estimation of temozolomide from biological samples.

    Science.gov (United States)

    Jain, Darshana; Athawale, Rajani; Bajaj, Amrita; Shrikhande, Shruti

    2014-11-01

    The role of temozolomide (TMZ) in treatment of high grade gliomas, melanomas and other malignancies is being defined by the current clinical developmental trials. Temozolomide belongs to the group of alkylating agents and is prescribed to patients suffering from most aggressive forms of brain tumors. The estimation techniques for temozolomide from the extracted plasma or biological samples includes high-performance liquid chromatography with UV detection (HPLC-UV), micellar electrokinetic capillary chromatography (MKEC) and liquid chromatography coupled to mass spectroscopy (LC-MS). These methods suffer from disadvantages like low resolution, low sensitivity, low recovery or cost involvement. An analytical method possessing capacity to estimate low quantities of TMZ in plasma samples with high extraction efficiency (%) and high resolution with cost effectiveness needs to be developed. Cost effective, robust and low plasma component interfering HPLC method using salting out liquid-liquid extraction (SALLE) technique was developed and validated for estimation of drug from plasma samples. The extraction efficiency (%) with conventional LLE technique with methanol, ethyl acetate, dichloromethane and acetonitrile was found to be 5.99±2.45, 45.39±4.56, 46.04±1.14 and 46.23±3.67 respectively. Extraction efficiency (%) improved with SALLE where sodium chloride was used as an electrolyte and was found to be 6.80±5.56, 52.01±3.13, 62.69±2.11 and 69.20±1.18 with methanol, ethyl acetate, dichloromethane and acetonitrile as organic solvent. Upon utilization of two salts for extraction (double salting liquid-liquid extraction) the extraction efficiency (%) was further improved and was twice of LLE. It was found that double salting liquid-liquid extraction technique yielded extraction efficiency (%) of 11.71±5.66, 55.62±3.44, 77.28±2.89 and 87.75±0.89. Hence a method based on double SALLE was developed for quantification of TMZ demonstrating linearity in the range of

  3. Salt effect of KBr on the liquid-liquid equilibrium of the water/ethanol/1-pentanol system

    Directory of Open Access Journals (Sweden)

    G.R. Santos

    2000-12-01

    Full Text Available Liquid-liquid equilibrium data for the water/ethanol/1-pentanol/potassium bromide systems were experimentally determined at 25° C and 40ºC. The experimental data were correlated through the NRTL and UNIFAC-Dortmund models for the activity coefficient, with the estimation of new binary interaction parameters for both models, corresponding to the salt-solvent and solvent-solvent interactions for the NRTL model and the ion-ion and solvent-ion interactions for the UNIFAC-Dortmund model. The results obtained have shown that the NRTL model was more able to represent equilibrium data for the studied systems.

  4. Liquid chromatography-tandem mass spectrometric assay for the tyrosine kinase inhibitor afatinib in mouse plasma using salting-out liquid-liquid extraction

    NARCIS (Netherlands)

    Sparidans, Rolf W; van Hoppe, Stephanie; Rood, Johannes J M; Schinkel, Alfred H; Schellens, Jan H M; Beijnen, Jos H

    2016-01-01

    A quantitative bioanalytical liquid chromatography-tandem mass spectrometric (LC-MS/MS) assay for afatinib, an irreversible inhibitor of the ErbB (erythroblastic leukemia viral oncogene homolog) tyrosine kinase family, was developed and validated. Plasma samples were pre-treated using salting-out as

  5. Ionic conductance behavior of polymeric gel electrolyte containing ionic liquid mixed with magnesium salt

    Science.gov (United States)

    Morita, Masayuki; Shirai, Takahiro; Yoshimoto, Nobuko; Ishikawa, Masashi

    A new polymeric gel electrolyte system conducting magnesium ion has been proposed. The gel electrolytes consisted of poly(ethylene oxide)-modified polymethacrylate (PEO-PMA) dissolving ionic liquid mixed with magnesium salt, Mg[(CF 3SO 2) 2N] 2. The polymeric gel films were self-standing, transparent and flexible with enough mechanical strength. The ionic conductance and the electrochemical properties of the gel films were investigated. Thermal analysis results showed that the polymeric gel is homogeneous and amorphous over a wide temperature range. The highest conductivity, 1.1 × 10 -4 S cm -1 at room temperature (20 °C), was obtained for the polymeric gel containing 50 wt.% of the ionic liquid in which the content of the magnesium salt was 20 mol%. The dc polarization of a Pt/Mg cell using the polymeric gel electrolyte proved that the magnesium ion (Mg 2+) is mobile in the present polymeric system.

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

    Institute of Scientific and Technical Information of China (English)

    刘建明; 刘慕文; 岳园园; 姚美焕; 卓克垒

    2012-01-01

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

  7. Cloud Point and Liquid-Liquid Equilibrium Behavior of Thermosensitive Polymer L61 and Salt Aqueous Two-Phase System.

    Science.gov (United States)

    Rao, Wenwei; Wang, Yun; Han, Juan; Wang, Lei; Chen, Tong; Liu, Yan; Ni, Liang

    2015-06-25

    The cloud point of thermosensitive triblock polymer L61, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO), was determined in the presence of various electrolytes (K2HPO4, (NH4)3C6H5O7, and K3C6H5O7). The cloud point of L61 was lowered by the addition of electrolytes, and the cloud point of L61 decreased linearly with increasing electrolyte concentration. The efficacy of electrolytes on reducing cloud point followed the order: K3C6H5O7 > (NH4)3C6H5O7 > K2HPO4. With the increase in salt concentration, aqueous two-phase systems exhibited a phase inversion. In addition, increasing the temperature reduced the concentration of salt needed that could promote phase inversion. The phase diagrams and liquid-liquid equilibrium data of the L61-K2HPO4/(NH4)3C6H5O7/K3C6H5O7 aqueous two-phase systems (before the phase inversion but also after phase inversion) were determined at T = (25, 30, and 35) °C. Phase diagrams of aqueous two-phase systems were fitted to a four-parameter empirical nonlinear expression. Moreover, the slopes of the tie-lines and the area of two-phase region in the diagram have a tendency to rise with increasing temperature. The capacity of different salts to induce aqueous two-phase system formation was the same order as the ability of salts to reduce the cloud point.

  8. Coupled neutronics/thermal-hydraulics and safety characteristics of liquid-fueled molten salt reactors

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Suizheng; Zhang, Dalin; Liu, Minghao; Liu, Limin; Xu, Rongshuan; Gong, Cheng; Su, Guanghui [Xi' an Jiaotong Univ. (China). State Key Laboratory of Multiphase Flow in Power Engineering

    2016-05-15

    Molten salt reactor (MSR) as one candidate of the Generation IV advanced nuclear power systems is attracted more attention in China due to its top ranked fuel cycle and thorium utilization. The MSRs are characterized by using liquid-fuel, which offers complicated coupling problem of neutronics and thermal hydraulics. In this paper, the fundamental model and numerical method are established to calculate and analyze the safety characteristics for liquid-fuel MSRs. The theories and methodologies are applied to the MOSART concept. The liquid-fuel flow effects on neutronics, reactivity coefficients and three operation parameters' influences at steady state are obtained, which provide the basic information for safety analysis. The unprotected loss of flow transient is calculated, the results of which shows the inherent safety characteristics of MOSART due to its strong negative reactivity feedbacks.

  9. Inorganic Salts Effect on Adsorption Behavior of Surfactant AEC at Liquid/Liquid Interface

    Directory of Open Access Journals (Sweden)

    Changhua Yang

    2013-07-01

    Full Text Available Behaviors of nonionic-anionic surfactant sodium fatty Alcohol polyoxyethylene Ether Carboxylate (AEC at dodecane/water interface influenced by inorganic salts NaCl, CaCl2 and MgCl2 were investigated by interfacial tension methods and molecular dynamics simulation. Contrasted distributions of various salts at interface and in aqueous solutions and resulting lowering the interfacial tension have been observed. Composition of surfactants-salts complex at interface surrounding different cations within 2.5 Å were found to be in two categories: (i the octahedral complexation of divalent cation was generated by the participation of surfactant head group and water molecule, (ii only water molecules were involved in the complexation. According to the simulation results, all the Na+ involved in type ii, without any direct interaction with surfactant head group, while Ca2+ and Mg2+ involved in type I, following the formula: Ca2++4 (surfactant +2(H2 O⇄ [Ca (surfactant4 [(H2 O]2]2+ M2+g+(surfactant+5 (H2 O⇄[Mg (surfactant [(H2 O]5 ]2+ This strongly chelate interaction between Ca2+ and surfactants makes surfactants more stretched at interface, thus more effective in oil/water interface.

  10. Pencil lead scratches on steel surfaces as a substrate for LIBS analysis of dissolved salts in liquids

    Energy Technology Data Exchange (ETDEWEB)

    Jijon, D; Costa, C, E-mail: judijival@hotmail.com [Departamento de Fisica, Escuela Politecnica Nacional, Ladron de Guevara E11-256, Apartado 17-12-866, Quito (Ecuador)

    2011-01-01

    A new substrate for the quantitative analysis of salts dissolved in liquids with Laser-induced Breakdown Spectroscopy (LIBS) is introduced for the first time. A steel surface scratched with HB pencil lead is introduced as a very efficient and sensitive substrate for quantitative analysis of dissolved salts in liquids. In this work we demonstrate the analytical quality of this system with the analysis of the crystalline deposits formed by the dried aqueous solutions of salts. We focused on analytical parameters such as sensitivity and linearity for the salt cations in each case. Four salts were studied (Sr(NO{sub 3}){sub 2}, LiSO{sub 4}, RbCl and BaCl), at nine different concentrations each. To improve linearity and lower the overall error in the calibration curves, we introduce a novel outlier removal method that takes into account the homogeneity of the dry deposits on the analytical surface.

  11. Predicting human intestinal absorption in the presence of bile salt with micellar liquid chromatography.

    Science.gov (United States)

    Waters, Laura J; Shokry, Dina S; Parkes, Gareth M B

    2016-10-01

    Understanding intestinal absorption for pharmaceutical compounds is vital to estimate the bioavailability and therefore the in vivo potential of a drug. This study considers the application of micellar liquid chromatography (MLC) to predict passive intestinal absorption with a selection of model compounds. MLC is already known to aid prediction of absorption using simple surfactant systems; however, with this study the focus was on the presence of a more complex, bile salt surfactant, as would be encountered in the in vivo environment. As a result, MLC using a specific bile salt has been confirmed as an ideal in vitro system to predict the intestinal permeability for a wide range of drugs, through the development of a quantitative partition-absorption relationship. MLC offers many benefits including environmental, economic, time-saving and ethical advantages compared with the traditional techniques employed to obtain passive intestinal absorption values. Copyright © 2016 John Wiley & Sons, Ltd.

  12. A Diazonium Salt-Based Ionic Liquid for Solvent-FreeModification of Carbon.

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Chengdu [ORNL; Huang, Jing-Fang [ORNL; Li, Zuojiang [ORNL; Luo, Huimin [ORNL; Dai, Sheng [ORNL

    2006-01-01

    A novel ionic liquid that consists of p-butylbenzenediazonium ions and bis(trifluoromethanesulfonyl)amidates (Tf{sub 2}N{sup -}) has been synthesized as a task-specific ionic liquid for the solvent-free modification of carbon materials. The use of anions Tf{sub 2}N{sup =} is the key to rendering the hydrophobicity, low liquidus temperature, and ionicity to this novel molten salt. This diazonium salt has a melting point of 7.2 C and a moderate electric conductivity of 527 {micro} s/cm at 25 C. The thermal stability of this diazonium ionic liquid has been investigated by high-resolution thermogravimetric analysis (HRTGA). The compound is stable up to about 90 C in nitrogen, which is only 10 C less than its solid tetrafluoroborate counterpart. The modification of carbon materials has been carried out through both thermal and electrochemical activations of diazonium ions to generate free radical intermediates without the use of any solvent. The surface-coverage loadings of 3.38 {micro} mol/m{sup 2} and 6.07 {micro} mol/m{sup 2} for covalently attached organic functionalities have been achieved by the thermally induced functionalization and electrochemically assisted reaction, respectively.

  13. Salting-out homogenous extraction followed by ionic liquid/ionic liquid liquid-liquid micro-extraction for determination of sulfonamides in blood by high performance liquid chromatography.

    Science.gov (United States)

    Liu, Zhongling; Yu, Wei; Zhang, Hanqi; Gu, Fanbin; Jin, Xiangqun

    2016-12-01

    Salting-out homogenous extraction followed by ionic liquid/ionic liquid dispersive liquid-liquid micro-extraction system was developed and applied to the extraction of sulfonamides in blood. High-performance liquid chromatography was applied to the determination of the analytes. The blood sample was centrifuged to obtain the serum. After the proteins in the serum were removed in the presence of acetonitrile, ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, dipotassium hydrogen phosphate, ionic liquid 1-Hexyl-3-methylimidazolium hexafluorophosphate were added into the resulting solution. After the resulting mixture was ultrasonically shaken and centrifuged, the precipitate was separated. The acetonitrile was added in the precipitate and the analytes were extracted into the acetonitrile phase. The parameters affecting the extraction efficiency, such as volume of ionic liquid, amount of dipotassium hydrogen phosphate, volume of dispersant, extraction time and temperature were investigated. The limits of detection of sulfamethizole (STZ), sulfachlorpyridazine (SCP), sulfamethoxazole (SMX) and Sulfisoxazole (SSZ) were 4.78, 3.99, 5.21 and 3.77μgL(-1), respectively. When the present method was applied to the analysis of real blood samples, the recoveries of analytes ranged from 90.0% to 113.0% and relative standard deviations were lower than 7.2%.

  14. Electrodeposition of alkali and alkali-earth metals on liquid lead cathodes in molten salts

    Energy Technology Data Exchange (ETDEWEB)

    Caravaca, C.; De Cordoba, G. [CIEMAT/DE/DFN/URAA. Avda. Complutense, 22. 28040 Madrid (Spain)

    2008-07-01

    Pyrochemical processing of spent nuclear fuel leads to the dissolution as chlorides of fission products (FPs) that have to be removed in order to recycle the salt. Precipitation technique have been tested for the removal of these FPs in the LiCl-KCl, salt selected as reference, with different results. Salt decontamination from lanthanides can be easily achieved as solid precipitates of oxychlorides or single phosphates; however, for the alkaline and alkaline-earth metals this technique is not suitable. Within the EUROPART project (VI FP of the EC), a new route that consist of the electrodeposition of these FP on a liquid lead cathode (LLC) has been considered, including the Li and K constituting the electrolyte. First results obtained with Sr and Cs are presented herein. Although according to the thermodynamic potential values, the electrodeposition order on LLC is Ba, Sr, Li, K and Cs, during our experiments it was not possible to distinguish the electrochemical signals corresponding to the individual elements. (authors)

  15. Fast, simple and efficient salting-out assisted liquid-liquid extraction of naringenin from fruit juice samples prior to their enantioselective determination by liquid chromatography.

    Science.gov (United States)

    Magiera, Sylwia; Kwietniowska, Ewelina

    2016-11-15

    In this study, an easy, simple and efficient method for the determination of naringenin enantiomers in fruit juices after salting-out-assisted liquid-liquid extraction (SALLE) and high-performance liquid chromatography (HPLC) with diode-array detection (DAD) was developed. The sample treatment is based on the use of water-miscible acetonitrile as the extractant and acetonitrile phase separation under high-salt conditions. After extraction, juice samples were incubated with hydrochloric acid in order to achieve hydrolysis of naringin to naringenin. The hydrolysis parameters were optimized by using a half-fraction factorial central composite design (CCD). After sample preparation, chromatographic separation was obtained on a Chiralcel® OJ-RH column using the mobile phase consisting of 10mM aqueous ammonium acetate:methanol:acetonitrile (50:30:20; v/v/v) with detection at 288nm. The average recovery of the analyzed compounds ranged from 85.6 to 97.1%. The proposed method was satisfactorily used for the determination of naringenin enantiomers in various fruit juices samples.

  16. Extended UNIQUAC Model for Correlation and Prediction of Vapor-Liquid-Liquid-Solid Equilibria in Aqueous Salt Systems Containing Non-Electrolytes. Part B. Alcohol (Ethanol, Propanols, Butanols) - Water-salt systems

    DEFF Research Database (Denmark)

    Thomsen, Kaj; Iliuta, Maria Cornelia; Rasmussen, Peter

    2004-01-01

    -Redlich-Kwong equation of state. The model only requires binary, temperature-dependent interaction parameters. It has previously been used to describe the excess Gibbs energy for aqueous electrolyte mixtures and aqueous electrolyte systems containing methanol. It has been found to be an adequate model for representing...... solid-liquid-vapor equilibrium and thermal property data for strongly non-ideal systems. In this work, the model is extended to aqueous salt systems containing higher alcohols. The calculations are based on an extensive database consisting of salt solubility data, vapor liquid equilibrium data...

  17. Simultaneous determination of dorzolomide and timolol in aqueous humor: a novel salting out liquid-liquid microextraction combined with HPLC.

    Science.gov (United States)

    Mohamed, Abdel-Maaboud Ismail; Abdel-Wadood, Hanaa Mohammed; Mousa, Heba Salah

    2014-12-01

    A Snovel method for the simultaneous separation and determination of two antiglaucoma drugs namely, dorzolamide hydrochloride (DOR) and timolol maleate (TIM) in aqueous humor samples (AH) was developed by using salting-out assisted liquid-liquid microextraction (SALLME) combined with HPLC-UV method. Box-Behnken experimental design and response surface methodology were employed to assist the optimization of SALLME conditions, including salt concentration, the pH of sample solution and vortex time as variable factors. The optimal extraction conditions were as follows: to 50 µL of AH sample, 100 µL of phosphate buffer (100 mmol L(-1), pH 11.9), 90 µL of acetonitrile (ACN) and 0.11 g of (NH4)2SO4 salt were added into an Eppendorf vial (1 mL) then vortexed for 1.1 min. As an effort to miniaturize SALLE system, a 1 mL syringe adapted with a capillary tube was employed as the phase separation device. Once the phase separation occurred, the upper layer could be narrowed into the capillary tube by pushing the plunger; thus, the collection of the upper layer solvent was simple and convenient. By miniaturization, the consumption of the organic solvent was decreased as low as possible. The chromatographic separation was achieved on Gemini C18 column using a mobile phase of ACN: 30 mmol L(-1) potassium dihydrogen phosphate buffer containing 0.1% triethylamine, pH 3.5 (20:80, v/v) at a flow rate of 1 mL min(-1) and UV detection at 254 and 295 nm for DOR and TIM, respectively. Mepivacaine hydrochloride was used as an internal standard. The described method showed better separation with enhanced sensitivities than the previously reported methods with limits of quantitation of 8.75 and 10.32 ng mL(-1) in aqueous solution and 15.97 and 23.53 ng mL(-1) in AH for DOR and TIM, respectively. The simple, rapid and eco-friendly SALLME-HPLC method has been successfully applied for the simultaneous pharmacokinetic studies of DOR and TIM in rabbit AH.

  18. Solvation of lithium salts in protic ionic liquids: a molecular dynamics study.

    Science.gov (United States)

    Méndez-Morales, Trinidad; Carrete, Jesús; Cabeza, Óscar; Russina, Olga; Triolo, Alessandro; Gallego, Luis J; Varela, Luis M

    2014-01-23

    The structure of solutions of lithium nitrate in a protic ionic liquid with a common anion, ethylammonium nitrate, at room temperature is investigated by means of molecular dynamics simulations. Several structural properties, such as density, radial distribution functions, hydrogen bonds, spatial distribution functions, and coordination numbers, are analyzed in order to get a picture of the solvation of lithium cations in this hydrogen-bonded, amphiphilically nanostructured environment. The results reveal that the ionic liquid mainly retains its structure upon salt addition, the interaction between the ammonium group of the cation and the nitrate anion being only slightly perturbed by the addition of the salt. Lithium cations are solvated by embedding them in the polar nanodomains of the solution formed by the anions, where they coordinate with the latter in a solid-like fashion reminiscent of a pseudolattice structure. Furthermore, it is shown that the average coordination number of [Li](+) with the anions is 4, nitrate coordinating [Li](+) in both monodentate and bidentate ways, and that in the second coordination layer both ethylammonium cations and other lithiums are also found. Additionally, the rattling motion of lithium ions inside the cages formed by their neighboring anions, indicative of the so-called caging effect, is confirmed by the analysis of the [Li](+) velocity autocorrelation functions. The overall picture indicates that the solvation of [Li](+) cations in this amphiphilically nanostructured environment takes place by means of a sort of inhomogeneous nanostructural solvation, which we could refer to as nanostructured solvation, and which could be a universal solvation mechanism in ionic liquids.

  19. Simple access to ionic liquids and organic salts containing the phosphaethynolate (PCO(-)) and Zintl (Sb11(3-)) anions.

    Science.gov (United States)

    Jost, Maximilian; Finger, Lars H; Sundermeyer, Jörg; von Hänisch, Carsten

    2016-10-07

    Herein we report the synthesis of the first ionic liquids with the highly reactive and synthetically valuable phosphaethynolate (PCO(-)) anion. They are simply synthesised by the reaction of organic methylcarbonate salts with P(SiMe3)3. The products are obtained in near to quantitative yields and they are highly viscous liquids at room temperature or have low melting points for symmetric cations. Moreover, extending this synthetic strategy towards Sb(SiMe3)3 we discovered a simple synthesis for [P(nBu)3Me](+)3[Sb11](3-), the first organic cation salt comprising the Zintl-anion [Sb11](3-).

  20. Bridging the gap between ionic liquids and molten salts: group 1 metal salts of the bistriflamide anion in the gas phase.

    Science.gov (United States)

    Leal, João P; da Piedade, Manuel E Minas; Canongia Lopes, José N; Tomaszowska, Alina A; Esperança, José M S S; Rebelo, Luís Paulo N; Seddon, Kenneth R

    2009-03-19

    Fourier transform ion cyclotron resonance mass spectrometry experiments showed that liquid Group 1 metal salts of the bistriflamide anion undergoing reduced-pressure distillation exhibit a remarkable behavior that is in transition between that of the vapor-liquid equilibrium characteristics of aprotic ionic liquids and that of the Group 1 metal halides: the unperturbed vapors resemble those of aprotic ionic liquids, in the sense that they are essentially composed of discrete ion pairs. However, the formation of large aggregates through a succession of ion-molecule reactions is closer to what might be expected for Group 1 metal halides. Similar experiments were also carried out with bis{(trifluoromethyl)sulfonyl}amine to investigate the effect of H(+), which despite being the smallest Group 1 cation, is generally regarded as a nonmetal species. In this case, instead of the complex ion-molecule reaction pattern found for the vapors of Group 1 metal salts, an equilibrium similar to those observed for aprotic ionic liquids was observed.

  1. Quantitative analysis of ammonium salts in coking industrial liquid waste treatment process based on Raman spectroscopy

    Science.gov (United States)

    Cao, Ya-Nan; Wang, Gui-Shi; Tan, Tu; Cai, Ting-Dong; Liu, Kun; Wang, Lei; Zhu, Gong-Dong; Mei, Jiao-Xu

    2016-10-01

    Quantitative analysis of ammonium salts in the process of coking industrial liquid waste treatment is successfully performed based on a compact Raman spectrometer combined with partial least square (PLS) method. Two main components (NH4SCN and (NH4)2S2O3) of the industrial mixture are investigated. During the data preprocessing, wavelet denoising and an internal standard normalization method are employed to improve the predicting ability of PLS models. Moreover, the PLS models with different characteristic bands for each component are studied to choose a best resolution. The internal and external calibration results of the validated model show a mass percentage error below 1% for both components. Finally, the repeatabilities and reproducibilities of Raman and reference titration measurements are also discussed. Project supported by the National Natural Science Foundation of China (Grant Nos. 41405022 and 61475068).

  2. Annular core liquid-salt cooled reactor with multiple fuel and blanket zones

    Science.gov (United States)

    Peterson, Per F.

    2013-05-14

    A liquid fluoride salt cooled, high temperature reactor having a reactor vessel with a pebble-bed reactor core. The reactor core comprises a pebble injection inlet located at a bottom end of the reactor core and a pebble defueling outlet located at a top end of the reactor core, an inner reflector, outer reflector, and an annular pebble-bed region disposed in between the inner reflector and outer reflector. The annular pebble-bed region comprises an annular channel configured for receiving pebble fuel at the pebble injection inlet, the pebble fuel comprising a combination of seed and blanket pebbles having a density lower than the coolant such that the pebbles have positive buoyancy and migrate upward in said annular pebble-bed region toward the defueling outlet. The annular pebble-bed region comprises alternating radial layers of seed pebbles and blanket pebbles.

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

    NARCIS (Netherlands)

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

    2009-01-01

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

  4. Analysis of biogenic amines in wines by salting-out assisted liquid-liquid extraction and high-performance liquid chromatography with fluorimetric detection.

    Science.gov (United States)

    Ramos, Rui Miguel; Valente, Inês Maria; Rodrigues, José António

    2014-06-01

    Biogenic amines are nitrogenous organic compounds of low molecular weight that are either formed or metabolized in cells of living organisms and can be found in several food products, being produced mainly by amino acid decarboxylation. When ingested in high concentrations they can induce several health problems in humans. In alcoholic beverages, and especially in wine, they are formed during the vinification process as a result of the action of microorganisms. In this work it is proposed a new methodology for the determination of biogenic amines in wines, which includes a sample preparation approach based on salting-out assisted liquid-liquid extraction, the use of dansyl chloride for the derivatization and chromatographic separation by high-performance liquid chromatography with fluorimetric detection. The salting-out effect is used to promote phase separation between water and a water-miscible organic solvent, while improving the extraction of organic or inorganic species. Several extraction parameters were optimized, such as the dansyl chloride concentration, pH and the effects caused by the order in which the extraction and derivatization were performed. Extraction of amines, and consequent detection, depends on the presence of dansyl chloride in solution prior to extraction. The results showed the possibility to simultaneously perform the extraction and the derivatization, making sample preparation easier and less time-consuming. The methodology was successfully applied to the determination of biogenic amines in five wines (white, red and rosé). This method has the potential to be a good alternative to existing methods since it is cheaper, easier and simplifies the sample preparation step.

  5. Preparation of salted meat products, e.g. cured bacon - by injecting liquid comprising meat proteins hydrolysed with enzymes

    DEFF Research Database (Denmark)

    1997-01-01

    Preparation of salted meat products comprises the following:(1) meat is chopped into fine pieces and mixed with water to form a slurry; (2) enzymes hydrolyse proteins in the meat; (3) adding a culture to the resulting medium, which comprises short peptide chains or amino acids; (4) forming...... flavourings as the culture is growing, and (5) injecting the liquid into pieces of meat....

  6. Salt Tolerance Enhancement of Liquid Chromatography-Matrix-Assisted Laser Desorption/Ionization-Mass Spectrometry Using Matrix Additive Methylenediphosphonic Acid

    Science.gov (United States)

    Ohta, Yuki; Iwamoto, Shinichi; Kawabata, Shin-ichirou; Tanimura, Ritsuko; Tanaka, Koichi

    2014-01-01

    Mass spectrometry (MS) is a highly sensitive analytical technique that is often coupled with liquid chromatography (LC). However, some buffering salts used in LC (e.g., phosphate and tris(hydroxymethyl)aminomethane (Tris)) are incompatible with MS since they cause ion-source contamination and signal suppression. In this study, we examined salt tolerance of MALDI and applied a matrix additive methylenediphosphonic acid (MDPNA) to reduce salt-induced signal suppression. MDPNA significantly improved the salt tolerance of MALDI-MS. Using ammonium formate buffer at pH 5.0, the effective range of buffering salt concentration in MALDI-MS using MDPNA was estimated up to 250 mM. MDPNA reduced signal suppression caused by buffering salts at pH 4.0 to 8.0. We observed that MDPNA effectively worked over a wide range of buffer conditions. MDPNA was further applied to hydrophilic interaction chromatography (HILIC) and chromatofocusing-MALDI-MS. As a result, the analytes in the eluent containing high-concentration salts were detected with high sensitivity. Thus, our study provides simple and fast LC-MALDI-MS analysis technique not having strict limitation of buffering condition in LC by using matrix additive MDPNA. PMID:26819873

  7. Photochemistry of ortho, ortho' dialkyl phenyl azides.

    Science.gov (United States)

    Tsao, Meng-Lin; Platz, Matthew S

    2003-10-01

    Phenyl azide, 2,6-diethylphenyl azide, 2,6-diisopropylphenyl azide, and 2,4,6-tri-tert-butylphenyl azide were studied by laser flash photolysis (LFP) methods. LFP (266 nm) of the azides in glassy 3-methylpentane at 77 K produces the transient UV-vis absorption spectra of the corresponding singlet nitrenes. At 77 K, the singlet nitrenes relax to the corresponding triplet nitrenes. The triplet nitrenes are persistent at 77 K and their spectra were recorded. The rate constants of singlet to triplet intersystem crossing were determined at this temperature. LFP of 2,4,6-tri-tert-butyl phenyl azide in pentane at ambient temperature again produces a singlet nitrene, which is too short-lived to detect by nanosecond spectroscopy under these conditions. Unlike the other azides, the first detectable intermediate produced upon LFP of 2,4,6-tri-tert-butyl phenyl azide at ambient temperature is the benzazirine (285 nm) which has a lifetime of 62 ns controlled by ring opening to a didehydroazepine. The results are interpreted with the aid of Density Functional Theoretical and Molecular Orbital Calculations.

  8. Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Gómez-González, Víctor; Docampo-Álvarez, Borja; Gallego, Luis J.; Varela, Luis M., E-mail: luismiguel.varela@usc.es [Grupo de Nanomateriais e Materia Branda, Departamento de Física da Materia Condensada, Universidade de Santiago de Compostela, Campus Vida s/n, E-15782 Santiago de Compostela (Spain); Cabeza, Oscar [Facultade de Ciencias, Universidade da Coruña, Campus A Zapateira s/n, E-15008 A Coruña (Spain); Fedorov, Maxim [Department of Physics, Scottish University Physics Alliance (SUPA), University of Strathclyde, John Anderson Bldg., 107 Rottenrow East, Glasgow G4 0NG (United Kingdom); Lynden-Bell, Ruth M. [Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom)

    2015-09-28

    We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF{sub 6}]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers. For the protic mixtures, the effect of salt concentration on the network of hydrogen bonds is also considered. Moreover, single-particle dynamics of the salt cations is studied by means of their velocity autocorrelation functions and vibrational densities of states, explicitly analyzing the influence of salt concentration, and cation charge and mass on these magnitudes. The effect of the valency of the salt cation on these properties is considered comparing the results with those for the corresponding mixtures with lithium salts. We found that the main structural and dynamic features of the local solvation of divalent cations in ionic liquids are similar to those of monovalent salts, with cations being localized in the polar nanoregions of the bulk mixture coordinated in monodentate and bidentate coordination modes by the [NO{sub 3}]{sup −} and [PF{sub 6}]{sup −} anions. However, stronger electrostatic correlations of these polar nanoregions than in mixtures with salts with monovalent cations are found. The vibrational modes of the ionic liquid (IL) are seen to be scarcely affected by the addition of the salt, and the effect of mass and charge on the vibrational densities of states of the dissolved cations is reported. Cation mass is seen to exert a deeper influence than charge on the low-frequency vibrational spectra, giving a red shift of the vibrational modes and a virtual suppression of the higher energy vibrational modes for the heavier Ca{sup 2

  9. Application of Proton Conductors to Hydrogen Monitoring for Liquid Metal and Molten Salt Systems

    Science.gov (United States)

    Kondo, Masatoshi; Muroga, Takeo; Katahira, Koji; Oshima, Tomoko

    The chemical control of impurity such as hydrogen and oxygen in coolants is one of the critical issues for the development of liquid metal cooled fast reactors and self-cooled liquid breeder blankets for fusion reactors. Especially, hydrogen (isotopes) level is the key parameter for corrosion and mechanical properties of the in-reactor components. For fission reactors, the monitor of hydrogen level in the melt is important for safety operation. The control of tritium is essential for the tritium breeding performance of the fusion reactors. Therefore, on-line hydrogen sensing is a key technology for these systems. In the present study, conceptual design for the on-line hydrogen sensor to be used in liquid sodium (Na), lead (Pb), lead-bismuth (Pb-Bi), lithium (Li), lead-lithium (Pb-17Li) and molten salt LiF-BeF2 (Flibe) was performed. The cell of hydrogen sensor is made of a solid electrolyte. The solid electrolyte proposed in this study is the CaZrO3-based ceramics, which is well-known as proton conducting ceramics. In this concept, the cell is immersed into the melt which is containing the hydrogen at the activity of PH1 of ambient atmosphere. Then, the cell is filled with Ar-H2 mixture gas at regulated hydrogen activity of PH2. The electromotive force (EMF) is obtained by the proton conduction in the electro chemical system expressed as Pt, Melt(PH1) | Proton conductor | PH2, Pt. The Nernst equation is used for the evaluation of the hydrogen activity from the obtained EMF. The evaluations of expected performance of the sensor in liquid Na, Pb, Pb-Bi, Pb-17Li, Li and Flibe were carried out by means of the measurement test in gas atmosphere at hydrogen activities equivalent to those for the melts in the reactor conditions. In the test, the hydrogen activity in the gas varied from 2.2x10-14 to 1. The sensor exhibited good response, stability and reproducibility.

  10. Integration of phase separation with ultrasound-assisted salt-induced liquid-liquid microextraction for analyzing the fluoroquinones in human body fluids by liquid chromatography.

    Science.gov (United States)

    Wang, Huili; Gao, Ming; Wang, Mei; Zhang, Rongbo; Wang, Wenwei; Dahlgren, Randy A; Wang, Xuedong

    2015-03-15

    Herein, we developed a novel integrated device to perform phase separation based on ultrasound-assisted salt-induced liquid-liquid microextraction for determination of five fluoroquinones (FQs) in human body fluids. The integrated device consisted of three simple HDPE components used to separate the extraction solvent from the aqueous phase prior to retrieving the extractant. A series of extraction parameters were optimized using the response surface method based on central composite design. Optimal conditions consisted of 945μL acetone extraction solvent, pH 2.1, 4.1min stir time, 5.9g Na2SO4, and 4.0min centrifugation. Under optimized conditions, the limits of detection (at S/N=3) were 0.12-0.66μgL(-1), the linear range was 0.5-500μgL(-1) and recoveries were 92.6-110.9% for the five FQs extracted from plasma and urine. The proposed method has several advantages, such as easy construction from inexpensive materials, high extraction efficiency, short extraction time, and compatibility with HPLC analysis. Thus, this method shows excellent prospects for sample pretreatment and analysis of FQs in human body fluids.

  11. Surface-induced liquid-gas transition in salt-free solutions of model charged colloids.

    Science.gov (United States)

    Budkov, Yu A; Frolov, A I; Kiselev, M G; Brilliantov, N V

    2013-11-21

    We report a novel phenomenon of a surface-induced phase transition in salt-free solutions of charged colloids. We develop a theory of this effect and confirm it by Molecular Dynamics simulations. To describe the colloidal solution we apply a primitive model of electrolyte with a strong asymmetry of charge and size of the constituent particles - macroions and counterions. To quantify interactions of the colloidal particles with the neutral substrate we use a short-range potential which models dispersion van der Waals forces. These forces cause the attraction of colloids to the surface. We show that for high temperatures and weak attraction, only gradual increase of the macroion concentration in the near-surface layer is observed with increase of interaction strength. If however temperature drops below some threshold value, a new dense (liquid) phase is formed in the near-surface layer. It can be interpreted as a surface-induced first-order phase transition with a critical point. Using an appropriately adopted Maxwell construction, we find the binodal. Interestingly, the observed near-surface phase transition can occur at the absence of the bulk phase transition and may be seemingly classified as prewetting transition. The reported effect could be important for various technological applications where formation of colloidal particle layers with the desired properties is needed.

  12. Effect of various salts on the stability of lansoprazole, omeprazole, and pantoprazole as determined by high-performance liquid chromatography.

    Science.gov (United States)

    Ekpe, A; Jacobsen, T

    1999-09-01

    A fast and reproducible reverse-phase high-performance liquid chromatography (HPLC) assay method has been developed for the simultaneous quantitation of omeprazole, lansoprazole, and pantoprazole. The three compounds were monitored at 280 nm using Zorbax Eclipse XDB C8 (5 microns, 150 cm x 4.6 mm i.d.) and a mobile phase consisting of 700:300 phosphate buffer:acetonitrile with the pH adjusted to 7.0 with phosphoric acid. The method was used to study the effect of pH and various salts on the stability of the three compounds. The pH rate profile curve showed that pantoprazole was the most stable compound and lansoprazole the least stable. The stabilities of the compounds in salt solutions were found to be in the following order: phosphate buffer bicarbonate < sodium chloride < water. The rate of degradation had a direct relationship with the H+ and salt concentration.

  13. Formation of liquid-crystalline structures in the bile salt-chitosan system and triggered release from lamellar phase bile salt-chitosan capsules.

    Science.gov (United States)

    Tangso, Kristian J; Lindberg, Seth; Hartley, Patrick G; Knott, Robert; Spicer, Patrick; Boyd, Ben J

    2014-08-13

    Nanostructured capsules comprised of the anionic bile salt, sodium taurodeoxycholate (STDC), and the biocompatible cationic polymer, chitosan, were prepared to assess their potential as novel tailored release nanomaterials. For comparison, a previously studied system, sodium dodecyl sulfate (SDS), and polydiallyldimethylammonium chloride (polyDADMAC) was also investigated. Crossed-polarizing light microscopy (CPLM) and small-angle X-ray scattering (SAXS) identified the presence of lamellar and hexagonal phase at the surfactant-polymer interface of the respective systems. The hydrophobic and electrostatic interactions between the oppositely charged components were studied by varying temperature and salt concentration, respectively, and were found to influence the liquid-crystalline nanostructure formed. The hexagonal phase persisted at high temperatures, however the lamellar phase structure was lost above ca. 45 °C. Both mesophases were found to dissociate upon addition of 4% NaCl solution. The rate of release of the model hydrophilic drug, Rhodamine B (RhB), from the lamellar phase significantly increased in response to changes in the solution conditions studied, suggesting that modulating the drug release from these bile salt-chitosan capsules is readily achieved. In contrast, release from the hexagonal phase capsules had no appreciable response to the stimuli applied. These findings provide a platform for these oppositely charged surfactant and polymer systems to function as stimuli-responsive or sustained-release drug delivery systems.

  14. 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.

    Science.gov (United States)

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

    2008-01-04

    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.

  15. MD simulations of the formation of stable clusters in mixtures of alkaline salts and imidazolium-based ionic liquids.

    Science.gov (United States)

    Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

    2013-03-21

    Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results.

  16. Transformation of Biopharmaceutical Classification System Class I and III Drugs Into Ionic Liquids and Lipophilic Salts for Enhanced Developability Using Lipid Formulations.

    Science.gov (United States)

    Williams, Hywel D; Ford, Leigh; Lim, Shea; Han, Sifei; Baumann, John; Sullivan, Hannah; Vodak, David; Igonin, Annabel; Benameur, Hassan; Pouton, Colin W; Scammells, Peter J; Porter, Christopher J H

    2017-05-23

    Higher lipid solubility of lipophilic salt forms creates new product development opportunities for high-dose liquid-filled capsules. The purpose of this study is to determine if lipophilic salts of Biopharmaceutical Classification System (BCS) Class I amlodipine and BCS Class III fexofenadine, ranitidine, and metformin were better lipid formulation candidates than existing commercial salts. Lipophilic salts were prepared from lipophilic anions and commercial HCl or besylate salt forms, as verified by (1)H-NMR. Thermal properties were assessed by differential scanning calorimetry and hot-stage microscopy. X-ray diffraction and polarized light microscopy were used to confirm the salt's physical form. All lipophilic salt forms were substantially more lipid-soluble (typically >10-fold) when compared to commercial salts. For example, amlodipine concentrations in lipidic excipients were limited to 100 mg/g when using the docusate salt. Higher lipid solubility of the lipophilic salts of each drug translated to higher drug loadings in lipid formulations. In vitro tests showed that lipophilic salts solubilized in a lipid formulation resulted in dispersion behavior that was at least as rapid as the dissolution rates of conventional salts. This study confirmed the applicability of forming lipophilic salts of BCS I and III drugs to promote the utility of lipid-based delivery systems. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  17. SAVANNAH RIVER SITE INCIPIENT SLUDGE MIXING IN RADIOACTIVE LIQUID WASTE STORAGE TANKS DURING SALT SOLUTION BLENDING

    Energy Technology Data Exchange (ETDEWEB)

    Leishear, R.; Poirier, M.; Lee, S.; Steeper, T.; Fowley, M.; Parkinson, K.

    2011-01-12

    This paper is the second in a series of four publications to document ongoing pilot scale testing and computational fluid dynamics (CFD) modeling of mixing processes in 85 foot diameter, 1.3 million gallon, radioactive liquid waste, storage tanks at Savannah River Site (SRS). Homogeneous blending of salt solutions is required in waste tanks. Settled solids (i.e., sludge) are required to remain undisturbed on the bottom of waste tanks during blending. Suspension of sludge during blending may potentially release radiolytically generated hydrogen trapped in the sludge, which is a safety concern. The first paper (Leishear, et. al. [1]) presented pilot scale blending experiments of miscible fluids to provide initial design requirements for a full scale blending pump. Scaling techniques for an 8 foot diameter pilot scale tank were also justified in that work. This second paper describes the overall reasons to perform tests, and documents pilot scale experiments performed to investigate disturbance of sludge, using non-radioactive sludge simulants. A third paper will document pilot scale CFD modeling for comparison to experimental pilot scale test results for both blending tests and sludge disturbance tests. That paper will also describe full scale CFD results. The final paper will document additional blending test results for stratified layers in salt solutions, scale up techniques, final full scale pump design recommendations, and operational recommendations. Specifically, this paper documents a series of pilot scale tests, where sludge simulant disturbance due to a blending pump or transfer pump are investigated. A principle design requirement for a blending pump is UoD, where Uo is the pump discharge nozzle velocity, and D is the nozzle diameter. Pilot scale test results showed that sludge was undisturbed below UoD = 0.47 ft{sup 2}/s, and that below UoD = 0.58 ft{sup 2}/s minimal sludge disturbance was observed. If sludge is minimally disturbed, hydrogen will not be

  18. PEG-salt aqueous two-phase systems: an attractive and versatile liquid-liquid extraction technology for the downstream processing of proteins and enzymes.

    Science.gov (United States)

    Glyk, Anna; Scheper, Thomas; Beutel, Sascha

    2015-08-01

    Nowadays, there is an increasing demand to establish new feasible, efficient downstream processing (DSP) techniques in biotechnology and related fields. Although several conventional DSP technologies have been widely employed, they are usually expensive and time-consuming and often provide only low recovery yields. Hence, the DSP is one major bottleneck for the commercialization of biological products. In this context, polyethylene glycol (PEG)-salt aqueous two-phase systems (ATPS) represent a promising, efficient liquid-liquid extraction technology for the DSP of various biomolecules, such as proteins and enzymes. Furthermore, ATPS can overcome the limitations of traditional DSP techniques and have gained importance for applications in several fields of biotechnology due to versatile advantages over conventional DSP methods, such as biocompatibility, technical simplicity, and easy scale-up potential. In the present review, various practical applications of PEG-salt ATPS are presented to highlight their feasibility to operate as an attractive and versatile liquid-liquid extraction technology for the DSP of proteins and enzymes, thus facilitating the approach of new researchers to this technique. Thereby, single- and multi-stage extraction, several process integration methods, as well as large-scale extraction and purification of proteins regarding technical aspects, scale-up, recycling of process chemicals, and economic aspects are discussed.

  19. Development of counter current salting-out homogenous liquid-liquid extraction for isolation and preconcentration of some pesticides from aqueous samples.

    Science.gov (United States)

    Farajzadeh, Mir Ali; Feriduni, Behruz; Afshar Mogaddam, Mohammad Reza

    2015-07-23

    In this paper, a new version of salting-out homogenous liquid-liquid extraction based on counter current mode combined with dispersive liquid-liquid microextraction has been developed for the extraction and preconcentration of some pesticides from aqueous samples and their determination by gas chromatography-flame ionization detection. In order to perform the method, aqueous solution of the analytes containing acetonitrile and 1,2-dibromoethane is transferred into a narrow bore tube which is filled partially with NaCl. During passing the solution through the tube, fine droplets of the organic phase are produced at the interface of solution and salt which go up through the tube and form a separated layer on the aqueous phase. The collected organic phase is removed and injected into de-ionized water for more enrichment of the analytes. Under the optimum extraction conditions, the method shows broad linear ranges for the target analytes. Enrichment factors and limits of detection for the selected pesticides are obtained in the ranges of 3480-3800 and 0.1-5μgL(-1), respectively. Relative standard deviations are in the range of 2-7% (n=6, C=50 or 100μgL(-1), each analyte). Finally, some aqueous samples were successfully analyzed using the developed method.

  20. Granular encapsulation of light hydrophobic liquids (LHL) in LHL-salt water systems: Particle induced densification with quartz sand.

    Science.gov (United States)

    Boglaienko, Daria; Tansel, Berrin; Sukop, Michael C

    2016-02-01

    Addition of granular materials to floating crude oil slicks can be effective in capturing and densifying the floating hydrophobic phase, which settles by gravity. Interaction of light hydrophobic liquids (LHL) with quartz sand was investigated in LHL-salt water systems. The LHLs studied were decane, tetradecane, hexadecane, benzene, toluene, ethylbenzene, m-xylene, and 2-cholorotoluene. Experiments were conducted with fine quartz sand (passing sieve No. 40 with openings 0.425 mm). Each LHL was dyed with few crystals of Sudan IV dye for ease of visual observation. A volume of 0.5 mL of each LHL was added to 100 mL salt water (34 g/L). Addition of one gram of quartz sand to the floating hydrophobic liquid layer resulted in formation of sand-encapsulated globules, which settled due to increased density. All LHLs (except for a few globules of decane) formed globules covered with fine sand particles that were heavy enough to settle by gravity. The encapsulated globules were stable and retained their shape upon settling. Polarity of hydrophobic liquids as the main factor of aggregation with minerals was found to be insufficient to explain LHL aggregation with sand. Contact angle measurements were made by submerging a large quartz crystal with the LHL drop on its surface into salt water. A positive correlation was observed between the wetting angle of LHL and the LHL volume captured (r = 0.75). The dependence of the globule density on globule radius was analyzed in relation to the coverage (%) of globule surface (LHL-salt water interface) by fine quartz particles. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Monitoring the oleuropein content of olive leaves and fruits using ultrasound- and salt-assisted liquid-liquid extraction optimized by response surface methodology and high-performance liquid chromatography.

    Science.gov (United States)

    Ismaili, Ahmad; Heydari, Rouhollah; Rezaeepour, Reza

    2016-01-01

    A novel and rapid ultrasound- and salt-assisted liquid-liquid extraction coupled with high-performance liquid chromatography has been optimized by response surface methodology for the determination of oleuropein from olive leaves. Box-Behnken design was used for optimizing the main parameters including ultrasound time (A), pH (B), salt concentration (C), and volume of miscible organic solvent (D). In this technique, a mixture of plant sample and extraction solvent was subjected to ultrasound waves. After ultrasound-assisted extraction, phase separation was performed by the addition of salt to the liquid phase. The optimal conditions for the highest extraction yield of oleuropein were ultrasound time, 30 min; volume of organic solvent, 2.5 mL; salt concentration, 25% w/v; and sample pH, 4. Experimental data were fitted with a quadratic model. Analysis of variance results show that BC interaction, A(2) , B(2) , C(2) , and D(2) are significant model terms. Unlike the conventional extraction methods for plant extracts, no evaporation and reconstitution operations were needed in the proposed technique.

  2. Nonafluorobutanesulfonyl azide as a shelf-stable highly reactive oxidant for the copper-catalyzed synthesis of 1,3-diynes from terminal alkynes.

    Science.gov (United States)

    Suárez, José Ramón; Collado-Sanz, Daniel; Cárdenas, Diego J; Chiara, Jose Luis

    2015-01-16

    Nonafluorobutanesulfonyl azide is a highly efficient reagent for the copper-catalyzed coupling of terminal alkynes to give symmetrical and unsymmetrical 1,3-diynes in good to excellent yields and with good functional group compatibility. The reaction is extremely fast (copper(I) or copper(II) salt (2–5 mol %) and an organic base (0.6 mol %). A possible mechanistic pathway is briefly discussed on the basis of model DFT theoretical calculations. The quantitative assessment of the safety of use and shelf stability of nonafluorobutanesulfonyl azide has confirmed that this reagent is a superior and safe alternative to other electrophilic azide reagents in use today.

  3. From salts to ionic liquids by systematic structural modifications: a rational approach towards the efficient modular synthesis of enantiopure imidazolium salts.

    Science.gov (United States)

    Ríos-Lombardía, Nicolás; Busto, Eduardo; Gotor-Fernández, Vicente; Gotor, Vicente; Porcar, Raúl; García-Verdugo, Eduardo; Luis, Santiago V; Alfonso, Ignacio; García-Granda, Santiago; Menéndez-Velázquez, Amador

    2010-01-18

    This paper reports a simple and robust modular synthetic strategy that leads to a large variety of configurationally and structurally diverse imidazole-based chiral ionic liquids (CILs) by lipase-catalyzed resolution. The intimate microscopic interactions of the supramolecular ionic network of these imidazolium chiral salts at the molecular level are investigated both spectroscopically (NMR, FT-IR-ATR) and theoretically, and a topological analysis of the experimental electron densities obtained by X-ray diffraction of single crystals is performed. Our results support the key role played by the relative configuration of the -OR group on the hydrogen-bonding pattern and its strong influence on the final physical properties of the imidazolium salt. We also obtained a reasonable correlation between the observed melting point and the non-covalent interactions. The spectroscopic data and the topological analysis reflect the key role played by hydrogen bonds between the OH and imidazolium C2H groups in both cation-anion and cation-cation interactions, with the presence of an OH group leading to an additional inter-cation interaction. This interaction significantly affects the properties of stereoisomeric salts. Even more interestingly, we also studied the effect of the chirality by comparing enantiopure CILs with their racemic mixtures and found that, with the exception of trans-Cy6-OH-Im-Bn-Br, the melting points of the racemic mixtures are higher than those of the corresponding enantiomerically pure forms. For stereoisomeric examples, we have successfully explained the differences in melting temperatures in light of the corresponding structural data. Chirality should therefore be taken into account as a highly attractive design vector in the preparation of ILs with specifically desired properties.

  4. Evaluation of aroma differences between high-salt liquid-state fermentation and low-salt solid-state fermentation soy sauces from China.

    Science.gov (United States)

    Feng, Yunzi; Cai, Yu; Su, Guowan; Zhao, Haifeng; Wang, Chenxia; Zhao, Mouming

    2014-02-15

    Two types of Chinese soy sauce, high-salt liquid-state fermentation soy sauce (HLFSS) and low-salt solid-state fermentation soy sauce (LSFSS), were used to investigate their differences in aroma profile by headspace solid-phase microextraction (HS-SPME) and gas chromatography-olfactometry/mass spectrometry (GC-O/MS). Results from descriptive sensory analysis showed that the alcoholic, cooked potato-like and caramel-like attributes were significantly higher in HLFSS, while LSFSS exhibited significantly higher sour and burnt attributes. In addition, aroma extract dilution analysis (AEDA) revealed 37 and 33 odour-active regions for HLFSS and LSFSS, respectively. Ethanol, 3-methyl-1-butanol, phenylacetaldehyde, 4-ethyl-2-methoxyphenol, 2-methoxy-4-vinylphenol and 3-(methylthio)propanal detected in HLFSS showed the highest flavour dilution (FD) factors, while 3-methylbutanal, phenylacetaldehyde and ethyl propanoate possessed the highest FD factors in LSFSS. Therefore, the traditional Chinese soy sauce HLFSS contained more complex volatiles and exhibited a richer aromatic profile compared with LSFSS.

  5. Development of tropine-salt aqueous two-phase systems and removal of hydrophilic ionic liquids from aqueous solution.

    Science.gov (United States)

    Wu, Haoran; Yao, Shun; Qian, Guofei; Song, Hang

    2016-08-26

    A novel aqueous two-phase systems (ATPS) composed of a small molecule organic compound tropine and an organic or inorganic salt aqueous solution has been developed for the first time. The phase behavior of tropine-salt ATPS was systemically investigated and the phase equilibrium data were measured in different temperatures and concentrations and correlated by the Merchuk equation with satisfactory results. The detection of the conductivity and particle size proved the formation of micelle in the process of forming tropine-salt ATPS. The separation application of the ATPS was assessed with the removal of hydrophilic benzothiazolium-based ionic liquids (ILs) from aqueous solution. The result showed that ILs were effectively extracted into the top tropine-rich phase. Finally, ILs in the top tropine-rich phase were further separated by the means of adsorption-desorption with DM301 macroporous resin and ethanol. The method of novel tropine-salt ATPS combined with adsorption-desorption is demonstrated a promising alternative thought and approach for the removal or recovery of hydrophilic compounds from aqueous media and also could provide a potential application for bio-separation.

  6. Salting-out assisted liquid-liquid extraction and partial least squares regression to assay low molecular weight polycyclic aromatic hydrocarbons leached from soils and sediments

    Science.gov (United States)

    Bressan, Lucas P.; do Nascimento, Paulo Cícero; Schmidt, Marcella E. P.; Faccin, Henrique; de Machado, Leandro Carvalho; Bohrer, Denise

    2017-02-01

    A novel method was developed to determine low molecular weight polycyclic aromatic hydrocarbons in aqueous leachates from soils and sediments using a salting-out assisted liquid-liquid extraction, synchronous fluorescence spectrometry and a multivariate calibration technique. Several experimental parameters were controlled and the optimum conditions were: sodium carbonate as the salting-out agent at concentration of 2 mol L- 1, 3 mL of acetonitrile as extraction solvent, 6 mL of aqueous leachate, vortexing for 5 min and centrifuging at 4000 rpm for 5 min. The partial least squares calibration was optimized to the lowest values of root mean squared error and five latent variables were chosen for each of the targeted compounds. The regression coefficients for the true versus predicted concentrations were higher than 0.99. Figures of merit for the multivariate method were calculated, namely sensitivity, multivariate detection limit and multivariate quantification limit. The selectivity was also evaluated and other polycyclic aromatic hydrocarbons did not interfere in the analysis. Likewise, high performance liquid chromatography was used as a comparative methodology, and the regression analysis between the methods showed no statistical difference (t-test). The proposed methodology was applied to soils and sediments of a Brazilian river and the recoveries ranged from 74.3% to 105.8%. Overall, the proposed methodology was suitable for the targeted compounds, showing that the extraction method can be applied to spectrofluorometric analysis and that the multivariate calibration is also suitable for these compounds in leachates from real samples.

  7. Salting-out assisted liquid-liquid extraction combined with capillary HPLC for the determination of sulfonylurea herbicides in environmental water and banana juice samples.

    Science.gov (United States)

    Gure, Abera; Lara, Francisco J; Moreno-González, David; Megersa, Negussie; del Olmo-Iruela, Monsalud; García-Campaña, Ana M

    2014-09-01

    A salting-out assisted liquid-liquid extraction (SALLE) combined with capillary high performance liquid chromatography with diode array detector (capillary HPLC-DAD) was proposed for extraction and determination of residues of nine sulfonylurea herbicides (SUHs) in environmental water and banana juice samples. Various parameters affecting the extraction process such as the type and volume of the organic solvent, sample volume, type and amount of salt, pH of the sample and vortex time were optimized. Under optimum conditions, matrix matched calibration curves were established using river water and banana juice samples. Good linear relationships as well as low limits of detection, LODs (0.4-1.3 and 3-13 µg/L) and quantification, LOQs (1.3-4.3 and 10-43 µg/L) were obtained in water and banana juice samples, respectively. The precision (intra- and inter-day) of the peak areas expressed as relative standard deviations (%, RSD), at two concentration levels were below 10 % in both matrices. Recoveries obtained from spiked environmental waters (river water and groundwater) and banana juice samples, at two concentration levels, ranged from 72 to 115%. The results of the analysis revealed that the proposed SALLE-capillary HPLC method is simple, rapid, cheap and environmentally friendly, being successfully applicable for the determination of SUH residues in waters and banana juices.

  8. Development of a robust ionic liquid-based dispersive liquid-liquid microextraction against high concentration of salt for preconcentration of trace metals in saline aqueous samples: Application to the determination of Pb and Cd

    Energy Technology Data Exchange (ETDEWEB)

    Yousefi, Seyed Reza [School of Chemistry, University College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Shemirani, Farzaneh, E-mail: shemiran@khayam.ut.ac.ir [School of Chemistry, University College of Science, University of Tehran, Tehran (Iran, Islamic Republic of)

    2010-06-11

    A new ionic liquid-based dispersive liquid-liquid microextraction method was developed for preconcentration and determination of compounds in aqueous samples containing very high salt concentrations. This method can solve the problems associated with the limited application of the conventional IL-based DLLME in these samples. This is believed to arise from dissolving of the ionic liquids in aqueous samples with high salt content. In this method, the robustness of microextraction system against high salt concentration (up to 40%, w/v) is increased by introducing a common ion of the ionic liquid into the sample solution. The proposed method was applied satisfactorily to the preconcentration of lead and cadmium in saline samples. After preconcentration, the settled IL-phase was dissolved in 100 {mu}L ethanol and aspirated into the flame atomic absorption spectrometer (FAAS) using a home-made microsample introduction system. Several variables affecting the microextraction efficiency were investigated and optimized. Under the optimized conditions and preconcentration of only 10 mL of sample, the enhancement factors of 273 and 311 and the detection limits of 0.6 {mu}g L{sup -1} and 0.03 {mu}g L{sup -1} were obtained for lead and cadmium, respectively. Validation of the method was performed by both an analysis of a certified reference material (CRM) and comparison of results with those obtained by ISO standard method.

  9. Miniaturized salting-out liquid-liquid extraction in a coupled-syringe system combined with HPLC-UV for extraction and determination of sulfanilamide.

    Science.gov (United States)

    Sereshti, Hassan; Khosraviani, Marzieh; Sadegh Amini-Fazl, Mohammad

    2014-04-01

    In salting-out liquid-liquid extraction (SALLE) technique, water-miscible organic solvents are used for extraction of polar analytes from saline solutions. In this study, for the first time, a coupled 1-mL syringes system was utilized to perform a miniaturized SALLE method. Sulfanilamide antibiotic was extracted and determined via the developed method followed by high performance liquid chromatography-ultraviolet detection (HPLC-UV). The extraction process was carried out by rapid shooting of acetonitrile as extraction solvent (syringe B) into saline aqueous sample solution (syringe A), and then the shooting was repeated several times at a rate of 1 cycles(-1). Thereby, an extremely large contact surface area was created between phases and led to a rapid equilibrium and mass transfer. In order to improve the efficiency of the method, the effect of extraction solvent (type and volume), shooting times, salt concentration, and pH on the extraction efficiency was investigated. The best performance of the method was achieved with 250 µL of acetonitrile, salt concentration of 250 mg mL(-1), pH of 7, and shooting times of 5. The linear dynamic range was 0.001-10 µg mL(-1) with the determination coefficient of 0.9999. The relative standard deviation (RSD; n=3, C=5 µg mL(-1)), and the limit of detection (LOD) were 1.55% and 0.3 ng mL(-1), respectively. The developed technique was successfully applied to genuine samples of tea, water, milk, honey, human urine, plasma and blood.

  10. Salt-assisted dispersive liquid-liquid microextraction coupled with programmed temperature vaporization gas chromatography-mass spectrometry for the determination of haloacetonitriles in drinking water.

    Science.gov (United States)

    Ma, Huilian; Li, Yun; Zhang, Haijun; Shah, Syed Mazhar; Chen, Jiping

    2014-09-01

    We report here a new analytical method for the simultaneous determination of seven haloacetonitriles (HANs) in drinking water by coupling salt-assisted dispersive liquid-liquid microextraction (SADLLME) with programmed temperature vaporizer-gas chromatography-mass spectrometry (PTV-GC-MS). The newly developed method involves the dispersion of the extractant in aqueous sample by addition of a few grams of salt and no dispersion liquid was required as compared to the traditional DLLME methods. The extractant (CH2Cl2, 50μL) and the salt (Na2SO4, 2.4g) were successively added to water (8mL) in a conical centrifuge tube that was shaken for 1min and centrifuged (3500rpm, 3min). The aliquot of sedimented phase (4μL) was then directly injected into the PTV-GC-MS system. The limits of detection and quantification for the HANs were 0.4-13.2ngL(-1) and 1.2-43.9ngL(-1), respectively. The calibration curves showed good linearity (r(2)≥0.9904) over 3 orders of magnitude. The repeatability of the method was investigated by evaluating the intra- and inter-day precisions. The relative standard deviations (RSDs) obtained were lower than 10.2% and 7.8% at low and high concentration levels. The relative recoveries ranged from 79.3% to 105.1%. The developed methodology was applied for the analysis of seven HANs in several drinking water samples in coastal and inland cities of China. It was demonstrated to be a simple, sensible, reproducible and environment friendly method for the determination of trace HANs in drinking water samples.

  11. Dual active ionic liquids and organic salts for inhibition of microbially influenced corrosion.

    Science.gov (United States)

    Seter, Marianne; Thomson, Melanie J; Stoimenovski, Jelena; MacFarlane, Douglas R; Forsyth, Maria

    2012-06-18

    We describe a series of novel compounds designed to combat the bacterial growth that leads to microbially induced corrosion on steel in the marine environment. A synergistic effect of the ionic components in these dual active organic salts is demonstrated.

  12. Molecular dynamics simulations of the structure of the graphene-ionic liquid/alkali salt mixtures interface.

    Science.gov (United States)

    Méndez-Morales, Trinidad; Carrete, Jesús; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Lynden-Bell, Ruth M; Varela, Luis M

    2014-07-14

    We performed molecular dynamics simulations of mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate with lithium tetrafluoroborate and potassium tetrafluoroborate between two charged and uncharged graphene walls, in order to analyze the structure of the well-known formation of layers that takes place on liquids under confinement. For this purpose, we studied the molecular density profiles, free energy profiles for bringing lithium and potassium cations from the bulk mixture to the graphene wall and the orientational distributions of imidazolium rings within the first adsorbed layer as a function of salt concentration and electrode potential. The charge densities in the electrodes were chosen to be zero and ±1 e nm(-2), and the salt molar percentages were %salt = 0, 10 and 25. We found that the layered structure extends up to 1-2 nm, where the bulk behaviour is recovered. In addition, whereas for the neutral surface the layers are composed of both ionic species, increasing the electrode potential, the structure changes to alternating cationic and anionic layers leading to an overcompensation of the charge of the previous layer. We also calculated the distribution of angles of imidazolium rings near neutral and charged graphene walls, finding a limited influence of the added salt. In addition, the average tilt of the imidazolium ring within the first layer goes from 36° with respect to a normal vector to the uncharged graphene wall to 62° in the presence of charged walls. The free energy profiles revealed that lithium and potassium ions are adsorbed on the negative surface only for the highest amount of salt, since the free energy barriers for approaching this electrode are considerably higher than kBT.

  13. Effect of salts on the solubility of ionic liquids in water: experimental and electrolyte Perturbed-Chain Statistical Associating Fluid Theory.

    Science.gov (United States)

    Neves, Catarina M S S; Held, Christoph; Mohammad, Sultan; Schleinitz, Miko; Coutinho, João A P; Freire, Mara G

    2015-12-21

    Due to scarce available experimental data, as well as due to the absence of predictive models, the influence of salts on the solubility of ionic liquids (ILs) in water is still poorly understood. To this end, this work addresses the solubility of the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]), at 298.15 K and 0.1 MPa, in aqueous salt solutions (from 0.1 to 1.5 mol kg(-1)). At salt molalities higher than 0.2 mol kg(-1), all salts caused salting-out of [C4C1im][NTf2] from aqueous solution with their strength decreasing in the following order: Al2(SO4)3 > ZnSO4 > K3C6H5O7 > KNaC4H4O6 > K3PO4 > Mg(CH3CO2)2 > K2HPO4 > MgSO4 > KH2PO4 > KCH3CO2. Some of these salts lead however to the salting-in of [C4C1im][NTf2] in aqueous medium at salt molalities lower than 0.2 mol kg(-1). To attempt the development of a model able to describe the salt effects, comprising both the salting-in and salting-out phenomena observed, the electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT) was applied using ion-specific parameters. The gathered experimental data was modelled using ePC-SAFT parameters complemented by fitting a single binary parameter between K(+) and the IL-ions to the IL solubility in K3PO4 aqueous solutions. Based on this approach, the description of anion-specific salting-out effects of the remaining potassium salts was found to be in good agreement with experimental data. Remarkably, ePC-SAFT is even able to predict the salting-in effect induced by K2HPO4, based on the single K(+)/IL-ions binary parameter which was fitted to an exclusively salting-out effect promoted by K3PO4. Finally, ePC-SAFT was applied to predict the influence of other sodium salts on the [C4C1im][NTf2] solubility in water, with experimental data taken from literature, leading to an excellent description of the liquid-liquid phase behaviour.

  14. In situ Fabrication of Monolithic Copper Azide

    Science.gov (United States)

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

    2016-04-01

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

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

    Science.gov (United States)

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

    2015-11-26

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

  16. AZIDE-ALKYNE CLICK POLYMERIZATION: AN UPDATE

    Institute of Scientific and Technical Information of China (English)

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

    2012-01-01

    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.

  17. Microextraction by packed sorbent and salting-out-assisted liquid-liquid extraction for the determination of aromatic amines formed from azo dyes in textiles.

    Science.gov (United States)

    Sánchez, Miguel del Nogal; Santos, Patricia Martín; Sappó, Cristina Pérez; Pavón, José Luis Pérez; Cordero, Bernardo Moreno

    2014-02-01

    EU legislation prohibits the use of certain azo dyes which, on reduction, form any of 22 aromatic amines listed in Regulation (EC) 1907/2006 at concentrations above the threshold limit of 30 mg Kg(-1). Two different extraction techniques for the determination of aromatic amines formed from azo dyes in textiles in combination with gas chromatography-mass spectrometry (GC-MS) are described. The first one is based on microextraction by packed sorbent (MEPS) and the other approach involves salting-out-assisted liquid-liquid extraction (SALLE). The influence of several parameters on the efficiency of the extraction using MEPS (sorbent material, sample volume, elution solvent, elution volume and washing steps, among others) and SALLE (extraction volume and amount of salt) were investigated. In addition, chromatographic separation was optimized and quadrupole mass spectrometry was evaluated using the synchronous SIM/scan data acquisition mode. The repeatability (n=8, S/N=3) of the methods, calculated as the relative standard deviation (RSD) was below 15 and 11% for all compounds when MEPS and SALLE were used, respectively. Standard additions procedure was used to quantify the aromatic amines in the textil samples. The detection limits in the samples for both methods were lower than the maximum value allowed by legislation. The results obtained in the analysis of textiles revealed the presence of o-anisidine, p-chloroaniline, 4-chloro-o-toluidine, 2-naphthylamine and 3,3'-dimethoxybenzidine in some of them. © 2013 Elsevier B.V. All rights reserved.

  18. Combination of dispersive solid-phase extraction and salting-out homogeneous liquid-liquid extraction for the determination of organophosphorus pesticides in cereal grains.

    Science.gov (United States)

    Jia, Chunhong; Zhu, Xiaodan; Wang, Jihua; Zhao, Ercheng; He, Min; Chen, Li; Yu, Pingzhong

    2014-07-01

    A new analytical method for the determination of organophosphorus pesticides in cereal samples was developed by combining dispersive SPE (d-SPE) and salting-out homogeneous liquid-liquid extraction (SHLLE). The pesticides were first extracted from cereal grains with acetonitrile, followed by d-SPE cleanup. A 2 mL aliquot of the extract was then added to a centrifuge tube containing 9.2 mL water and 3.3 g NaCl for SHLLE. Analysis of the extract was carried out by gas chromatography coupled with flame photometric detection. The d-SPE procedure effectively provides the necessary cleanup of the extract while SHLLE is used as an efficient concentration technique. Experimental parameters influencing the extraction efficiency including amounts of added water and salt were investigated. Recovery studies were carried out at three fortification levels, yielding recoveries in the range of 57.7-98.1% with the RSD from 3.7 to 10.9%. The reported limits of determination obtained from this study were 1 μg/kg, which is better than the conventional methods. In the analysis of 40 wheat and corn samples taken from Beijing suburbs, only two wheat samples have chlorpyrifos residue over the limits of determination.

  19. Determination of the diffusion coefficient of salts in non-Newtonian liquids by the Taylor dispersion method

    Energy Technology Data Exchange (ETDEWEB)

    Mey, Paula; Varges, Priscilla R.; Mendes, Paulo R. de Souza [Dept. of Mechanical Engineering. Pontificia Universidade Catolica do RJ (PUC-Rio), RJ (Brazil)], e-mails: prvarges@puc-rio.br, pmendes@puc-rio.br

    2010-07-01

    This research looked for a method to determine the binary diffusion coefficient D of salts in liquids (especially in drilling fluids) not only accurately, but in a reasonable time. We chose to use the Taylor Dispersion Method. This technique has been used for measuring binary diffusion coefficients in gaseous, liquid and supercritical fluids, due to its simplicity and accuracy. In the method, the diffusion coefficient is determined by the analysis of the dispersion of a pulse of soluble material in a solvent flowing laminarly through a tube. This work describes the theoretical basis and the experimental requirements for the application of the Taylor Dispersion Method, emphasizing the description of our experiment. A mathematical formulation for both Newtonian and non-Newtonian fluids is presented. The relevant sources of errors are discussed. The experimental procedure and associated analysis are validated by applying the method in well known systems, such as NaCl in water.D of salts in liquids (especially in drilling fluids) not only accurately, but in a reasonable time. We chose to use the Taylor Dispersion Method. This technique has been used for measuring binary diffusion coefficients in gaseous, liquid and supercritical fluids, due to its simplicity and accuracy. In the method, the diffusion coefficient is determined by the analysis of the dispersion of a pulse of soluble material in a solvent flowing laminarly through a tube. This work describes the theoretical basis and the experimental requirements for the application of the Taylor Dispersion Method, emphasizing the description of our experiment. A mathematical formulation for both Newtonian and non-Newtonian fluids is presented. The relevant sources of errors are discussed. The experimental procedure and associated analysis are validated by applying the method in well known systems, such as NaCl in water. (author)

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

    Science.gov (United States)

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

    2008-01-01

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

  1. A Simple Halide-to-Anion Exchange Method for Heteroaromatic Salts and Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Neus Mesquida

    2012-04-01

    Full Text Available A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form in non-aqueous media. The anion loading of the AER (OH− form was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7 and the anion exchange was equally successful with both lipophilic cations and anions.

  2. Effect of salts on the solubility of ionic liquids in water: experimental and electrolyte Perturbed-Chain Statistical Associating Fluid Theory†

    Science.gov (United States)

    Mohammad, Sultan; Schleinitz, Miko; Coutinhoa, João A. P.; Freire, Mara G.

    2016-01-01

    Due to scarce available experimental data, as well as due to the absence of predictive models, the influence of salts on the solubility of ionic liquids (ILs) in water is still poorly understood. To this end, this work addresses the solubility of the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]), at 298.15 K and 0.1 MPa, in aqueous salt solutions (from 0.1 to 1.5 mol kg−1). At salt molalities higher than 0.2 mol kg−1, all salts caused salting-out of [C4C1im][NTf2] from aqueous solution with their strength decreasing in the following order: Al2(SO4)3 > ZnSO4 > K3C6H5O7 > KNaC4H4O6 > K3PO4 > Mg(CH3CO2)2 > K2HPO4 > MgSO4 > KH2PO4 > KCH3CO2. Some of these salts lead however to the salting-in of [C4C1im][NTf2] in aqueous medium at salt molalities lower than 0.20 mol kg−1. To attempt the development of a model able to describe the salt effects, comprising both the salting-in and salting-out phenomena observed, the electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT) was applied using ion-specific parameters. The gathered experimental data was modelled using ePC-SAFT parameters complemented by fitting a single binary parameter between K+ and the IL-ions to the IL solubility in K3PO4 aqueous solutions. Based on this approach, the description of anion-specific salting-out effects of the remaining potassium salts was found to be in good agreement with experimental data. Remarkably, ePC-SAFT is even able to predict the salting-in effect induced by K2HPO4, based on the single K+/IL-ions binary parameter which was fitted to an exclusively salting-out effect promoted by K3PO4. Finally, ePC-SAFT was applied to predict the influence of other sodium salts on the [C4C1im][NTf2] solubility in water, with experimental data taken from literature, leading to an excellent description of the liquid–liquid phase behaviour. PMID:26575280

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

    Directory of Open Access Journals (Sweden)

    Herwig Schottenberger

    2012-03-01

    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.

  4. A concomitant allylic azide rearrangement/intramolecular azide-alkyne cycloaddition sequence.

    Science.gov (United States)

    Vekariya, Rakesh H; Liu, Ruzhang; Aubé, Jeffrey

    2014-04-04

    An intramolecular Huisgen cycloaddition of an interconverting set of isomeric allylic azides with alkynes affords substituted triazoles in high yield. The stereoisomeric vinyl-substituted triazoloxazines formed depend on the rate of cycloaddition of the different allylic azide precursors when the reaction is carried out under thermal conditions. In contrast, dimerized macrocyclic products were obtained when the reaction was done using copper(I)-catalyzed conditions, demonstrating the ability to control the reaction products through changing conditions.

  5. Synthesis of Azide-Functionalized Hydroxyl-Terminated Polybutadiene

    Science.gov (United States)

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

    2016-10-01

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

  6. Liquid-liquid extraction of ion-association complexes of cobalt(II-4-(2-pyridylazoresorcinol with ditetrazolium salts

    Directory of Open Access Journals (Sweden)

    Divarova Vidka V.

    2015-01-01

    Full Text Available The formation and liquid-liquid extraction of ion-association complexes between Co(II-4-(2-Pyridylazoresorcinol (PAR anionic chelates and cations of three ditetrazolium chlorides were studied: Blue Tetrazolium chloride (BTC, Neotetrazolium chloride (NTC and Nitro Blue Tetrazolium chloride (NBT. The optimum conditions for the formation and solvent extraction of the ion-association comlpex chelates were determined. It has been found that in the systems of Co(II-PAR-DTS, the reactants are reacted in molar ratios 1:2:1 and the general formula of complexes was suggested. The extraction equilibria were investigated and quantitatively characterized by the equilibrium constants and the recovery factors. The analytical characteristics of the complexes were calculated.

  7. Development of a new extraction method based on counter current salting-out homogenous liquid-liquid extraction followed by dispersive liquid-liquid microextraction: Application for the extraction and preconcentration of widely used pesticides from fruit juices.

    Science.gov (United States)

    Farajzadeh, Mir Ali; Feriduni, Behruz; Mogaddam, Mohammad Reza Afshar

    2016-01-01

    In this paper, a new extraction method based on counter current salting-out homogenous liquid-liquid extraction (CCSHLLE) followed by dispersive liquid-liquid microextraction (DLLME) has been developed for the extraction and preconcentration of widely used pesticides in fruit juice samples prior to their analysis by gas chromatography-flame ionization detection (GC-FID). In this method, initially, sodium chloride as a separation reagent is filled into a small column and a mixture of water (or fruit juice) and acetonitrile is passed through the column. By passing the mixture sodium chloride is dissolved and the fine droplets of acetonitrile are formed due to salting-out effect. The produced droplets go up through the remained mixture and collect as a separated layer. Then, the collected organic phase (acetonitrile) is removed with a syringe and mixed with 1,1,2,2-tetrachloroethane (extraction solvent at µL level). In the second step, for further enrichment of the analytes the above mixture is injected into 5 mL de-ionized water placed in a test tube with conical bottom in order to dissolve acetonitrile into water and to achieve a sedimented phase at µL-level volume containing the enriched analytes. Under the optimal extraction conditions (extraction solvent, 1.5 mL acetonitrile; pH, 7; flow rate, 0.5 mL min(-1); preconcentration solvent, 20 µL 1,1,2,2-tetrachloroethane; NaCl concentration; 5%, w/w; and centrifugation rate and time, 5000 rpm and 5 min, respectively), the extraction recoveries and enrichment factors ranged from 87% to 96% and 544 to 600, respectively. Repeatability of the proposed method, expressed as relative standard deviations, ranged from 2% to 6% for intra-day (n=6, C=250 or 500 µg L(-1)) and inter-days (n=4, C=250 or 500 µg L(-1)) precisions. Limits of detection are obtained between 2 and 12 µg L(-1). Finally, the proposed method is applied for the determination of the target pesticide residues in the juice samples.

  8. Status of Physics and Safety Analyses for the Liquid-Salt-Cooled Very High-Temperature Reactor (LS-VHTR)

    Energy Technology Data Exchange (ETDEWEB)

    Ingersoll, DT

    2005-12-15

    A study has been completed to develop a new baseline core design for the liquid-salt-cooled very high-temperature reactor (LS-VHTR) that is better optimized for liquid coolant and that satisfies the top-level operational and safety targets, including strong passive safety performance, acceptable fuel cycle parameters, and favorable core reactivity response to coolant voiding. Three organizations participated in the study: Oak Ridge National Laboratory (ORNL), Idaho National Laboratory (INL), and Argonne National Laboratory (ANL). Although the intent was to generate a new reference LS-VHTR core design, the emphasis was on performing parametric studies of the many variables that constitute a design. The results of the parametric studies not only provide the basis for choosing the optimum balance of design options, they also provide a valuable understanding of the fundamental behavior of the core, which will be the basis of future design trade-off studies. A new 2400-MW(t) baseline design was established that consists of a cylindrical, nonannular core cooled by liquid {sup 7}Li{sub 2}BeF{sub 4} (Flibe) salt. The inlet and outlet coolant temperatures were decreased by 50 C, and the coolant channel diameter was increased to help lower the maximum fuel and vessel temperatures. An 18-month fuel cycle length with 156 GWD/t burnup was achieved with a two-batch shuffling scheme, while maintaining a core power density of 10 MW/m{sup 3} using graphite-coated uranium oxicarbide particle fuel enriched to 15% {sup 235}U and assuming a 25 vol-% packing of the coated particles in the fuel compacts. The revised design appears to have excellent steady-state and transient performance. The previous concern regarding the core's response to coolant voiding has been resolved for the case of Flibe coolant by increasing the coolant channel diameter and the fuel loading. Also, the LSVHTR has a strong decay heat removal performance and appears capable of surviving a loss of forced

  9. Azide anions inhibit GH-18 endochitinase and GH-20 Exo β-N-acetylglucosaminidase from the marine bacterium Vibrio harveyi.

    Science.gov (United States)

    Sirimontree, Paknisa; Fukamizo, Tamo; Suginta, Wipa

    2016-02-01

    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.

  10. High-throughput salting-out assisted liquid-liquid extraction with acetonitrile for the determination of anandamide in plasma of hemodialysis patients with liquid chromatography tandem mass spectrometry.

    Science.gov (United States)

    Xiong, Xin; Zhang, Lei; Cheng, Litao; Mao, Wei

    2015-09-01

    Anandamide (AEA) is an endocannabinoid present in human plasma that is associated with several physiological functions and disease states. However, low AEA plasma levels pose challenges in terms of analytical characterization. Classical liquid-based lipid extraction and solid-phase extraction require complicated procedures and the drying down of relatively large volumes of solvents, making them unsuitable for high-throughput analysis. Here a high-throughput salting-out assisted liquid-liquid extraction (SALLE) method with acetonitrile and mass spectrometry compatible salts for liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis of AEA in human plasma has been developed and validated. The seamless interface of SALLE and LC-MS eliminated the drying-down step, only 100 μL of plasma is required and minimal volumes of organic solvent are used. Good reproducibility, accuracy and precision were demonstrated during the method validation. The method is linear up to 10 ng/mL with a lower limit of quantitation of 0.1 ng/mL for AEA, the accuracy for AEA was from 93.3 to 96.7% and the precision was <8.57%. This new methodology was successfully applied to analysis of clinical samples from maintenance hemodialysis patients.

  11. Design, testing, fabrication and launch support of a liquid chemical barium release payload (utilizing the liquid fluorine-barium salt/hydrazine system)

    Science.gov (United States)

    Stokes, C. S.; Smith, E. W.; Murphy, W. J.

    1972-01-01

    A payload was designed which included a cryogenic oxidizer tank, a fuel tank, and burner section. Release of 30 lb of chemicals was planned to occur in 2 seconds at the optimum oxidizer to fuel ratio. The chemicals consisted of 17 lb of liquid fluorine oxidizer and 13 lb of hydrazine-barium salt fuel mixture. The fuel mixture was 17% barium chloride, 16% barium nitrate, and 67% hydrazine, and contained 2.6 lb of available barium. Two significant problem areas were resolved during the program: explosive valve development and burner operation. The release payload was flight tested, from Wallops Island, Virginia. The release took place at an altitude of approximately 260 km. The release produced a luminous cloud which expanded very rapidly, disappearing to the human eye in about 20 seconds. Barium ion concentration slowly increased over a wide area of sky until measurements were discontinued at sunrise (about 30 minutes).

  12. Separation, concentration and determination of chloramphenicol in environment and food using an ionic liquid/salt aqueous two-phase flotation system coupled with high-performance liquid chromatography.

    Science.gov (United States)

    Han, Juan; Wang, Yun; Yu, Cuilan; Li, Chunxiang; Yan, Yongsheng; Liu, Yan; Wang, Liang

    2011-01-31

    Ionic liquid-salt aqueous two-phase flotation (ILATPF) is a novel, green, non-toxic and sensitive samples pretreatment technique. ILATPF coupled with high-performance liquid chromatography (HPLC) was developed for the analysis of chloramphenicol, which combines ionic liquid aqueous two-phase system (ILATPS) based on imidazolium ionic liquid (1-butyl-3-methylimidazolium chloride, [C(4)mim]Cl) and inorganic salt (K(2)HPO(4)) with solvent sublation. In ILATPF systems, phase behaviors of the ILATPF were studied for different types of ionic liquids and salts. The sublation efficiency of chloramphenicol in [C(4)mim]Cl-K(2)HPO(4) ILATPF was influenced by the types of salts, concentration of K(2)HPO(4) in aqueous solution, solution pH, nitrogen flow rate, sublation time and the amount of [C(4)mim]Cl. Under the optimum conditions, the average sublation efficiency is up to 98.5%. The mechanism of ILATPF contains two principal processes. One is the mechanism of IL-salt ILATPS formation, the other is solvent sublation. This method was practical when applied to the analysis of chloramphenicol in lake water, feed water, milk, and honey samples with the linear range of 0.5-500 ng mL(-1). The method yielded limit of detection (LOD) of 0.1 ng mL(-1) and limit of quantification (LOQ) of 0.3 ng mL(-1). The recovery of CAP was 97.1-101.9% from aqueous samples of environmental and food samples by the proposed method. Compared with liquid-liquid extraction, solvent sublation and ionic liquid aqueous two-phase extraction, ILATPF can not only separate and concentrate chloramphenicol with high sublation efficiency, but also efficiently reduce the wastage of IL. This novel technique is much simpler and more environmentally friendly and is suggested to have important applications for the concentration and separation of other small biomolecules.

  13. Salt Effect on the Liquid-Liquid Equilibrium of (Water + Propionic Acid + Cyclohexanol) System at T=(298.2,303.2,and 308.2) K

    Institute of Scientific and Technical Information of China (English)

    Bahram Ghalami-Choobar; Ali Ghanadzadeh and Shahram Kousarimehr

    2011-01-01

    Effects of salt and temperature on the liquid phase equilibrium of the(water + propionic acid + cyclohexanol) system were investigated.The liquid-liquid equilibrium data in the presence of KCl for various salt ionic strength of 0.5,1.0,1.5,2.0,and 2.5 mol·dm3 and in absence of the salt at T=(298.2,303.2,and 308.2)K were determined.The experimental results were correlated based on the Othmer-Tobias equation and Pitzer ion-interaction model.Thermodynamic properties such as distribution coefficients and activity coefficients of propionic acid in water + cyclohexanol were determined.In addition,the separation factor,S,of the chosen solvent was obtained for the investigated system.

  14. Effect of lithium salts addition on the ionic liquid based extraction of essential oil from Farfarae Flos.

    Science.gov (United States)

    Li, Zhen-Yu; Zhang, Sha-Sha; Jie-Xing; Qin, Xue-Mei

    2015-01-01

    In this study, an ionic liquids (ILs) based extraction approach has been successfully applied to the extraction of essential oil from Farfarae Flos, and the effect of lithium chloride was also investigated. The results indicated that the oil yields can be increased by the ILs, and the extraction time can be reduced significantly (from 4h to 2h), compared with the conventional water distillation. The addition of lithium chloride showed different effect according to the structures of ILs, and the oil yields may be related with the structure of cation, while the chemical compositions of essential oil may be related with the anion. The reduction of extraction time and remarkable higher efficiency (5.41-62.17% improved) by combination of lithium salt and proper ILs supports the suitability of the proposed approach.

  15. Influence of ionic liquid and ionic salt on protein against the reactive species generated using dielectric barrier discharge plasma.

    Science.gov (United States)

    Attri, Pankaj; Sarinont, Thapanut; Kim, Minsup; Amano, Takaaki; Koga, Kazunori; Cho, Art E; Choi, Eun Ha; Shiratani, Masaharu

    2015-12-10

    The presence of salts in biological solution can affect the activity of the reactive species (RS) generated by plasma, and so they can also have an influence on the plasma-induced sterilization. In this work, we assess the influence that diethylammonium dihydrogen phosphate (DEAP), an ionic liquid (IL), and sodium chloride (NaCl), an ionic salt (IS), have on the structural changes in hemoglobin (Hb) in the presence of RS generated using dielectric barrier discharge (DBD) plasma in the presence of various gases [O2, N2, Ar, He, NO (10%) + N2 and Air]. We carry out fluorescence spectroscopy to verify the generation of (•)OH with or without the presence of DEAP IL and IS, and we use electron spin resonance (ESR) to check the generation of H(•) and (•)OH. In addition, we verified the structural changes in the Hb structure after treatment with DBD in presence and absence of IL and IS. We then assessed the structural stability of the Hb in the presence of IL and IS by using molecular dynamic (MD) simulations. Our results indicate that the IL has a strong effect on the conservation of the Hb structure relative to that of IS against RS generated by plasma.

  16. Chromatographic retention behaviour, modelling and separation optimisation of the quaternary ammonium salt isometamidium chloride and related compounds on a range of reversed-phase liquid chromatographic stationary phases.

    Science.gov (United States)

    Schad, Gesa J; Euerby, Melvin R; Skellern, Graham G; Tettey, Justice N A

    2012-07-01

    This paper describes the reversed-phase liquid chromatographic behaviour of the trypanocidal quaternary ammonium salt isometamidium chloride and its related compounds on a range of liquid chromatographic phases possessing alkyl and phenyl ligands on the same inert silica. In a parallel study with various extended polar selectivity phases which possessed different hydrophobic/silanophilic (hydrogen bonding) activity ratios, the chromatographic retention/selectivities of the quaternary ammonium salts was shown to be due to a co-operative mechanism between hydrophobic and silanophilic interactions. The highly aromatic and planar isometamidium compounds were found to be substantially retained on stationary phases containing aromatic functionality via strong π-π interactions. The chemometric approach of principal component analysis was used to characterise the chromatographic behaviour of the isometamidium compounds on the differing phases and to help identify the dominant retention mechanism(s). Two-dimensional (temperature/gradient) retention modelling was employed to develop and optimise a rapid liquid chromatography method for the separation of the six quaternary ammonium salts within 2.5 min which would be suitable for bioanalysis using liquid chromatography-mass spectrometry. This is the first reported systematic study of the relationship between stationary phase chemistries and retention/selectivity for a group of quaternary ammonium salts.

  17. Optimization of a phase separation based magnetic-stirring salt-induced liquid-liquid microextraction method for determination of fluoroquinolones in food.

    Science.gov (United States)

    Gao, Ming; Wang, Huili; Ma, Meiping; Zhang, Yuna; Yin, Xiaohan; Dahlgren, Randy A; Du, Dongli; Wang, Xuedong

    2015-05-15

    Herein, we developed a novel integrated apparatus to perform phase separation based on magnetic-stirring, salt-induced, liquid-liquid microextraction for determination of five fluoroquinolones in animal-based foods by HPLC analysis. The novel integrated apparatus consisted of three simple HDPE (high density polyethylene) parts that were used to separate the solvent from the aqueous solution prior to retrieving the extractant. The extraction parameters were optimized using the response surface method based on central composite design: 791 μL of acetone solvent, 2.5 g of Na2SO4, pH 1.7, 3.0 min of stir time, and 5.5 min centrifugation. The limits of detection were 0.07-0.53 μg kg(-1) and recoveries were 91.6-105.0% for the five fluoroquinolones from milk, eggs and honey. This method is easily constructed from inexpensive materials, extraction efficiency is high, and the approach is compatible with HPLC analysis. Thus, it has excellent prospects for sample pre-treatment and analysis of fluoroquinolones in animal-based foods. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Rapid screening of haloacetamides in water using salt-assisted liquid-liquid extraction coupled injection-port silylation gas chromatography-mass spectrometry.

    Science.gov (United States)

    Chen, Tzu-Ling; Tzing, Shin-Hwa; Ding, Wang-Hsien

    2015-11-27

    The rapid screening of trace amounts of the nitrogenous disinfection by-products, haloacetamides (HAcAms), in drinking and swimming pool water was performed by a simple and reliable procedure based on salt-assisted liquid-liquid extraction (SALLE) combined with injection-port silylation gas chromatography-mass spectrometry (IPS-GC-MS) method. The optimal SALLE conditions involved the injection of 4-mL of ethyl acetate into a 10-mL water sample (pH 7) containing 3-g of sodium sulfate. After vortex extraction for 1min and centrifugation, 10μL of the extract (mixed with 1μL of MTBSTFA) was directly determined by IPS-GC-MS. The limits of quantitation (LOQs) were determined to be 0.03-0.3μg/L. Precision, as indicated by relative standard deviations (RSDs), was less than 10% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 76% and 94%. The SALLE plus IPS-GC-MS was successfully applied to quantitatively determine HAcAms from drinking and swimming pool water samples, and the total concentrations of the compounds ranged from 0.43 to 4.03μg/L.

  19. Liquid-liquid reductive extraction in molten fluoride salt/liquid aluminium as a core of process for the An/Ln group separation

    Energy Technology Data Exchange (ETDEWEB)

    Conocar, O

    2007-06-15

    This report concerns a pyrochemical process based on liquid-liquid extraction in a molten fluoride/liquid aluminium system as a core process for actinide (An)/lanthanide (Ln) group separation, studied at CEA. The basic and demonstrative experiments have established the feasibility of the An/Ln group separation in the molten fluoride/liquid aluminium system (U, Pu, Np, Am, Cm traces from Nd, Ce, Eu, Sm, Eu, La - An/Ln separation factors over 1000 - An recovery yield over 98 % in one batch). The main experimental efforts must now be targeted on the recovery of actinides from the Al matrix. A thermodynamic and bibliographical survey has been done. It shows that back-extraction in a molten chloride melt could be a promising technique for this purpose.

  20. High-throughput salting-out-assisted liquid-liquid extraction for the simultaneous determination of atorvastatin, ortho-hydroxyatorvastatin, and para-hydroxyatorvastatin in human plasma using ultrafast liquid chromatography with tandem mass spectrometry.

    Science.gov (United States)

    Yang, Yong; Xu, Qiufang; Zhou, Lei; Zhong, Dafang; Chen, Xiaoyan

    2015-03-01

    A high-throughput, specific, and rapid liquid chromatography with tandem mass spectrometry method was established and validated for the simultaneous determination of atorvastatin and its two major metabolites, ortho-hydroxyatorvastatin and para-hydroxyatorvastatin, in human plasma. A simple salting-out-assisted liquid-liquid extraction using acetonitrile and a mass-spectrometry-friendly salt, ammonium acetate, was employed to extract the analytes from human plasma. A recovery of more than 81% for all analytes was achieved in 1 min extraction time. Chromatographic separation was performed on a Kinetex XB C18 column utilizing a gradient elution starting with a 60% of water solution (1% formic acid), followed by increasing percentages of acetonitrile. Analytes were detected on a tandem mass spectrometer equipped with an electrospray ionization source that was operated in the positive mode, using the transitions of m/z 559.3 → m/z 440.2 for atorvastatin, and m/z 575.3 → m/z 440.2 for both ortho- and para-hydroxyatorvastatin. Deuterium-labeled compounds were used as the internal standards. The method was validated over the concentration ranges of 0.0200-15.0 ng/mL for atorvastatin and ortho-hydroxyatorvastatin, and 0.0100-2.00 ng/mL for para-hydroxyatorvastatin with acceptable accuracy and precision. It was then successfully applied in a bioequivalence study of atorvastatin.

  1. Use of ferric- and ferrous-salts in liquid waste treatment processes

    Energy Technology Data Exchange (ETDEWEB)

    Efremenkov, V.M.; Toropov, I.G.; Toropova, V.V.; Satsukevich, V.M.; Davidov, J.P.; Jabrodsky, V.N.; Prokshin, N.E.

    1995-12-31

    Treatment of spent decontamination solutions is the most complicated task in the whole problem of management of liquid radioactive waste, because quite often they have complex compositions, which makes it difficult to find for them effective and non-expensive treatment technology. New methods of treatment of such a waste is proposed based on use of specific sorption ability of ferro- and ferri-species in solution. These species are often present in solution as the by-products, and in combination with other components of decontamination solution they can be used as initial substances for synthesis of valuable sorbents directly in treating solution. Using specific compositions and conditions in solution, it is possible to make liquid waste treatment process more effective and less expensive. Particular examples of this process is presented in this work.

  2. Rapid determination of triclosan in personal care products using new in-tube based ultrasound-assisted salt-induced liquid-liquid microextraction coupled with high performance liquid chromatography-ultraviolet detection.

    Science.gov (United States)

    Chen, Ming-Jen; Liu, Ya-Ting; Lin, Chiao-Wen; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

    2013-03-12

    This paper describes the development of a novel, simple and efficient in-tube based ultrasound-assisted salt-induced liquid-liquid microextraction (IT-USA-SI-LLME) technique for the rapid determination of triclosan (TCS) in personal care products by high performance liquid chromatography-ultraviolet (HPLC-UV) detection. IT-USA-SI-LLME method is based on the rapid phase separation of water-miscible organic solvent from the aqueous phase in the presence of high concentration of salt (salting-out phenomena) under ultrasonication. In the present work, an indigenously fabricated home-made glass extraction device (8-mL glass tube inbuilt with a self-scaled capillary tip) was utilized as the phase separation device for USA-SI-LLME. After the extraction, the upper extractant layer was narrowed into the self-scaled capillary tip by pushing the plunger plug; thus, the collection and measurement of the upper organic solvent layer was simple and convenient. The effects of various parameters on the extraction efficiency were thoroughly evaluated and optimized. Under optimal conditions, detection was linear in the concentration range of 0.4-100ngmL(-1) with correlation coefficient of 0.9968. The limit of detection was 0.09ngmL(-1) and the relative standard deviations ranged between 0.8 and 5.3% (n=5). The applicability of the developed method was demonstrated for the analysis of TCS in different commercial personal care products and the relative recoveries ranged from 90.4 to 98.5%. The present method was proven to be a simple, sensitive, less organic solvent consuming, inexpensive and rapid procedure for analysis of TCS in a variety of commercially available personal care products or cosmetic preparations.

  3. High-Pressure Synthesis of a Pentazolate Salt

    Energy Technology Data Exchange (ETDEWEB)

    Steele, Brad A.; Stavrou, Elissaios; Crowhurst, Jonathan C.; Zaug, Joseph M.; Prakapenka, Vitali B.; Oleynik, Ivan I.

    2017-01-24

    The pentazolates, the last all-nitrogen members of the azole series, have been notoriously elusive for the last hundred years despite enormous efforts to make these compounds in either gas or condensed phases. Here, we report a successful synthesis of a solid state compound consisting of isolated pentazolate anions N5–, which is achieved by compressing and laser heating cesium azide (CsN3) mixed with N2 cryogenic liquid in a diamond anvil cell. The experiment was guided by theory, which predicted the transformation of the mixture at high pressures to a new compound, cesium pentazolate salt (CsN5). Electron transfer from Cs atoms to N5 rings enables both aromaticity in the pentazolates as well as ionic bonding in the CsN5 crystal. This work provides critical insight into the role of extreme conditions in exploring unusual bonding routes that ultimately lead to the formation of novel high nitrogen content species.

  4. Towards the Synthesis of Graphene Azide from Graphene Oxide

    OpenAIRE

    2015-01-01

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

  5. Design of Complex Systems to Achieve Passive Safety: Natural Circulation Cooling of Liquid Salt Pebble Bed Reactors

    Science.gov (United States)

    Scarlat, Raluca Olga

    This dissertation treats system design, modeling of transient system response, and characterization of individual phenomena and demonstrates a framework for integration of these three activities early in the design process of a complex engineered system. A system analysis framework for prioritization of experiments, modeling, and development of detailed design is proposed. Two fundamental topics in thermal-hydraulics are discussed, which illustrate the integration of modeling and experimentation with nuclear reactor design and safety analysis: thermal-hydraulic modeling of heat generating pebble bed cores, and scaled experiments for natural circulation heat removal with Boussinesq liquids. The case studies used in this dissertation are derived from the design and safety analysis of a pebble bed fluoride salt cooled high temperature nuclear reactor (PB-FHR), currently under development in the United States at the university and national laboratories level. In the context of the phenomena identification and ranking table (PIRT) methodology, new tools and approaches are proposed and demonstrated here, which are specifically relevant to technology in the early stages of development, and to analysis of passive safety features. A system decomposition approach is proposed. Definition of system functional requirements complements identification and compilation of the current knowledge base for the behavior of the system. Two new graphical tools are developed for ranking of phenomena importance: a phenomena ranking map, and a phenomena identification and ranking matrix (PIRM). The functional requirements established through this methodology were used for the design and optimization of the reactor core, and for the transient analysis and design of the passive natural circulation driven decay heat removal system for the PB-FHR. A numerical modeling approach for heat-generating porous media, with multi-dimensional fluid flow is presented. The application of this modeling

  6. Response Surface Optimization of Lead Azide for Explosive Detonators

    National Research Council Canada - National Science Library

    McCulloh, Ian; Massie, Darrell; Cordaro, Emily

    2006-01-01

    The Armament Research, Development and Engineering Center, Picatinny (ARDEC) has been tasked with developing a new chemical process to produce lead azide, the key explosive ingredient in detonators...

  7. Integral and Separate Effects Tests for Thermal Hydraulics Code Validation for Liquid-Salt Cooled Nuclear Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Peterson, Per

    2012-10-30

    The objective of the 3-year project was to collect integral effects test (IET) data to validate the RELAP5-3D code and other thermal hydraulics codes for use in predicting the transient thermal hydraulics response of liquid salt cooled reactor systems, including integral transient response for forced and natural circulation operation. The reference system for the project is a modular, 900-MWth Pebble Bed Advanced High Temperature Reactor (PB-AHTR), a specific type of Fluoride salt-cooled High temperature Reactor (FHR). Two experimental facilities were developed for thermal-hydraulic integral effects tests (IETs) and separate effects tests (SETs). The facilities use simulant fluids for the liquid fluoride salts, with very little distortion to the heat transfer and fluid dynamics behavior. The CIET Test Bay facility was designed, built, and operated. IET data for steady state and transient natural circulation was collected. SET data for convective heat transfer in pebble beds and straight channel geometries was collected. The facility continues to be operational and will be used for future experiments, and for component development. The CIET 2 facility is larger in scope, and its construction and operation has a longer timeline than the duration of this grant. The design for the CIET 2 facility has drawn heavily on the experience and data collected on the CIET Test Bay, and it was completed in parallel with operation of the CIET Test Bay. CIET 2 will demonstrate start-up and shut-down transients and control logic, in addition to LOFC and LOHS transients, and buoyant shut down rod operation during transients. Design of the CIET 2 Facility is complete, and engineering drawings have been submitted to an external vendor for outsourced quality controlled construction. CIET 2 construction and operation continue under another NEUP grant. IET data from both CIET facilities is to be used for validation of system codes used for FHR modeling, such as RELAP5-3D. A set of

  8. Vortex- and CO2 -gas-assisted liquid-liquid microextraction with salt addition for the high-performance liquid chromatographic determination of furanic compounds in concentrated juices and dried fruits.

    Science.gov (United States)

    Abu-Bakar, Nur-Bahiyah; Makahleh, Ahmad; Saad, Bahruddin

    2016-03-01

    A novel microextraction method based on vortex- and CO2 -assisted liquid-liquid microextraction with salt addition for the isolation of furanic compounds (5-hydroxymethyl-2-furaldehyde, 5-methyl-2-furaldehyde, 2-furaldehyde, 3-furaldehyde, 2-furoic and 3-furoic acids) was developed. Purging the sample with CO2 was applied after vortexing to enhance the phase separation and mass transfer of the analytes. The optimum extraction conditions were: extraction solvent (volume), propyl acetate (125 μL); sample pH, 2.4; vortexing time, 45 s; salt concentration, 25% w/v and purging time, 5 min. The analytes were separated using an ODS Hypersil C18 column (250×4.6 mm i.d, 5 μm) under gradient flow. The proposed method showed good linearities (r(2) >0.999), low detection limits (0.08-1.9 μg/L) and good recoveries (80.7-122%). The validated method was successfully applied for the determination of the furanic compounds in concentrated juice (mango, date, orange, pomegranate, roselle, mangosteen and soursop) and dried fruit (prune, date and apricot paste) samples.

  9. Polyelectrolyte-stabilized graphene oxide liquid crystals against salt, pH, and serum.

    Science.gov (United States)

    Zhao, Xiaoli; Xu, Zhen; Xie, Yang; Zheng, Bingna; Kou, Liang; Gao, Chao

    2014-04-08

    Stabilization of colloids is of great significance in nanoscience for their fundamental research and practical applications. Electrostatic repulsion-stabilized anisotropic colloids, such as graphene oxide (GO), can form stable liquid crystals (LCs). However, the electrostatic field would be screened by ions. To stabilize colloidal LCs against electrolyte is an unsolved challenge. Here, an effective strategy is proposed to stabilize GO LCs under harsh conditions by association of polyelectrolytes onto GO sheets. Using sodium poly(styrene sulfonate) (PSS) and poly[2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (PMEDSAH), a kind of polyzwitterion, GO LCs were well-maintained in the presence of NaCl (from 0 M to saturated), extreme pH (from 1 to 13), and serum. Moreover, PSS- or PMEDSAH-coated chemically reduced GO (rGO) also showed stability against electrolyte.

  10. Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems

    Energy Technology Data Exchange (ETDEWEB)

    Muralidharan, Govindarajan; Wilson, Dane Francis; Holcomb, David Eugene

    2017-06-20

    An alloy consists essentially of, in terms of weight percent: 6 to 8.5 Cr, 5.5 to 13.5 Mo, 0.4 to 7.5 W, 1 to 2 Ti, 0.7 to 0.85 Mn, 0.05 to 0.3 Al, up to to 0.1 Co, 0.08 to 0.5 C, 1 to 5 Ta, 1 to 4 Nab, 1 to 3 Hf, balance Ni. The alloy is characterized by, at 850.degree. C., a yield strength of at least 36 Ksi, a tensile strength of at least 40 Ksi, a creep rupture life at 12 Ksi of at least 72.1 hours, and a corrosion rate, expressed in weight loss [g/(cm2sec)].times.10.sup.-11 during a 1000 hour immersion in liquid FLiNaK at 850.degree. C., in the range of 8 to 25.

  11. Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems

    Energy Technology Data Exchange (ETDEWEB)

    Muralidharan, Govindarajan; Wilson, Dane Francis; Holcomb, David Eugene

    2017-06-20

    An alloy is composed essentially of, in terms of weight percent: 6 to 8.5 Cr, 5.5 to 13.5 Mo, 0.4 to 7.5 W, 1 to 2 Ti, 0.7 to 0.85 Mn, 0.05 to 0.3 Al, 0.08 to 0.5 C, 0 to 1 Nb, with the balance Ni, the alloy being characterized by, at 850.degree. C., a yield strength of at least 25 Ksi, a tensile strength of at least 30 Ksi, a creep rupture life at 12 Ksi of at least 45 hours, and a corrosion rate, expressed in weight loss [g/(cm.sup.2 sec)]10.sup.-11 during a 1000 hour immersion in liquid FLiNaK at 850.degree. C., in the range of 6 to 39.

  12. The Gruneisen parameter for silver azide

    Science.gov (United States)

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

    2011-12-01

    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.

  13. Ionic Liquid-salt Aqueous Two-phase System, a Novel System for the Extraction of Abused Drugs

    Institute of Scientific and Technical Information of China (English)

    She Hong LI; Chi Yang HE; Hu Wei LIU; Ke An LI; Feng LIU

    2005-01-01

    A 1-butyl-3-methylimidazolium chloride-salt aqueous two-phase system was studied on extraction of abused drugs. The effects of sorts of salts, temperature, concentration of salt and drugs on system were investigated systematically. A satisfactory extraction efficiency of 93%was obtained for papaverine while that of morphine was 65%. The extraction mechanism was primarily discussed.

  14. Heterogeneous nucleation of calcium phosphate salts at a solid/liquid interface examined by scanning angle reflectometry

    Science.gov (United States)

    Ngankam, P. A.; Schaaf, P.; Voegel, J. C.; Cuisinier, F. J. G.

    1999-03-01

    Mineralization of calcium phosphate salts at a solid/liquid silica interface was examined by means of scanning angle reflectometry (SAR). A critical supersaturation of 7.60±0.15 mM was found to be the lowest calcium phosphate concentration at pH 6.85 at which the reflectivity at the Brewster angle started to vary. The analyses of the signals by mean of the homogeneous isotropic layer model led to layer thicknesses of about 3.5 μm also characterized by very low mean refractive index increments. These observations were completed by complementary experiments. Scanning and transmission electron microscopy led to similar layer thicknesses with crystallites dispersed in the whole layer confirming thus SAR results. X-ray analyses showed a presence of brushite (DCPD) at the silica interface. A pH of 5.44 was estimated for the acidic silica interface for which DCPD is nucleated after addition of 7.60±0.15 mM calcium and phosphate. However, at this pH value, the solution is largely supersaturated with respect to hydroxyapatite (HAP theoretical saturating concentration: 1.37 mM). A faster growth of DCPD crystals compared to HAP crystals is thus assumed to explain our observations.

  15. [Simultaneous determination of canthaxanthin and Sudan Red in salted duck egg yolk by reversed-phase high performance liquid chromatography].

    Science.gov (United States)

    Wang, Quanlin; Shi, Pingping; Zhang, Shufen; Shen, Jian; Fu, Xiao

    2007-11-01

    A reversed-phase high performance liquid chromatographic (RP-HPLC) method for the simultaneous determination of canthaxanthin, Sudan Red I , Sudan Red II , Sudan Red III and Sudan Red IV in salted duck egg yolk has been developed. These canthaxanthin and Sudan Red dyes were extracted with a mixture of acetonitrile, methanol, and chloroform (1 : 0.5 : 0.5, v/v). The extract was dried by a rotary evaporator. The residue was transferred to a graduated tube and diluted to 10 mL with acetonitrile. The canthaxanthin and Sudan Red dyes were separated on a XDB-C18 column (250 mm x 4.6 mm), with acetonitrile-water (95:5, v/v) as mobile phase. They were then detected at 478 nm - 520 nm - 471 nm at different retention times by UV/Vis spectrophotometer. The recoveries of sudan I , sudan II, sudan II, sudan IV, and canthaxanthin were 97.34%, 89.56%, 90.98%, 93.63% and 95.15% respectively. The relative standard deviations (RSDs) were 4.7%, 4.3%, 5.1%, 4.9% and 3.1%, respectively. The method is simple, rapid and accurate.

  16. Extraction and purification of wheat-esterase using aqueous two-phase systems of ionic liquid and salt.

    Science.gov (United States)

    Jiang, Bin; Feng, Zhibiao; Liu, Chunhong; Xu, Yingcao; Li, Dongmei; Ji, Guo

    2015-05-01

    To explore a new and simple rapid extraction and purification technique for wheat-esterase, an ionic liquids (ILs)-based aqueous two-phase system (ATPS) was developed for the purification of wheat-esterase from wheat extracts. Effects of various process parameters such as the concentrations of [Bmim]BF4, the types and concentrations of phase-forming salt, the system pH and the temperature on partitioning of wheat-esterase were evaluated. The obtained data indicated that wheat-esterase was preferentially partitioned into the ILs-rich phase and the ATPS composed of 20 % [Bmim]BF4 (w/w) and 25 % (w/w) NaH2PO4(pH = 4.8) showed good selectivity on wheat-esterase. Under the optimum conditions, wheat-esterase was purified with an acceptable yield (88.93 %), but produced wheat-esterase was 4.23 times as pure. It was obvious that temperature shows little influence on the purification between 10 and 50 °C. Sephadex G-150FF revealed that the band intensity of contaminating proteins in ATPS fraction almost disappeared. Therefore, ILs-based ATPS was an effective method for partitioning and recovery of wheat-esterase from wheat crude extracts.

  17. Ionic liquid-polymer gel electrolytes based on morpholinium salt and PVdF(HFP) copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ki-Sub; Park, Seung-Yeob; Choi, Sukjeong; Lee, Huen [Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, Daejeon 305-701 (Korea, Republic of)

    2006-04-21

    New ionic liquid-polymer gel electrolytes (IPGEs) are prepared from N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide (Mor{sub 1,2}TFSI) and poly(vinylidene fluoride)-hexafluoropropylene copolymer (PVdF(HFP)). To investigate the effect of propylene carbonate (PC) on the ionic conductivity of the IPGEs, the preparation methods are roughly divided into two groups according to the presence or absence of PC. The ionic conductivity for each IPGE is measured with increasing temperature and changing weight ratio of Mor{sub 1,2}TFSI. The results show that the ionic conductivity increases as the temperature and weight ratio of the Mor{sub 1,2}TFSI increase, and that the added PC improves the ionic conductivity of the IPGEs. In addition, thermogravimetric analysis and the data from infrared spectroscopy demonstrate the thermal stability of each IPGE and the presence of PC in the polymer network. Although the IPGEs that contain PC display high conductivity ({approx}1.1x10{sup -2}Scm{sup -1}) at 60{sup o}C, they are thermally unstable. (author)

  18. High strength alloys for high temperature service in liquid-salt cooled energy systems

    Energy Technology Data Exchange (ETDEWEB)

    Holcomb, David E.; Muralidharan, Govindarajan; Wilson, Dane F.

    2017-01-10

    An essentially cobalt-free alloy consists essentially of, in terms of weight percent: 6.3 to 7.2 Cr, 0.5 to 2 Al, 0 to 5 Fe, 0.7 to 0.8 Mn, 9 to 12.5 Mo, 0 to 6 Ta, 0.75 to 3.5 Ti, 0.01 to 0.25 Nb, 0.2 to 0.6 W, 0.02 to 0.04 C, 0 to 0.001 B, 0.0001 to 0.002 N, balance Ni. The alloy is characterized by a .gamma.' microstructural component in the range of 3 to 17.6 weight percent of the total composition. The alloy is further characterized by, at 850.degree. C., a yield strength of at least 60 Ksi, a tensile strength of at least 70 Ksi, a creep rupture life at 12 Ksi of at least 700 hours, and a corrosion rate, expressed in weight loss [g/(cm.sup.2sec)]10.sup.-11 during a 1000 hour immersion in liquid FLiNaK at 850.degree. C., in the range of 5.5 to 17.

  19. Creep-resistant, cobalt-free alloys for high temperature, liquid-salt heat exchanger systems

    Science.gov (United States)

    Holcomb, David E; Muralidharan, Govindarajan; Wilson, Dane F.

    2016-09-06

    An essentially Fe- and Co-free alloy is composed essentially of, in terms of weight percent: 6.0 to 7.5 Cr, 0 to 0.15 Al, 0.5 to 0.85 Mn, 11 to 19.5 Mo, 0.03 to 4.5 Ta, 0.01 to 9 W, 0.03 to 0.08 C, 0 to 1 Re, 0 to 1 Ru, 0 to 0.001 B, 0.0005 to 0.005 N, balance Ni, the alloy being characterized by, at 850.degree. C., a yield strength of at least 25 Ksi, a tensile strength of at least 38 Ksi, a creep rupture life at 12 Ksi of at least 25 hours, and a corrosion rate, expressed in weight loss [g/(cm.sup.2 sec)]10.sup.-11 during a 1000 hour immersion in liquid FLiNaK at 850.degree. C., in the range of 3 to 10.

  20. High strength alloys for high temperature service in liquid-salt cooled energy systems

    Science.gov (United States)

    Holcomb, David E.; Muralidharan, Govindarajan; Wilson, Dane F.

    2017-01-10

    An essentially cobalt-free alloy consists essentially of, in terms of weight percent: 6.3 to 7.2 Cr, 0.5 to 2 Al, 0 to 5 Fe, 0.7 to 0.8 Mn, 9 to 12.5 Mo, 0 to 6 Ta, 0.75 to 3.5 Ti, 0.01 to 0.25 Nb, 0.2 to 0.6 W, 0.02 to 0.04 C, 0 to 0.001 B, 0.0001 to 0.002 N, balance Ni. The alloy is characterized by a .gamma.' microstructural component in the range of 3 to 17.6 weight percent of the total composition. The alloy is further characterized by, at 850.degree. C., a yield strength of at least 60 Ksi, a tensile strength of at least 70 Ksi, a creep rupture life at 12 Ksi of at least 700 hours, and a corrosion rate, expressed in weight loss [g/(cm.sup.2sec)]10.sup.-11 during a 1000 hour immersion in liquid FLiNaK at 850.degree. C., in the range of 5.5 to 17.

  1. Creep-resistant, cobalt-free alloys for high temperature, liquid-salt heat exchanger systems

    Energy Technology Data Exchange (ETDEWEB)

    Holcomb, David E; Muralidharan, Govindarajan; Wilson, Dane F.

    2016-09-06

    An essentially Fe- and Co-free alloy is composed essentially of, in terms of weight percent: 6.0 to 7.5 Cr, 0 to 0.15 Al, 0.5 to 0.85 Mn, 11 to 19.5 Mo, 0.03 to 4.5 Ta, 0.01 to 9 W, 0.03 to 0.08 C, 0 to 1 Re, 0 to 1 Ru, 0 to 0.001 B, 0.0005 to 0.005 N, balance Ni, the alloy being characterized by, at 850.degree. C., a yield strength of at least 25 Ksi, a tensile strength of at least 38 Ksi, a creep rupture life at 12 Ksi of at least 25 hours, and a corrosion rate, expressed in weight loss [g/(cm.sup.2 sec)]10.sup.-11 during a 1000 hour immersion in liquid FLiNaK at 850.degree. C., in the range of 3 to 10.

  2. Alkylation of Methyl Linoleate with Propene in Ionic Liquids in the Presence of Metal Salts

    Directory of Open Access Journals (Sweden)

    Christian Silvio Pomelli

    2015-12-01

    Full Text Available Vegetable oils and fatty acid esters are suitable precursor molecules for the production of a variety of bio-based products and materials, such as paints and coatings, plastics, soaps, lubricants, cosmetics, pharmaceuticals, printing inks, surfactants, and biofuels. Here, we report the possibility of using Lewis acidic ionic liquids (ILs to obtain polyunsaturated ester dimerization-oligomerization and/or, in the presence of another terminal alkene (propene, co-polymerization. In particular, we have tested the Lewis acidic mixtures arising from the addition of a proper amount of GaCl3 (Χ > 0.5 to two chloride-based (1-butyl-3-methylimidazolium chloride, [bmim]Cl, and 1-butylisoquinolium chloride, [BuIsoq]Cl or by dissolution of a smaller amount of Al(Tf2N3 (Χ = 0.1 in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonylimide, [bmim][Tf2N]. On the basis of product distribution studies, [bmim][Tf2N]/Al(Tf2N3 appears the most suitable medium in which methyl linoleate alkylation with propene can compete with methyl linoleate or propene oligomerization.

  3. Extended UNIQUAC model for correlation and prediction of vapour-liquid-solid equilibria in aqueous salt systems containing non-electrolytes

    DEFF Research Database (Denmark)

    Iliuta, Maria C.; Thomsen, Kaj; Rasmussen, Peter

    2000-01-01

    . The calculations are based on an extensive database consisting of salt solubility data in pure and mixed solvents, VLE data for solvent mixtures and mixed solvent-electrolyte systems and thermal properties for mixed solvent solutions. Application of the model to the methanol-water system in the presence of several...... to aqueous salt systems containing non-electrolytes in order to demonstrate its ability in representing solid-liquid-vapour (SLV) equilibrium and thermal property data for these strongly non-ideal systems. The model requires only pure component and binary temperature-dependent interaction parameters...... behaviour of methanol-water-three salts systems is illustrated. (C) 2000 Elsevier Science Ltd. All rights reserved....

  4. Salting-out assisted liquid-liquid extraction for the determination of biogenic amines in fruit juices and alcoholic beverages after derivatization with 1-naphthylisothiocyanate and high performance liquid chromatography.

    Science.gov (United States)

    Jain, Archana; Gupta, Manju; Verma, Krishna K

    2015-11-27

    A new method for determining biogenic amines in fruit juices and alcoholic beverages is described involving reaction of biogenic amines with 1-naphthylisothiocyanate followed by extraction of 1-naphthylthiourea derivatives with water-miscible organic solvent acetonitrile when solvents phase separation occurred using ammonium sulphate, a process called salting-out assisted liquid-liquid extraction. The extract was analyzed by high-performance liquid chromatography with UV detection at 254nm. The new reagent avoided many of the inconveniences as observed with existing derivatizing agents, such as dansyl chloride and benzoyl chloride, in regard to their inselectivity, instability, adverse effect of excess reagent, and necessity to remove excess reagent. The procedure has been optimized with respect to reaction time and temperature, water-miscible extraction solvent, and salt for solvents phase separation. Use of reagent as dispersed phase in aqueous medium produced derivatives in high yield. A linear calibration was obtained between the amount of biogenic amines in range 1-1000μgL(-1) and peak areas of corresponding thioureas formed; the correlation coefficient was 0.9965, and the limit of detection and limit of quantification found were 1.1μgL(-1) and 3.2μgL(-1), respectively. The pre-concentration method gave an average enrichment factor of 94. The application of the method has been demonstrated in the determination of biogenic amines in commercial samples of fruit juices and alcoholic beverages. In spiking experiments to real samples, the average recovery found by the present method was 94.5% that agreed well with 95.8% obtained by established comparison methods.

  5. Variation of Boiling Point with Salting Effect in Vapor-Liquid Equilibrium%汽液平衡盐效应中的沸点变化

    Institute of Scientific and Technical Information of China (English)

    孙仁义; 朱元举; 冷春莉

    2003-01-01

    测定了在恒压(100.0kPa)条件下若干含盐双液系(甲醇-水,乙醇-水,正丙醇-水)的沸点变化.实验结果表明引起溶液沸点降低"反常现象"发生的必要条件是易挥发组分被盐析或难挥发组分被盐溶.经热力学分析表明上述实验结果是一个具有普遍意义的结论.%The influence of some nonvolatile salts on boiling point of methanol-water, ethanol-water andn-propanol-water systems was determined at fixed liquid composition and given pressure (100.0 kPa).The experimental results indicate that the requisite of boiling point depression is that the more volatilecomponent must be salted out, the less volatile component must be salted in. This conclusion, basedon thermodynamical consideration, can be taken as a universal rule that governs the variation of boilingpoint when a little nonvolatile salt dissolves in liquid mixture with constant composition.

  6. Salting-out assisted liquid-liquid extraction coupled to ultra-high performance liquid chromatography-tandem mass spectrometry for the determination of tetracycline residues in infant foods.

    Science.gov (United States)

    Moreno-González, David; García-Campaña, Ana M

    2017-04-15

    The use of salting-out assisted liquid-liquid extraction (SALLE) combined with ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) has been evaluated for the determination of tetracyclines in infant foods based on meat and vegetables or in milk. To obtain satisfactory extraction efficiencies for the studied analytes, several parameters affecting the SALLE procedure were optimized. Analytical performances of the method were satisfactory, obtaining limits of quantification lower than 0.48μgkg(-1) in all cases. The precision, expressed as relative standard deviation (%, RSD) was below 11.3%. The extraction efficiency for fortified samples ranged from 89.2 to 96.8%, with RSDs lower than 7.3%. Matrix effect was evaluated for all samples studied, being lower than |21|% in all cases. In relation to the low solvent consumption, the proposed methodology could be considered rapid, cheap and environmentally friendly. Its applicability has been successfully tested in a wide range of infant foods.

  7. Alkali-metal azides interacting with metal-organic frameworks.

    Science.gov (United States)

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

    2013-01-14

    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.

  8. 耐盐乳酸菌添加对高盐稀态酱油风味的影响%The Impact of Adding Salt-tolerant Lactic Acid Bacteria on the Flavor of High-salt Liquid Soy Sauce

    Institute of Scientific and Technical Information of China (English)

    戚晨晨; 王猛; 沈艾彬

    2016-01-01

    In the fermentation process of high-salt liquid soy sauce,the addition of salt-tolerant lactic acid bacteria has a great influence on the final flavor components of soy sauce.Through adding salt-tolerant lactic acid bacteria on the 30th and 45th day of fermentation,research the content of total acids,saltless solids and flavor compounds.The results show that adding salt-tolerant lactic acid bacteria on the 45th day,the content of total acids,saltless solids and flavor compounds is higher than that adding and without adding salt-tolerant lactic acid bacteria on the 30th day.The research has laid a foundation for its future application in the industrial production of brewed soy sauce with good flavor.%高盐稀态酱油发酵过程中,耐盐乳酸菌的添加时间对于酱油最终风味成分的影响很大。通过分别在发酵30,45天添加耐盐乳酸菌、未添加乳酸菌发酵的酱油对照,研究总酸、无盐固形物、风味物质的含量。研究表明:发酵45天添加耐盐乳酸菌,总酸、无盐固形物、风味物质的含量均高于30天添加和未添加乳酸菌发酵的酱油对照,为其以后应用于工业生产酿造出风味良好的酱油打下基础。

  9. Solid-liquid (S-L) an liquid (L-L) phase transfer of salts via ‘encapsulated’ crown ether cation complexes

    NARCIS (Netherlands)

    Reinhoudt, D.N.

    1983-01-01

    In recent years crown ethers have been successfully used for the transport of salts, both inorganic and organic, from an aqueous phase to organic solvents. Our work has extended the applicability of these crown ethers to the transport of salts from the solid state into solution both aqueous and nona

  10. Vapor pressures and enthalpies of vaporization of azides

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-11-15

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

  11. Octaammine Eu{sup II} and Yb{sup II} azides and their thermal decompositions to the nitrides

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, Thomas G.; Mogk, Jochen; Conrad, Matthias; Kraus, Florian [Anorganische Chemie, Fluorchemie, Fachbereich Chemie, Philipps-Universitaet Marburg, 35032, Marburg (Germany)

    2016-09-15

    The common preparation for many nitrides is the synthesis from the corresponding metals and nitrogen at quite high temperatures and/or high pressures. Here we present a route to metal nitrides by the use of ammine metal azides under relatively mild conditions. Europium(II) and ytterbium(II) azides are prepared in liquid ammonia at -36 C in form of their temperature-sensitive octaammine complexes. These were investigated by single-crystal X-ray diffraction at low temperatures, and their structures seem to be the first evidence for the existence of homoleptic ammine Eu{sup II} and Yb{sup II} complexes, as well as that the coordination number of these divalent cations can go beyond six with NH{sub 3} ligands. In one of the cases presented here the observed coordination polyhedron is better described as a bicapped trigonal prism (C{sub 2v}), in one case better as square-antiprismatic (D{sub 4d}). Warming of these compounds to room temperature leads to the lanthanoid metal azides still containing approximately 1 equiv. of ammonia. The behaviour of these azides towards further heating was investigated: By very careful and slow decomposition, the nitrides of europium(III) and ytterbium(III) are obtained at only 230 C at ambient pressure. This method may be suitable to obtain other metal nitrides at remarkably low temperatures and pressures. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. The potential of incorporation of binary salts and ionic liquid in P(VP-co-VAc) gel polymer electrolyte in electrochemical and photovoltaic performances

    Science.gov (United States)

    Ming, Ng Hon; Ramesh, S.; Ramesh, K.

    2016-06-01

    In this study, dye-sensitized solar cells (DSSCs) has been assembled with poly(1-vinylpyrrolidone-co-vinyl acetate) (P(VP-co-VAc)) gel polymer electrolytes (GPEs) which have been incorporated with binary salt and an ionic liquid. The potential of this combination was studied and reported. The binary salt system GPEs was having ionic conductivity and power conversion efficiency (PCE) that could reach up to 1.90 × 10‑3 S cm‑1 and 5.53%, respectively. Interestingly, upon the addition of the ionic liquid, MPII into the binary salt system the ionic conductivity and PCE had risen steadily up to 4.09 × 10‑3 S cm‑1 and 5.94%, respectively. In order to know more about this phenomenon, the electrochemical impedance studies (EIS) of the GPE samples have been done and reported. Fourier transform infrared studies (FTIR) and thermogravimetric analysis (TGA) have also been studied to understand more on the structural and thermal properties of the GPEs. The Nyquist plot and Bodes plot studies have been done in order to understand the electrochemical properties of the GPE based DSSCs and Tafel polarization studies were done to determine the electrocatalytic activity of the GPE samples.

  13. Multiclass method for the determination of pharmaceuticals and personal care products in compost from sewage sludge using ultrasound and salt-assisted liquid-liquid extraction followed by ultrahigh performance liquid chromatography-tandem mass spectrometry analysis.

    Science.gov (United States)

    Luque-Muñoz, A; Vílchez, J L; Zafra-Gómez, A

    2017-07-21

    An analytical method for the analysis of 16 pharmaceuticals and personal care products in compost from sewage sludge is successfully validated. Ultrasound assisted extraction with a mixture of acetonitrile:ethyl acetate (1:1, v/v) containing 10% (v/v) of acetic acid was carried out. Two cycles of extraction of 10min were applied. A clean-up of the extracts using salt-assisted liquid-liquid extraction (SALLE) was also included. Experimental design was used for the optimization of the main parameters involved in the extraction and cleaned-up steps. The chromatographic separation was carried out by ultrahigh performance liquid chromatography using a mobile phase gradient mixture of a 13mM buffer ammonium formate solution (pH 9.25) (solvent A) and methanol (solvent B). An ACQUITY UPLC(®) BEH C18 column (1.7μm; 2.1×50mm) column was used. Analytes were separated in less than 11min. The compounds were detected and quantified using single reaction monitoring electrospray tandem mass spectrometry. The limits of detection calculated ranged from 0.5 to 4ngg(-1)d.w., and the limits of quantification from 2 to 13ngg(-1)d.w. Recoveries from 93% to 111%, with relative standar deviations lower than 11% in all cases, were obtained. The method was applied to natural compost samples. High concentrations of some analytes were found. Ketoprofen (510ngg(-1)d.w.), methylparaben (240ngg(-1)d.w.), diclofenac (175ngg(-1)d.w.) and flufenamic acid (128ngg(-1)d.w.) were the most abundant. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Ionic liquid and aqueous two-phase extraction based on salting-out coupled with high-performance liquid chromatography for the determination of seven rare ginsenosides in Xue-Sai-Tong injection.

    Science.gov (United States)

    Li, Lan-Jie; Jin, Yong-Ri; Wang, Xiao-Zhong; Liu, Ying; Wu, Qian; Shi, Xiao-Lei; Li, Xu-Wen

    2015-09-01

    A method of ionic liquid salt aqueous two-phase extraction coupled with high-performance liquid chromatography has been developed for the analysis of seven rare ginsenosides including Rg6 , F4 , 20(S)-Rg3 , 20(R)-Rg3 , Rk3 , Rk1 , and Rg5 in Xue-Sai-Tong injection. The injection was mixed with ionic liquid 1-butyl-3-methylimidazolium bromide aqueous solution, and a mixture was obtained. With the addition of sodium dodecyl sulfate and dipotassium phosphate into the mixture, the aqueous two-phase mixture was formed after ultrasonic treatment and centrifuged. Rare ginsenosides were extracted into the upper phase. To obtain a high extraction factors, various influences were considered systematically, such as the volume of ionic liquid, the category and amount of salts, the amount of sodium dodecyl sulfate, the pH value of system, and the time of ultrasonic treatment. Under the optimal condition, rare ginsenosides in Xue-Sai-Tong injection were enriched and detected, the recoveries of seven rare ginsenosides ranged from 90.05 to 112.55%, while relative standard deviations were lower than 2.50%. The developed method was reliable, rapid and sensitive for the determination of seven rare ginsenosides in the injections.

  15. Preliminary Studies on Pulsed Electric Field Breakdown of Lead Azide

    Science.gov (United States)

    1976-10-01

    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

  16. Visible Light Sensitization of Vinyl Azides by Transition Metal Photocatalysis

    Science.gov (United States)

    Farney, Elliot P.; Yoon, Tehshik P.

    2014-01-01

    Irradiation of vinyl and aryl azides with visible light in the presence of Ru photocatalysts results in the formation of reactive nitrenes, which can undergo a variety of C–N bond-forming reactions. The ability to use low-energy visible light instead of UV in the photochemical activation of azides avoids competitive photodecomposition processes that have long been a significant limitation on the synthetic utility of these reactions. PMID:24281908

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

    Institute of Scientific and Technical Information of China (English)

    Jin Han; Chao Gao

    2010-01-01

    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.

  18. An azide-modified nucleoside for metabolic labeling of DNA.

    Science.gov (United States)

    Neef, Anne B; Luedtke, Nathan W

    2014-04-14

    Metabolic incorporation of azido nucleoside analogues into living cells can enable sensitive detection of DNA replication through copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and strain-promoted azide-alkyne cycloaddition (SPAAC) "click" reactions. One major limitation to this approach is the poor chemical stability of nucleoside derivatives containing an aryl azide group. For example, 5-azido-2'-deoxyuridine (AdU) exhibits a 4 h half-life in water, and it gives little or no detectable labeling of cellular DNA. In contrast, the benzylic azide 5-(azidomethyl)-2'-deoxyuridine (AmdU) is stable in solution at 37 °C, and it gives robust labeling of cellular DNA upon addition of fluorescent alkyne derivatives. In addition to providing the first examples of metabolic incorporation into and imaging of azide groups in cellular DNA, these results highlight the general importance of assessing azide group stability in bioorthogonal chemical reporter strategies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Multi-residue quantification of veterinary drugs in milk with a novel extraction and cleanup technique: salting out supported liquid extraction (SOSLE).

    Science.gov (United States)

    Kaufmann, A; Butcher, P; Maden, K; Walker, S; Widmer, M

    2014-04-11

    A quantitative liquid chromatography coupled with high-resolution mass spectrometry method was developed for the determination of more than one hundred compounds belonging to a variety of veterinary drug classes in bovine milk. Salting out supported liquid extraction (SOSLE), a novel extraction and cleanup technique, was introduced to ensure high extraction efficiency and good sample cleanup. The high salt (ammonium sulfate) concentration in the aqueous donor phase permits supported liquid/liquid extraction (SLE) with a relative polar organic acceptor phase (acetonitrile). This is different from traditional SLE, in which the need for phase separation results in the selection of organic solvents with intermediate polarities (e.g., ethyl acetate or dichloromethane). Hence, SOSLE is more efficient in recovering polar analytes than conventional SLE. SOSLE was also compared to classical approaches like solid phase extraction, QuEChERS and ultra-filtration. The proposed technique resulted in extracts of equal or superior cleanliness and with higher average recoveries than those obtained with QuEChERS or SPE. The recovery (median for all compounds) was 73% for QuEChERS, 83% for SPE and 91% for SOSLE. The most significant improvements were observed for polar analytes (penicillines, quinolones and tetracyclines) which are hardly recovered by QuEChERS. The chromatographic separation and detection was based on an ultra-high-performance liquid chromatography Q-Orbitrap system (Q-Exactive plus). The developed analytical method has been validated (based on the commission decision 2002/957/EC) as required for quantitative veterinary drug methods.

  20. Effect of Added Salts or Polyols on the Cloud Point and the Liquid-Crystalline Structures of Polyoxyethylene-Modified Silicone.

    Science.gov (United States)

    Iwanaga; Kunieda

    2000-07-15

    The effect of added salts (NaCl, Na(2)SO(4), and NaSCN) or polyols (glycerin (Gly), 1,3-butanediol (1,3-BD), ethylene glycol (EG), and polyethylene glycol (PEG400)) on the hexagonal liquid-crystalline structure of polyoxyethylene-modified silicone was investigated by means of small angle X-ray scattering (SAXS). The effective cross-sectional area of the lipophilic part of the aggregate, a(s), in the hexagonal phase decreases upon the addition of salts, on one hand, lowering the cloud point in the dilute aqueous siloxane surfactant solutions. On the other hand, if added salt raises the cloud point, the a(s) increases. Similar results were obtained in the case of the addition of polyols. Since the a(s) mainly depends on the EO chain length, the above results are direct evidence that the hydration or dehydration of the EO chain is affected by these additives. The static fluorescence probe method was applied to the Gly and 1,3-BD systems using 8-anilino-1-naphthalene-sulfonic acid, ANS, to know the change in hydration of the EO chains. In the Gly system, the hydration of the EO chain monotonically decreases whereas 1,3-BD first increases the hydration and then decreases it at high 1,3-BD content. These results are very consistent with the SAXS and cloud temperature results. Copyright 2000 Academic Press.

  1. Hunting liquid micro-pockets in snow and ice: Phase transition in salt solutions at the bulk and interface with X-ray photoelectron spectroscopy.

    Science.gov (United States)

    Bartels-Rausch, Thorsten; Orlando, Fabrizio; Kong, Xiangrui; Waldner, Astrid; Artiglia, Luca; Ammann, Markus; Huthwelker, Thomas

    2016-04-01

    Sea salt, and in particular chloride, is an important reactant in the atmosphere. Chloride in air-borne sea salt aerosol is - once chemically converted to a molecular halogen (Cl2, BrCl) and released to the atmosphere - well known as important atmospheric reactant, driving large-scale changes to the atmospheric composition and in particular to ozone levels in remote areas, but also in coastal mega cities. Similar chemistry has been proposed for sea salt deposits in polar snow covers. A crucial factor determining the overall reactivity is the local physical environment of the chloride ion. For example, the reactivity of liquid aerosols decreases significantly upon crystallization. Surprisingly, the phases of NaCl-containing systems are still under debate, partially due to the limited availability of in situ measurements directly probing the local environment at the surface of frozen NaCl-water binary systems. Using core electron spectroscopy of the oxygen atoms in water, we previously showed that these systems follow the phase rules at the air-ice interface. This finding contrasts some earlier observations, where the presence of liquid below the eutectic point of bulk solutions was postulated. In the present study, we present new electron yield near-edge X-ray absorption fine structure spectroscopy (NEXAFS) data obtained at near-ambient pressures up to 20 mbar of NaCl frozen solutions. The method is sensitive to small changes in the local environment of the chlorine atom. The measurements were performed at the PHOENIX beamline at SLS. The study indicates frapant differences in the phases of NaCl - water mixtures at temperatures blow the freezing point for the surface of the ice vs. the bulk. This has significant impact on modelling chemical reactions in snow or ice and it's environmental consequences.

  2. Sensitivity of cuprous azide towards heat and impact

    Directory of Open Access Journals (Sweden)

    Kartar Singh

    1958-07-01

    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."

  3. Guest-responsive covalent frameworks by the cross-linking of liquid-crystalline salts: tuning of lattice flexibility by the design of polymerizable units.

    Science.gov (United States)

    Ishida, Yasuhiro; Sakata, Hiroaki; Achalkumar, Ammathnadu S; Yamada, Kuniyo; Matsuoka, Yuki; Iwahashi, Nobutaka; Amano, Sayaka; Saigo, Kazuhiko

    2011-12-23

    Cross-linked polymers prepared by the in-situ polymerization of liquid-crystalline salts were found to work as solid-state hosts with a flexible framework. As a component of such hosts, four kinds of polymerizable amphiphilic carboxylic acids bearing alkyl chains with acryloyloxy (A), dienyl (D), and/or nonreactive (N) chain ends (monomeric carboxylic acids; M(AAA), M(ANA), M(DDD), and M(DND)) were used. The carboxylic acids were mixed with an equimolar amount of a template unit, (1R,2S)-norephedrine (guest amine; G(RS)), to form the corresponding salts. Every salt exhibited a rectangular columnar LC phase at room temperature, which was successfully polymerized by (60)Co γ-ray-induced polymerization without serious structural disordering to afford the salt of cross-linked carboxylic acid (polymeric carboxylic acid; P(AAA), P(ANA), P(DDD), and P(DND)) with G(RS) . Owing to the noncovalency of the interactions between the polymer framework P and the template G(RS), the cross-linked polymers could reversibly release and capture a meaningful amount of G(RS). In response to the desorption and adsorption of G(RS), the cross-linked polymers dramatically switched their nanoscale structural order. A systematic comparison of the polymers revealed that the choice of polymerizable groups has a significant influence on the properties of the resultant polymer frameworks as solid-state hosts. Among these polymers, P(DDD) was found to be an excellent solid-state host, in terms of guest-releasing/capturing ability, guest-recognition ability, durability to repetitive usage, and unique structural switching mode.

  4. Condensation of Self-Assembled Lyotropic Chromonic Liquid Crystal Sunset Yellow in Aqueous Solutions Crowded with Polyethylene Glycol and Doped with Salt

    Energy Technology Data Exchange (ETDEWEB)

    Park, Heung-Shik; Kang, Shin-Woong; Tortora, Luana; Kumar, Satyendra; Lavrentovich, Oleg D. (Chonbuk); (Kent)

    2012-10-10

    We use optical and fluorescence microscopy, densitometry, cryo-transmission electron microscopy (cryo-TEM), spectroscopy, and synchrotron X-ray scattering to study the phase behavior of the reversible self-assembled chromonic aggregates of an anionic dye Sunset Yellow (SSY) in aqueous solutions crowded with an electrically neutral polymer polyethylene glycol (PEG) and doped with the salt NaCl. PEG causes the isotropic SSY solutions to condense into a liquid-crystalline region with a high concentration of SSY aggregates, coexisting with a PEG-rich isotropic (I) region. PEG added to the homogeneous nematic (N) phase causes separation into the coexisting N and I domains; the SSY concentration in the N domains is higher than the original concentration of PEG-free N phase. Finally, addition of PEG to the highly concentrated homogeneous N phase causes separation into the coexisting columnar hexagonal (C) phase and I phase. This behavior can be qualitatively explained by the depletion (excluded volume) effects that act at two different levels: at the level of aggregate assembly from monomers and short aggregates and at the level of interaggregate packing. We also show a strong effect of a monovalent salt NaCl on phase diagrams that is different for high and low concentrations of SSY. Upon the addition of salt, dilute I solutions of SSY show appearance of the condensed N domains, but the highly concentrated C phase transforms into a coexisting I and N domains. We suggest that the salt-induced screening of electric charges at the surface of chromonic aggregates leads to two different effects: (a) increase of the scission energy and the contour length of aggregates and (b) decrease of the persistence length of SSY aggregates.

  5. Preparation of salted meat products, e.g. cured bacon - by injecting liquid comprising meat proteins hydrolysed with enzymes

    DEFF Research Database (Denmark)

    1997-01-01

    Preparation of salted meat products comprises the following:(1) meat is chopped into fine pieces and mixed with water to form a slurry; (2) enzymes hydrolyse proteins in the meat; (3) adding a culture to the resulting medium, which comprises short peptide chains or amino acids; (4) forming...

  6. Copper-catalyzed azide alkyne cycloaddition polymer networks

    Science.gov (United States)

    Alzahrani, Abeer Ahmed

    -CuAAC reaction and a chain-growth acrylate homopolymerization were demonstrated and used to form branched polymer structures. A bulk, organic soluble initiation system consisting of a Cu(II) salt and a primary amine was also examined in both model reactions and in bulk polymerizations. The system was shown to be highly efficient, leading to nearly complete CuAAC polymerization at ambient temperature. Increasing the ratio of amine to copper from 1 to 4 increases the CuAAC reaction rate significantly from 4 mM/min for 1:1 ratio of Cu(II):hexyalmine to 14mM/min for 1:4 ratio. The concentration dependence of the amine on the reaction rate enables the polymerization rate to be controlled simply by manipulating the hexylamine concentration. Sequential thiol--acrylate and photo-CuAAC click reactions were utilized to form two-stage reactive polymer networks capable of generating wrinkles in a facile manner. The click thiol-Michael addition reaction was utilized to form a cross-linked polymer with residual, reactive alkyne sites that remained tethered throughout the network. The latent, unreacted alkyne sites are subsequently reacted with diazide monomers via a photoinduced Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction to increase the cross-link density. Increased cross-linking raised the modulus and glass transition temperature from 1.6 MPa and 2 °C after the thiol-acrylate reaction to 4.4 MPa and 22 °C after the CuAAC reaction, respectively. The double click reaction approach led to micro-wrinkles with well-controlled wavelength and amplitude of 8.50 +/- 1.6 and 1.4 μm, respectively, for a polymer with a 1280 μm total film thickness. Additionally, this approach further enables spatial selectivity of wrinkle formation by photo-patterning. The CuAAC-based polymerization was also used to design smart, responsive porous materials from well-defined CuAAC networks, which possesses a high glass transition temperature (Tg= 115°C) due to the formation of the triazole linkages

  7. Applications of azide-based bioorthogonal click chemistry in glycobiology.

    Science.gov (United States)

    Zhang, Xiu; Zhang, Yan

    2013-06-19

    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.

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

    DEFF Research Database (Denmark)

    Johansson, Karl Henrik; Pedersen, D.S.

    2012-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Xiu Zhang

    2013-06-01

    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.

  10. Complex Formation in a Liquid-Liquid Extraction System Containing Co(II), 4-(2-Thiazolylazo)resorcinol and Monotetrazolium Salt.

    Science.gov (United States)

    Divarova, Vidka; Stojnova, Kirila; Racheva, Petya; Lekova, Vanya

    2016-01-01

    The ion-associated complex formed between anionic chelate of Co(II)-4-(2-Thiazolylazo)resorcinol (TAR) with the monotetrazolium cation of 2-(4-Iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (INT) in the liquid-liquid extraction system Co(II)-TAR-INT-H(2)O-CHCl(3) was studied by the spectrophotometric method. The optimum extraction conditions of Co(II) were found. The extraction equilibria were studied. The equilibrium constants, the recovery factor and some analytical characteristics were calculated. The validity of Beer's law was checked. The molar ratio of the components in the ternary ion-associated complex Co(II)-TAR-INT was determined. The general formula of the complex was suggested. The effect of various foreign ions and reagents on the process of complex formation in the liquid-liquid extraction system was studied.

  11. Sacrificial salts: Compensating the initial charge irreversibility in lithium batteries

    Energy Technology Data Exchange (ETDEWEB)

    Shanmukaraj, Devaraj; Grugeon, Sylvie; Laruelle, Stephane; Douglade, Gregory; Tarascon, Jean-Marie; Armand, Michel [Laboratoire de Reactivite et de Chimie des Solides, UMR CNRS 6007, Universite de Picardie Jules Verne, Amiens (France)

    2010-10-15

    Lithium salts enlisting azide, oxocarbons, dicarboxylates and hydrazides have been identified as a practical mean to compensate the irreversible capacity loss of LIBs negative electrodes. During the first charge, the anion loses electrons and converts to gaseous N{sub 2}, CO or CO{sub 2}, within an acceptable potential range (3 to 4.5 V). We report an electrochemical study on these easily accessible 'sacrificial salts'. (author)

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

    Indian Academy of Sciences (India)

    Lalthazuala Rokhum; Ghanashyam Bez

    2012-05-01

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

  13. Novel sensors for detection of azide and dopamine: Electrochemical studies

    Science.gov (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

  14. [Sodium azide--clinical course of the poisoning and treatment].

    Science.gov (United States)

    Łopaciński, Bogdan; Kołacinski, Zbigniew; Winnicka, Renata

    2007-01-01

    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

  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)

    1996-12-31

    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. Silver-Catalyzed Decarboxylative Azidation of Aliphatic Carboxylic Acids.

    Science.gov (United States)

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

    2015-10-02

    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.

  17. Synthesis of Salt Soluble Proteins in Barley. Pulse-Labeling Study of Grain Filling in Liquid-Cultured Detached Spikes

    DEFF Research Database (Denmark)

    Giese, Nanna Henriette; Hejgaard, Jørn

    1984-01-01

    The accumulation of salt-soluble proteins in the endosperm of developing barley (Hordeum vulgare L.) grains was examined. Detached spikes of barley were cultured at different levels of nitrogen nutrition and pulse-labeled with [14C] sucrose at specific times after anthesis. Proteins were extracted...... to increased nitrogen nutrition. Two major components, β-amylase and protein Z in particular, had a synthesis profile almost identical to that of the endosperm storage protein, hordein....

  18. Computational Studies of Structures and Dynamics of 1, 3-Dimethylimidazolim Salt Liquid and their Interfaces Using Polarizable Potential Models

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Tsun-Mei; Dang, Liem X.

    2009-03-12

    The structures, thermodynamics, dynamical properties of bulk and air/liquid interfaces of three ionic liquids, 1,3-dimethylimidazolium [dmim]+, Cl-, Br-, and I- are studied using molecular dynamics techniques. In bulk melts, the radial distribution functions reveal a significant long-range structural correlation in these ionic liquids. From the angular distribution analysis, the imidazolium rings are found to lie parallel to each other at short distances, consistent with the structures observed in the crystal state. The single-ion dynamics are studied via mean-square-displacements, velocity and orientational correlation functions. The diffusion coefficients and reorientational times are found to be much smaller than H2O. We also observe that anion size plays an important role in the dynamics of ionic liquids. The computed density profiles of the ionic liquid/vapor interface exhibit oscillatory behavior, indicative of surface layering at the interface. Further analysis reveals that the [dmim]+ ions show preferred orientation at the interface with the ring parallel to the surface and methyl group attached to the ring pointing into the vapor phase. The computed surface tensions indicated small differences between these ionic liquids and are inline with recent experimental measurements. The calculated potential drops of these ionic liquids are found to be small and negative. These results could imply that the cation dipoles are likely to orient in the plane that parallel to the surface normal axis. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  19. 低温液相合成Engel复盐晶体研究%Low Temperature Liquid Synthesis of Engel Double Salt Crystal

    Institute of Scientific and Technical Information of China (English)

    张文辉; 张茜; 谷守玉; 万亚珍

    2013-01-01

    It was of great importance in plotting the phase diagram of the Engel double salt crystal for the aim to control the production process.The best conditions of synthesis Engel double salt by low temperature liquid synthesis method were studied.The results shown the basic magnesium carbonate was putting the saturated solution of potassium bicarbonate according to the ratio as following; potassium bicarbonate; basic magnesium carbonate ( wt.) = 39.0: 0.2 and then reacted under the hydrothermal condition as 40 ℃ for 10 min, the mixture solution was crystallized rapidly cooling down to 25℃ and water-bathed for 7 h for the crystal growth process , the Engel double salt crystal were synthesized.The crystal was tested by X-ray powder diffraction ( XRD), which proved that it was in agreeing with the standard spectra.The result showed that the crystal's morphology was of good crystallization.%Engel复盐晶体合成对于准确绘制Engel复盐相图及指导实际生产有重要意义.论文研究了低温条件下液相合成Engel复盐晶体的适宜条件,即碳酸氢钾饱和溶液中加入碱式碳酸镁,其重量比39.0 g/0.2 g,在40℃下水热反应10 min;然后反应溶液从40℃冷却降温到25℃进行析晶,析晶过程持续约7.0h,制备出Engel复盐晶体;对产物进行了XRD及晶体形貌分析,其衍射峰与标准图谱一致,晶体形貌规则,结晶良好.

  20. Reporter-free potentiometric sensing of boronic acids and their reactions by using quaternary ammonium salt-functionalized polymeric liquid membranes.

    Science.gov (United States)

    Wang, Xuewei; Yue, Dengfeng; Lv, Enguang; Wu, Lei; Qin, Wei

    2014-02-18

    The tremendous applications of boronic acids (BAs) in chemical sensing, medical chemistry, molecular assembly, and organic synthesis lead to an urgent demand for developing effective sensing methods for BAs. This paper reports a facile and sensitive potentiometric sensor scheme for heterogeneous detection of BAs based on their unexpected potential responses on quaternary ammonium salt-doped polymeric liquid membranes. (11)B NMR data reveal that a quaternary ammonium chloride can trigger the hydrolysis of an electrically neutral BA in an aprotic solvent. Using the quaternary ammonium salt as the receptor, the BA molecules can be extracted from the sample solution into the polymeric membrane phase and undergo the concomitant hydrolysis. Such salt-triggered hydrolysis generates H(+) ions, which can be coejected into the aqueous phase with the counterions (e.g., Cl(-)) owing to their high hydrophilicities. The perturbation on the ionic partition at the sample-membrane interface changes the phase boundary potential and thus enables the potentiometric sensing of BAs. In contrast to other transduction methods for BAs, for which labeled or separate reporters are exclusively required, the present heterogeneous sensing scheme allows the direct detection of BAs without using any reporter molecules. This technique shows superior detection limits for BAs (e.g., 1.0 × 10(-6) M for phenylboronic acid) as compared to previously reported methods based on colorimetry, fluorimetry, and mass spectrometry. The proposed sensing strategy has also been successfully applied to potentiometric indication of the BA reactions with hydrogen peroxide and saccharides, which allows indirect and sensitive detection of these important species.

  1. Analysis of Organic Acids Accumulated in Kochia Scoparia Shoots and Roots by Reverse-phase High Performance Liquid Chromatography Under Salt and Alkali Stress

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Several organic acids accumulated in Kochia Scoparia shoots and roots were studied by means of reverse-phase high performance liquid chromatography with a C18 column. Five types of binary organic acids were separated. The organic acid concentrations were determined in K. Scoparia seedlings stressed by saline (NaCl) and alkaline(NaHCO3) at the same Na + concentration. Concentrations of organic acids are stimulated by alkaline because the cells will adjust their pH values through the accumulation of organic acids, when the environment is basic. The concentrations of oxalic acid and succinic acid are higher than those of other organic acids, including tartaric acid and malic acid, and the concentration of citric acid is the lowest. The concentrations of the organic acids in the roots are higher than those in the shoots under salt(NaCl) stress, but the results are opposite while the roots are under alkali (NaHCO3) stress. This indicates that there are different adaptive strategies for K. Scoparia seedlings in organic acid metabolism under salt and alkali stress.

  2. Chaotropic salts in liquid chromatographic method development for the determination of pramipexole and its impurities following quality-by-design principles.

    Science.gov (United States)

    Vemić, Ana; Rakić, Tijana; Malenović, Anđelija; Medenica, Mirjana

    2015-01-01

    The aim of this paper is to present a development of liquid chromatographic method when chaotropic salts are used as mobile phase additives following the QbD principles. The effect of critical process parameters (column chemistry, salt nature and concentration, acetonitrile content and column temperature) on the critical quality attributes (retention of the first and last eluting peak and separation of the critical peak pairs) was studied applying the design of experiments-design space methodology (DoE-DS). D-optimal design is chosen in order to simultaneously examine both categorical and numerical factors in minimal number of experiments. Two ways for the achievement of quality assurance were performed and compared. Namely, the uncertainty originating from the models was assessed by Monte Carlo simulations propagating the error equal to the variance of the model residuals and propagating the error originating from the model coefficients' calculation. The baseline separation of pramipexole and its five impurities is achieved fulfilling all the required criteria while the method validation proved its reliability.

  3. Determination of atorvastatin in human serum by salting out assisted solvent extraction and reversed-phase high-performance liquid chromatography–UV detection

    Directory of Open Access Journals (Sweden)

    Jalal Hassan

    2014-01-01

    Full Text Available A simple and rapid technique based on salting out assisted solvent extraction was developed for extraction of atorvastatin from serum sample and high performance liquid chromatography–UV was used for its detection. In the present study, 1.0 mL serum was extracted by 0.5 mL of acetonitrile and some parameters that can affect extraction such as type and volume of extraction solvent, type of salt, and pH were optimized. Under optimized experimental conditions, the calibration curve was found to be linear in the range of 0.001–10 ng mL−1 in human serum and the correlation coefficient (R2 and the limits of detection were >0.99 and 0.0005 ng mL−1, respectively. The accuracy of the method in terms of average recovery of the compound in spiked serum and water samples was better than 90%.

  4. Periodic DFT approaches to crystalline alkali metal azides

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    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".

  5. Proceedings of the Symposium on Lead and Copper Azides

    Science.gov (United States)

    1966-10-26

    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

  6. The Manufacture of Silver Azide R.D. 1336

    Science.gov (United States)

    1950-02-01

    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

  7. Influence of acids on the decomposition of azide polymers

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-12-31

    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.

  8. Azide SHS of aluminium nitride nanopowder and its application for obtaining Al-Cu-AlN cast nanocomposite

    Science.gov (United States)

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

    2016-11-01

    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.

  9. Soft X-ray absorption spectra of aqueous salt solutions with highly charged cations in liquid microjets

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Craig P.; Uejio, Janel S.; Duffin, Andrew M.; Drisdell, Walter S.; Smith, Jared D.; Saykally, Richard J.

    2010-03-11

    X-ray absorption spectra of 1M aqueous solutions of indium (III) chloride, yttrium (III) bromide, lanthanum (III) chloride, tin (IV) chloride and chromium (III) chloride have been measured at the oxygen K-edge. Relatively minor changes are observed in the spectra compared to that of pure water. SnCl{sub 4} and CrCl{sub 3} exhibit a new onset feature which is attributed to formation of hydroxide or other complex molecules in the solution. At higher energy, only relatively minor, but salt-specific changes in the spectra occur. The small magnitude of the observed spectral changes is ascribed to offsetting perturbations by the cations and anions.

  10. Silver-Catalyzed Decarboxylative Radical Azidation of Aliphatic Carboxylic Acids in Aqueous Solution.

    Science.gov (United States)

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

    2015-08-12

    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.

  11. Production and some properties of salt-tolerant beta-xylosidases from a shoyu koji mold, Aspergillus oryzae in solid and liquid cultures.

    Science.gov (United States)

    Hashimoto, T; Morishita, M; Iwashita, K; Shimoi, H; Nakata, Y; Tsuji, Y; Ito, K

    1999-01-01

    Beta-xylosidase production from a shoyu (soy sauce) koji mold, Aspergillus oryzae HL15, cultured in solid and liquid media was examined and some properties of the enzymes were studied. Three beta-xylosidases (Xy11, Xy12 and Xy13) were easily extracted with 0.5% NaCl from a solid medium and purified homogeneously on SDS-PAGE by chromatography. On the other hand, in a liquid medium, A. oryzae HL15 produced mainly cell-wall-bound beta-xylosidases which could not be extracted with 0.5% NaCl or any detergent. Cell-wall-bound beta-xylosidases, Xy11-CB and Xy12-CB, were liberated by digestion of mycelia with Yatalase and purified to a homogeneous state on SDS-PAGE by HPLC column chromatography. Four beta-xylosidases (Xy11, Xy12, Xy11-CB and Xy12-CB) exhibited not only high activity at high NaCl concentrations, but also similar properties; on the other hand, Xy13 differed in terms of thermostability and halophilic properties. The salt tolerance of beta-xylosidases in A. oryzae suggests that these enzymes are highly active and involved in releasing xylose in shoyu moromi mash.

  12. Molecular dynamics analysis of the effect of electronic polarization on the structure and single-particle dynamics of mixtures of ionic liquids and lithium salts.

    Science.gov (United States)

    Lesch, Volker; Montes-Campos, Hadrián; Méndez-Morales, Trinidad; Gallego, Luis Javier; Heuer, Andreas; Schröder, Christian; Varela, Luis M

    2016-11-28

    We report a molecular dynamics study on the effect of electronic polarization on the structure and single-particle dynamics of mixtures of the aprotic ionic liquid 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide ([EMIM][TFSI]) doped with a lithium salt with the same anion at 298 K and 1 bar. In particular, we analyze the effect of electron density fluctuations on radial distribution functions, velocity autocorrelation functions, cage correlation functions, mean-squared displacements, and vibrational densities of states, comparing the predictions of the quantum-chemistry-based Atomistic Polarizable Potential for Liquids, Electrolytes, & Polymers (APPLE&P) with those of its nonpolarizable version and those of the standard non-polarizable Optimized Potentials for Liquid Simulations-All Atom (OPLS-AA). We found that the structure of the mixture is scarcely modified by the fluctuations in electron charge of their constituents, but their transport properties are indeed quite drastically changed, with larger mobilities being predicted for the different species in the bulk mixtures with the polarizable force field. Specifically, the mean-squared displacements are larger for the polarizable potentials at identical time intervals and the intermediate subdiffusive plateaus are greatly reduced, so the transition to the diffusive regime takes place much earlier than in the non-polarizable media. Moreover, the correlations of the added cations inside their cages are weakened out earlier and their vibrational densities of states are slightly red-shifted, reflecting the weakening effect of the electronic polarization on the Coulomb coupling in these dense ionic media. The comparison of OPLS-AA with non-polarizable APPLE&P indicates that adding polarization to OPLS-AA is not sufficient to achieve results close to experiments.

  13. Molecular dynamics analysis of the effect of electronic polarization on the structure and single-particle dynamics of mixtures of ionic liquids and lithium salts

    Science.gov (United States)

    Lesch, Volker; Montes-Campos, Hadrián; Méndez-Morales, Trinidad; Gallego, Luis Javier; Heuer, Andreas; Schröder, Christian; Varela, Luis M.

    2016-11-01

    We report a molecular dynamics study on the effect of electronic polarization on the structure and single-particle dynamics of mixtures of the aprotic ionic liquid 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide ([EMIM][TFSI]) doped with a lithium salt with the same anion at 298 K and 1 bar. In particular, we analyze the effect of electron density fluctuations on radial distribution functions, velocity autocorrelation functions, cage correlation functions, mean-squared displacements, and vibrational densities of states, comparing the predictions of the quantum-chemistry-based Atomistic Polarizable Potential for Liquids, Electrolytes, & Polymers (APPLE&P) with those of its nonpolarizable version and those of the standard non-polarizable Optimized Potentials for Liquid Simulations-All Atom (OPLS-AA). We found that the structure of the mixture is scarcely modified by the fluctuations in electron charge of their constituents, but their transport properties are indeed quite drastically changed, with larger mobilities being predicted for the different species in the bulk mixtures with the polarizable force field. Specifically, the mean-squared displacements are larger for the polarizable potentials at identical time intervals and the intermediate subdiffusive plateaus are greatly reduced, so the transition to the diffusive regime takes place much earlier than in the non-polarizable media. Moreover, the correlations of the added cations inside their cages are weakened out earlier and their vibrational densities of states are slightly red-shifted, reflecting the weakening effect of the electronic polarization on the Coulomb coupling in these dense ionic media. The comparison of OPLS-AA with non-polarizable APPLE&P indicates that adding polarization to OPLS-AA is not sufficient to achieve results close to experiments.

  14. Optimization of a ligand immobilization and azide group endcapping concept via "Click-Chemistry" for the preparation of adsorbents for antibody purification.

    Science.gov (United States)

    Horak, Jeannie; Hofer, Stefan; Lindner, Wolfgang

    2010-12-15

    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

  15. Synthesis, Structural Analysis and Antimicrobial Activities of Novel Water Soluble Ionic Liquids Derived from N-Heterocyclic Carbene Salts

    Directory of Open Access Journals (Sweden)

    Ahmet Kunduracıoğlu

    2016-06-01

    Full Text Available Six N-heterocyclic Carbene based Ionic Liquids (ILs have been synthesized by conventional methods. The ILs were spectroscopically characterized by NMR and FT-IR techniques. Their in vitro antimicrobial activities were determined towards gram-positive and gram-negative bacterias and yeast strains using minimum inhibition concentration (MIC assay. The best inhibition performances were obtained with compound 1 due to its more hydrophilic nature compared with the others. It exhibited 1 mg L–1 MIC value against to the most bacteria while the others showed 4 mg L–1. This work is licensed under a Creative Commons Attribution 4.0 International License.

  16. Fuel and Core Design Options to Overcome the Heavy Metal Loading Limit and Improve Performance and Safety of Liquid Salt Cooled Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Petrovic, Bojan [Georgia Inst. of Technology, Atlanta, GA (United States); Maldonado, Ivan [Univ. of Tennessee, Knoxville, TN (United States)

    2016-04-14

    The research performed in this project addressed the issue of low heavy metal loading and the resulting reduced cycle length with increased refueling frequency, inherent to all FHR designs with solid, non-movable fuel based on TRISO particles. Studies performed here focused on AHTR type of reactor design with plate (“plank”) fuel. Proposal to FY12 NEUP entitled “Fuel and Core Design Options to Overcome the Heavy Metal Loading Limit and Improve Performance and Safety of Liquid Salt Cooled Reactors” was selected for award, and the 3-year project started in August 2012. A 4-month NCE was granted and the project completed on December 31, 2015. The project was performed by Georgia Tech (Prof. Bojan Petrovic, PI) and University of Tennessee (Prof. Ivan Maldonado, Co-PI), with a total funding of $758,000 over 3 years. In addition to two Co-PIs, the project directly engaged 6 graduate students (at doctoral or MS level) and 2 postdoctoral researchers. Additionally, through senior design projects and graduate advanced design projects, another 23 undergraduate and 12 graduate students were exposed to and trained in the salt reactor technology. We see this as one of the important indicators of the project’s success and effectiveness. In the process, 1 journal article was published (with 3 journal articles in preparation), together with 8 peer-reviewed full conference papers, 8 peer-reviewed extended abstracts, as well as 1 doctoral dissertation and 2 master theses. The work included both development of models and methodologies needed to adequately analyze this type of reactor, fuel, and its fuel cycle, as well as extensive analyses and optimization of the fuel and core design.

  17. A Direct Comparison of Azide and Nitrile Vibrational Probes

    Science.gov (United States)

    Gai, Xin Sonia; Coutifaris, Basil A.; Brewer, Scott H.; Fenlon, Edward E.

    2011-01-01

    The synthesis of 2′-azido-5-cyano-2′-deoxyuridine, N3CNdU (1), from trityl-protected 2′-amino-2′-deoxyuridine was accomplished in four steps with a 12.5% overall yield. The IR absorption positions and profiles of the azide and nitrile group of N3CNdU were investigated in 14 different solvents and water/DMSO solvent mixtures. The azide probe was superior to the nitrile probe in terms of its extinction coefficient, which is 2–4 times larger. However, the nitrile IR absorbance profile is generally less complicated by accidental Fermi resonance. The IR frequencies of both probes undergo a substantial red shift upon going from water to aprotic solvents such as THF or DMSO. DFT calculations supported the hypothesis that the molecular origin of the higher observed frequency in water is primarily due to hydrogen bonds between the probes and water molecules. PMID:21336362

  18. Development of SHS azide technology of silicon carbide nanopowder

    Science.gov (United States)

    Titova, Y. V.; Illarionov, A. Yu; Amosov, A. P.; Maidan, D. A.; Smetanin, K. S.

    2017-02-01

    The possibility of increasing the purity and yield of the SiC nanopowder using an intermediate synthesis of silicon nitride (Si3N4) by azide technology of self-propagating high-temperature synthesis based on the use of a powder of sodium azide (NaN3) as a nitriding reagent was investigated. As a result of combustion of the initial mixture of powders ‘19Si + 6NaN3 + (NH4)2SiF6 + 20’, a powdery product was obtained, consisting almost entirely of SiC (about 90%) with an admixture of Si3N4 and Si (about 5% each), and representing nanoparticles (80-150 nm) combined into agglomerates with the size up to 50 µm.

  19. Data for the size of cholesterol-fat micelles as a function of bile salt concentration and the physico-chemical properties of six liquid experimental pine-derived phytosterol formulations in a cholesterol-containing artificial intestine fluid

    Directory of Open Access Journals (Sweden)

    Jinsoo Yi

    2017-02-01

    Full Text Available The data in this paper are additional information to the research article entiltled “Inhibition of cholesterol transport in an intestine cell model by pine-derived phytosterols” (Yi et al.,2016 [1]. The data derived from the measurement on six liquid formulations of commercial pine-derived phytosterol (CPP by dynamic light scattering. The data cover micelle size and the zeta-potential for formulations with cholesterol including monoglyceride, oleic acid, and bile salt. The data demonstrate the critical effect of the bile salt concentration on the size of cholesterol-digested fat micelles.

  20. Deep eutectic liquid organic salt as a new solvent for liquid-phase microextraction and its application in ligandless extraction and preconcentraion of lead and cadmium in edible oils.

    Science.gov (United States)

    Karimi, Mehdi; Dadfarnia, Shayessteh; Shabani, Ali Mohammad Haji; Tamaddon, Fatemeh; Azadi, Davood

    2015-11-01

    Deep eutectic liquid organic salt was used as the solvent and a liquid phase microextraction (DES-LPME) combined with electrothermal atomic absorption spectrometry (ETAAS) was developed for separation, preconcentration and determination of lead and cadmium in edible oils. A 4:1 mixture of deep eutectic solvent and 2% nitric acid (200 µL) was added to an oil sample. The mixture was vortexed and transferred into a water bath at 50 °C and stirred for 5 minutes. After the extraction was completed, the phases were separated by centrifugation, and the enriched analytes in the deep eutectic solvent phase were determined by ETAAS. Under optimized extraction conditions and for an oil sample of 28 g, enhancement factors of 198 and 195 and limits of detection (defined as 3 Sb/m) of 8 and 0. 2 ng kg(-1) were achieved for lead and cadmium respectively. The method was successfully applied to the determination of lead and cadmium in various edible oils.

  1. Sensitization of High Density Silver Azide to Stab Initiation

    Science.gov (United States)

    1983-05-01

    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

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

    Indian Academy of Sciences (India)

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

    2016-10-01

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

  3. Molecular dynamics simulation of the structure and interfacial free energy barriers of mixtures of ionic liquids and divalent salts near a graphene wall.

    Science.gov (United States)

    Gómez-González, Víctor; Docampo-Álvarez, Borja; Méndez-Morales, Trinidad; Cabeza, Oscar; Ivaništšev, Vladislav B; Fedorov, Maxim V; Gallego, Luis J; Varela, Luis M

    2016-12-21

    A molecular dynamics study of mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) with magnesium tetrafluoroborate (Mg[BF4]2) confined between two parallel graphene walls is reported. The structure of the system is analyzed by means of ionic density profiles, lateral structure of the first layer close to the graphene surface and angular orientations of imidazolium cations. Free energy profiles for divalent magnesium cations are calculated using two different methods in order to evaluate the height of the potential barriers near the walls, and the results are compared with those of mixtures of the same ionic liquid and a lithium salt (Li[BF4]). Preferential adsorption of magnesium cations is analyzed using a simple model and compared to that of lithium cations, and vibrational densities of states are calculated for the cations close to the walls analyzing the influence of the graphene surface charge. Our results indicate that magnesium cations next to the graphene wall have a roughly similar environment to that in the bulk. Moreover, they face higher potential barriers and are less adsorbed on the charged graphene walls than lithium cations. In other words, magnesium cations have a more stable solvation shell than lithium ones.

  4. Novel industrial wastewater treatment integrated with recovery of water and salt under a zero liquid discharge concept.

    Science.gov (United States)

    Rajamani, Sengodagounder

    2016-03-01

    Conventional industrial effluent treatment systems are designed to reduce biochemical oxygen demand (BOD), chemical oxygen demand (COD) but not total dissolved solids (TDS), mainly contributed by chlorides. In addition to the removal of TDS, it is necessary to recover water for reuse to meet the challenges of shortage of quality water. To recover water, the wastewater needs to be further treated by adopting treatment systems including microfilters, low pressure membrane units such as ultrafiltration (UF), membrane bioreactors (MBR), etc., for the application of reverse osmosis (RO) systems. By adopting the RO system, 75%-80% of quality water with water rejected from the RO system with high TDS concentration is being addressed by methods such as forced evaporation systems. The recovery of water from domestic and industrial waste for reuse has become a reality. The membrane system has been used for different applications. It has become mandatory to achieve zero liquid discharge (ZLD) in many states in India and other countries such as Spain, China, etc., and resulted in development of new treatment technologies to suit the local conditions.

  5. Thermochemical Properties of Nicotine Salts

    Directory of Open Access Journals (Sweden)

    Riggs DM

    2014-12-01

    Full Text Available The thermal gravimetric analysis (TGA and differential scanning calorimetry (DSC results presented in this report clearly show that the thermal stability and the endothermic peak nicotine release temperatures are different for different nicotine salts and these temperatures appear to be linked to the general microstructural details of the salt itself. In addition, the peak nicotine release temperatures are highly dependent upon the sample size used. The heat of vaporization for neat (non-protonated nicotine is also sample-size dependent. The TGA data showed that the least stable of the salts tested at elevated temperatures was the liquid salt nicotine triacetate followed by the crystalline materials (e.g., nicotine gallate and finally, the amorphous salts (e.g., nicotine alginate. The DSC results revealed that the liquid and crystalline salts exhibit nicotine release endotherms that are strongly related to the sample weight being tested. The amorphous salts show nicotine endotherm peak temperatures that are nearly independent of the sample weight. The range of peak nicotine release temperatures varied depending upon the specific salts and the sample size from 83 oC to well over 200 oC. Based on these results, the evolution of nicotine from the nicotine salt should be expected to vary based on the composition of the salt, the details of its microstructure, and the amount of nicotine salt tested.

  6. Study of selected benzyl azides by UV photoelectron spectroscopy and mass spectrometry

    Science.gov (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.

    2010-09-01

    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.

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

    Science.gov (United States)

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

    2016-07-01

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

  8. Structural effect of glyme-Li(+) salt solvate ionic liquids on the conformation of poly(ethylene oxide).

    Science.gov (United States)

    Chen, Zhengfei; McDonald, Samila; Fitzgerald, Paul A; Warr, Gregory G; Atkin, Rob

    2016-06-01

    The conformation of 36 kDa polyethylene oxide (PEO) dissolved in three glyme-Li(+) solvate ionic liquids (SILs) has been investigated by small angle neutron scattering (SANS) and rheology as a function of concentration and compared to a previously studied SIL. The solvent quality of a SIL for PEO can be tuned by changing the glyme length and anion type. Thermogravimetric analysis (TGA) reveals that PEO is dissolved in the SILs through Li(+)-PEO coordinate bonds. All SILs (lithium triglyme bis(trifluoromethanesulfonyl)imide ([Li(G3)]TFSI), lithium tetraglyme bis(pentafluoroethanesulfonyl)imide ([Li(G4)]BETI), lithium tetraglyme perchlorate ([Li(G4)]ClO4) and the recently published [Li(G4)]TFSI) are found to be moderately good solvents for PEO but solvent quality decreases in the order [Li(G4)]TFSI ∼ [Li(G4)]BETI > [Li(G4)]ClO4 > [Li(G3)]TFSI due to decreased availability of Li(+) for PEO coordination. For the same glyme length, the solvent qualities of SILs with TFSI(-) and BETI(-) anions ([Li(G4)]TFSI and [Li(G4)]BETI) are very similar because they weakly coordinate with Li(+), which facilitates Li(+)-PEO interactions. [Li(G4)]ClO4 presents a poorer solvent environment for PEO than [Li(G4)]BETI because ClO4(-) binds more strongly to Li(+) and thereby hinders interactions with PEO. [Li(G3)]TFSI is the poorest PEO solvent of these SILs because G3 binds more strongly to Li(+) than G4. Rheological and radius of gyration (Rg) data as a function of PEO concentration show that the PEO overlap concentrations, c* and c**, are similar in the three SILs.

  9. Stability of a Ag/AgCl reference electrode equipped with an ionic liquid salt bridge composed of 1-methyl-3-octylimidazolium bis(trifluoromethanesulfonyl)-amide in potentiometry of pH standard buffers.

    Science.gov (United States)

    Shibata, Manabu; Yamanuki, Mikito; Iwamoto, Yasukazu; Nomura, Satoshi; Kakiuchi, Takashi

    2010-01-01

    The stability of a Ag/AgCl reference electrode equipped with a gelled ionic liquid, 1-methyl-3-octylimidazolium bis(trifluoromethanesulfonyl)amide (C(8)mimC(1)C(1)N), as a salt bridge, was examined in the potentiometry of pH standard solutions. The variation in the liquid junction potential (LJP) of the ionic liquid (IL)-type reference electrode, measured with respect to a double junction-type KCl reference electrode, was within 1 mV when one standard solution was replaced by another, except for the phthalate standard. The time course of the potential of the IL-type reference electrode showed a standard deviation of ±0.3 mV in all buffer solutions. The reproducible deviation of the potential of the IL-type reference electrode in the phthalate pH standard amounted to 5 mV. The deviation is due to the partition of the hydrogen phthalate in the C(8)mimC(1)C(1)N, influencing the phase boundary potential (PBP) across the interface between C(8)mimC(1)C(1)N and the phthalate standard. If a citrate standard is used instead of the phthalate buffer, the IL salt bridge works satisfactorily as a salt bridge for a reference electrode suitable for potentiometoric pH measurements.

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

    Science.gov (United States)

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

    2016-09-01

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

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

    DEFF Research Database (Denmark)

    Gromov, I; Marchesini, A; Farver, O

    1999-01-01

    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...

  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)

    2007-12-31

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

  13. Adjusting the surface areal density of click-reactive azide groups by kinetic control of the azide substitution reaction on bromine-functional SAMs.

    Science.gov (United States)

    Zhang, Shuo; Maidenberg, Yanir; Luo, Kai; Koberstein, Jeffrey T

    2014-06-03

    Azide-alkyne click chemistry has emerged as an important and versatile means for tethering a wide variety of guest molecules to virtually any substrate. In many of these applications, it is important to exercise control over the areal density of surface functional groups to achieve a desired areal density of the tethered guest molecule of interest. We demonstrate herein that the areal density of surface azide groups on flat germanium surfaces and nanoparticle substrates (silica and iron oxide) can be controlled kinetically by appropriately timed quenching of the S(N)2 substitution reaction of bromo-alkane-silane monolayers induced by the addition of sodium azide. The kinetics of the azide substitution reaction on monolayers formed on flat Ge substrates, determined by attenuated total reflection infrared spectroscopy (ATR-IR), are found to be identical to those for monolayers formed on both silica and iron oxide nanoparticles, the latter determined by transmission infrared spectroscopy. To validate the method, the percentages of surface bromine groups converted to azide groups after various reaction times were measured by quenching the S(N)2 reaction followed by analysis with ATR-IR (for Ge) and thermogravimetric analysis (after a subsequent click reaction with an alkyne-terminal polymer) for the nanoparticle substrates. The conversions found after quenching agree well with those expected from the standard kinetic curves. The latter result suggests that the kinetic method for the control of azide group areal density is a versatile means for functionalizing substrates with a prescribed areal density of azide groups for subsequent click reactions, and that the method is universal for any substrate, flat or nanoparticle, that can be modified with bromo-alkane-silane monolayers. Regardless of the surface geometry, we find that the azide substitution reaction is complete within 2-3 h, in sharp contrast to previous reports that indicate times of 48-60 h required for

  14. A DFT study of the mechanism of copper-catalyzed synthesis of 2H-indazoles from aryl azide.

    Science.gov (United States)

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

    2014-01-07

    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.

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

    Institute of Scientific and Technical Information of China (English)

    张小航; 高占先

    2001-01-01

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

  16. Exchange reactions between a molten salt and a solution of tri-butyl phosphate in a liquid silicone; Reactions d'echange entre un sel fondu et une solution de phosphate de tributyle dans un silicone liquide

    Energy Technology Data Exchange (ETDEWEB)

    Hertzog, D. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-07-01

    Present interest centred around molten salts can be explained by their possible use in the field of nuclear energy, in particular as a support for fuels and also as reprocessing agents. It seemed of interest to consider the molten salt as a solvent and to study partition phenomena with a second phase stable at high temperatures. The salt chosen is a ternary eutectic of alkali nitrates and the second phase is a solution of tri-butyl phosphate in a liquid silicone. The working temperature is fixed at 150 deg. C. We have studied first of all the stability of the two phases and their mutual solubilities at this temperature. It has been shown that the two solvents are immiscible and stable. We have also described the extraction by the silicone solution of various products in solution in the salt phase, and have determined the partition coefficients and the formulae of the extracted molecules. It has been possible to calculate the partition coefficients of the following ions extracted as nitrates: Li{sup +}, Na{sup +}, K{sup +}, Sr{sup 2+}, Ca{sup 2+}, Ba{sup 2+}, Hg{sup 2+} whose partition coefficients are very low: Mg{sup 2+}, Ni{sup 2+}, Co{sup 2+}, Zn{sup 2+} whose extraction yields are greater than 50 per cent; finally Ce{sup 3+}, La{sup 3+}, UO{sub 2}{sup 2+}, highly extracted. Also the following anions have been extracted in the form of alkali salts: F{sup -}, Cl{sup -}, Br{sup -}, I{sup -}, IO{sub 3}{sup -}, CN{sup -}, SO{sub 4}{sup -}, C{sub 2}O{sub 4}{sup -}, NO{sub 2}{sup -}. Amongst these, only the halogens have non-negligible partition coefficients. In certain particular cases we have been able to study the influence of complex formation on the extraction phenomena. Two applications are described: - The separation of two products by complex formation and extraction (separation of magnesium from cobalt, nickel and zinc); - The calculation of the equilibrium constant of a complex by measurement of the variation in the partition coefficient of the ion complexed

  17. Evolving Structural Diversity and Metallicity in Compressed Lithium Azide

    KAUST Repository

    Prasad, Dasari L. V. K.

    2013-10-10

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-12-31

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

  19. Tylosin and chlortetracycline effects during swine manure digestion: influence of sodium azide.

    Science.gov (United States)

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

    2010-12-01

    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. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  20. The influence of salt matrices on the reversed-phase liquid chromatography behavior and electrospray ionization tandem mass spectrometry detection of glyphosate, glufosinate, aminomethylphosphonic acid and 2-aminoethylphosphonic acid in water.

    Science.gov (United States)

    Skeff, Wael; Recknagel, Constantin; Schulz-Bull, Detlef E

    2016-12-02

    The analysis of highly polar and amphoteric compounds in seawater is a continuing challenge in analytical chemistry due to the possible formation of complexes with the metal cations present in salt-based matrices. Here we provide information for the development of analytical methods for glyphosate, glufosinate, AMPA, and 2-AEP in salt water, based on studies of the effects of salt matrices on reversed-phase liquid chromatography-heated electrospray ionization-tandem mass spectrometry (RP-LC-HESI-MS/MS) after derivatization of the target compounds with FMOC-Cl. The results showed that glyphosate was the only analyte with a strong tendency to form glyphosate-metal complexes (GMC), which clearly influenced the analysis. The retention times (RTs) of GMC and free glyphosate differed by approximately 7.00min, reflecting their distinct RP-LC behaviors. Divalent cations, but not monovalent (Na(+), K(+)) or trivalent (Al(3+), Fe(3+)) cations, contributed to this effect and their influence was concentration-dependent. In addition, Cu(2+), Co(2+), Zn(2+), and Mn(2+) prevented glyphosate detection whereas Ca(2+), Mg(2+), and Sr(2+) altered the retention time. At certain tested concentrations of Ca(2+) and Sr(2+) glyphosate yielded two peaks, which violated the fundamental rule of LC, that under the same analytical conditions a single substance yields only one LC-peak with a specific RT. Salt-matrix-induced ion suppression was observed for all analytes, especially under high salt concentrations. For glyphosate and AMPA, the use of isotopically labeled internal standards well-corrected the salt-matrix effects, with better results achieved for glufosinate and 2-AEP with the AMPA internal standard than with the glyphosate internal standard. Thus, our study demonstrated that Ca(2+), Mg(2+), and Sr(2+) can be used together with FMOC-Cl to form GMC-FMOC which is suitable for RP-LC-HESI-MS/MS analysis.

  1. Hygroscopic Salts on Mars

    Science.gov (United States)

    Melchiorri, R.; Davila, A. F.; Chittenden, J.; Haberle, R. M.

    2008-12-01

    We present preliminary results on the influence of a salt-rich regolith in the water cycle of Mars. Global climate modeling shows that the relative humidity on the Martian surface often reaches values above the deliquescence point of salts that are common components of the regolith. At the deliquescence point, these salts will absorb atmospheric water vapor and form a saturated, transient liquid solution that is stable under a range of temperatures. If atmospheric temperatures fall below the eutectic point of the solution, the later will freeze in the pore space of the regolith, thereby resulting in a net transport of water from the vapor phase in the atmosphere, to the solid state in the regolith. This simple model partially accounts for some the distribution of water on the Martian surface as revealed by Mars Odyssey, in particular, we find that: even though the Cl and surface water distributions detected by HEND/ODYSSEY are highly correlated, salt deliquescence under the the present atmospheric conditions does not explain the overall distribution of water in the near surface regolith. However deliquescence of salt-rich soils could be an important contributor to the distribution of water in the regolith at high obliquity. In that scenario the water in the near-surface regolith would be the remnant of high obliquity conditions salt deliquescence is still active in different regions on Mars today, and it should be introduced as a parameter in the modern GCMs as a new ground/atmosphere interaction

  2. Extending and Verification of RELAP5 Code for Liquid Fueled Molten Salt Reactor%RELAP5应用于液态燃料熔盐堆的扩展及验证

    Institute of Scientific and Technical Information of China (English)

    施承斌; 程懋松; 刘桂民

    2016-01-01

    为将RELAP5程序应用于液态燃料熔盐堆的建模分析,需要对RELAP5的模型进行扩展.基于RELAP5原有的点堆模型和热工水力模型,新增了液态燃料熔盐堆点堆模型和相应的带有内热源的热工水力模型,并通过熔盐实验堆(MSRE)实验数据进行验证.结果表明,扩展后的RELAP5程序能够适用于液态燃料熔盐堆系统建模分析.%In order to analyze the liquid fueled molten salt reactor using RELAP5 code,models in RELAP5 code need to be extended.This paper attempts to add new point kinetic model of liquid fueled reactor and thermo-hydraulics model with internal heat source based on the original RELAP5 models,then the code is verified using MSRE experimental datum.The results indicate that the extended RELAP5 code can be applied to model and analyze the liquid fueled molten salt reactor.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1983-01-01

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

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

    Science.gov (United States)

    Bhaskar, V Vijay

    2004-12-01

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

  5. Kinetics and mechanism of the reaction of sodium azide with hypochlorite in aqueous solution.

    Science.gov (United States)

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

    2010-10-15

    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.

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

    Directory of Open Access Journals (Sweden)

    Sharma Anuj

    2012-12-01

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

  7. Electrochemically Protected Copper(I)-Catalyzed Azide-Alkyne Cycloaddition

    Science.gov (United States)

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

    2012-01-01

    The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction has found broad application in myriad fields. For the most demanding applications requiring 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. The simple procedure efficiently achieves excellent yields of CuAAC products involving 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 described. Cyclic voltammetry revealed reversible or quasi-reversible electrochemical redox behavior of copper complexes of the TBTA derivative (2; E1/2 = 60 mV vs. Ag/AgCl), sulfonated bathophenanthroline (3; E1/2 = -60 mV), and sulfonated tris(benzimidazoylmethyl)amine (4; E1/2 ~ -70 mV), and showed catalytic turnover to be rapid relative to the voltammetry time scale. Under the influence of a -200 mV potential established using a reticulated vitreous carbon working electrode, CuSO4 and 3 formed a superior catalyst. Electrochemically-protected bioconjugations in air were performed using bacteriophage Qβ derivatized with azide moieties at surface lysine residues. The complete addressing of more than 600 reactive sites per particle was demonstrated within 12 hours of electrolysis with sub-stoichiometric quantities of Cu•3. PMID:18504727

  8. Electrochemically protected copper(I)-catalyzed azide-alkyne cycloaddition.

    Science.gov (United States)

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

    2008-06-16

    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.

  9. Liquid Salts as Media for Process Heat Transfer from VHTR's: Forced Convective Channel Flow Thermal Hydraulics, Materials, and Coating

    Energy Technology Data Exchange (ETDEWEB)

    Sridharan, Kumar; Anderson, Mark; Allen, Todd; Corradini, Michael

    2012-01-30

    The goal of this NERI project was to perform research on high temperature fluoride and chloride molten salts towards the long-term goal of using these salts for transferring process heat from high temperature nuclear reactor to operation of hydrogen production and chemical plants. Specifically, the research focuses on corrosion of materials in molten salts, which continues to be one of the most significant challenges in molten salts systems. Based on the earlier work performed at ORNL on salt properties for heat transfer applications, a eutectic fluoride salt FLiNaK (46.5% LiF-11.5%NaF-42.0%KF, mol.%) and a eutectic chloride salt (32%MgCl2-68%KCl, mole %) were selected for this study. Several high temperature candidate Fe-Ni-Cr and Ni-Cr alloys: Hastelloy-N, Hastelloy-X, Haynes-230, Inconel-617, and Incoloy-800H, were exposed to molten FLiNaK with the goal of understanding corrosion mechanisms and ranking these alloys for their suitability for molten fluoride salt heat exchanger and thermal storage applications. The tests were performed at 850C for 500 h in sealed graphite crucibles under an argon cover gas. Corrosion was noted to occur predominantly from dealloying of Cr from the alloys, an effect that was particularly pronounced at the grain boundaries Alloy weight-loss due to molten fluoride salt exposure correlated with the initial Cr-content of the alloys, and was consistent with the Cr-content measured in the salts after corrosion tests. The alloys weight-loss was also found to correlate to the concentration of carbon present for the nominally 20% Cr containing alloys, due to the formation of chromium carbide phases at the grain boundaries. Experiments involving molten salt exposures of Incoloy-800H in Incoloy-800H crucibles under an argon cover gas showed a significantly lower corrosion for this alloy than when tested in a graphite crucible. Graphite significantly accelerated alloy corrosion due to the reduction of Cr from solution by graphite and formation

  10. Fast, Cell-compatible Click Chemistry with Copper-chelating Azides for Biomolecular Labeling**

    Science.gov (United States)

    Uttamapinant, Chayasith; Tangpeerachaikul, Anupong; Grecian, Scott; Clarke, Scott; Singh, Upinder; Slade, Peter; Gee, Kyle R.; Ting, Alice. Y.

    2012-01-01

    We report that azides capable of copper-chelation undergo much faster “Click chemistry” (copper-accelerated azide-alkyne cycloaddition, or CuAAC) than nonchelating azides under a variety of biocompatible conditions. This kinetic enhancement allowed us to perform site-specific protein labeling on the surface of living cells with only 10–40 µM CuI/II and much higher signal than could be obtained using the best previously-reported live-cell compatible CuAAC labeling conditions. Detection sensitivity was also increased for CuAAC detection of alkyne-modified proteins and RNA labeled by metabolic feeding. PMID:22555882

  11. The chemistry of molten salt mixtures: application to the reductive extraction of lanthanides and actinides by a liquid metal; Chimie des melanges de sels fondus. Application a l'extraction reductrice d'actinides et de lanthanides par un metal liquide

    Energy Technology Data Exchange (ETDEWEB)

    Finne, J

    2005-10-15

    The design of a process of An/Ln separation by liquid - liquid extraction can be used for on-line purification of the molten salt in a molten salt nuclear reactor (Generation IV) as well as reprocessing various spent fuels. In order to establish the chemical properties of An and Ln in molten salt mediums, E - pO{sub 2} - diagrams were established for the relevant chemical elements. With the purpose of checking the possibilities of separating the An from Ln, the real activity coefficients in liquid metals were measured. An experimental protocol was developed and validated on the Gd/Ga system. It was then transferred to radioactive environment to measure the activity coefficient of Pu in Ga. The results made it possible to estimate the effectiveness of the Pu extraction and its separation from Gd and Ce. The selectivity was shown to decrease with the temperature and Al and Ga showed a good selectivity between Pu and the Ce in fluoride medium. (author)

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

    Science.gov (United States)

    1991-09-01

    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

  13. Complete mapping of crystallization pathways during cholesterol precipitation from model bile: influence of physical-chemical variables of pathophysiologic relevance and identification of a stable liquid crystalline state in cold, dilute and hydrophilic bile salt-containing systems.

    Science.gov (United States)

    Wang, D Q; Carey, M C

    1996-03-01

    Using complementary physical-chemical techniques we defined five different crystallization pathways as functions of time (30 days) and increasing lecithin (egg yolk) content in pathophysiologically relevant model biles super-saturated (cholesterol saturation indices, 1.2 - 2.7) by dilution of approximately equal to 29 g/dl bile salt-lecithin-cholesterol micellar solutions. As evidenced by quasi-elastic light-scattering spectroscopy, supersaturation was heralded by the appearance of unilamellar vesicles. With the lowest lecithin contents, arc-like crystals with habit and density (d 1.030 g/mL) consistent with anhydrous cholesterol appeared first and evolved via helical and tubular crystals to form plate-like cholesterol monohydrate crystals (d 1.045 g/mL). With higher lecithin fractions, cholesterol monohydrate crystals appeared earlier than arc and other transitional crystals. With typical physiological lecithin contents, early liquid crystals (d 1.020 g/mL) were followed by cholesterol monohydrate crystals and subsequent appearances of arc and other intermediate crystals. With higher lecithin contents, liquid crystals were followed by cholesterol monohydrate crystals only, and at the highest lecithin mole fractions, liquid crystals appeared that did not generate solid crystals. Added calcium increased solid crystal number in proportion to its concentration (5 - 20 mM) but did not influence appearance times, crystallization pathways, or micellar cholesterol solubilities. Decreases in temperature (37 degrees --> 4 degrees C), total lipid concentration (7.3 --> 2.4 g/dL), and bile salt hydrophobicity (3 alpha, 12 alpha --> 3 alpha, 7 alpha, 12 alpha --> 3 alpha, 7 beta hydroxylated taurine conjugates) progressively shifted all crystallization pathways to lower lecithin contents, retarded crystallization, and decreased micellar cholesterol solubilities. The lecithin content of mother biles decreased markedly during crystallization especially where liquid crystals were

  14. Influence of azide incorporation on binding affinity by small papain inhibitors.

    Science.gov (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

    2014-10-15

    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.

  15. Copper-mediated amidation of alkenylzirconocenes with acyl azides: formation of enamides.

    Science.gov (United States)

    Liu, Hailan; Zhou, Yiqing; Yan, Xiaoyu; Chen, Chao; Liu, Qingbin; Xi, Chanjuan

    2013-10-18

    Copper-mediated amidation of alkenylzirconocenes generated in situ from alkynes and zirconocenes with acyl azides is accomplished under mild conditions. The reaction can be used to prepare various enamides.

  16. Copper-chelating azides for efficient click conjugation reactions in complex media.

    Science.gov (United States)

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

    2014-06-02

    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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Liquid Salts as Media for Process Heat Transfer from VHTR's: Forced Convective Channel Flow Thermal Hydraulics, Materials, and Coating

    Energy Technology Data Exchange (ETDEWEB)

    Sridharan, Kumar; Anderson, Mark; Allen, Todd; Corradini, Michael

    2012-01-30

    The goal of this NERI project was to perform research on high temperature fluoride and chloride molten salts towards the long-term goal of using these salts for transferring process heat from high temperature nuclear reactor to operation of hydrogen production and chemical plants. Specifically, the research focuses on corrosion of materials in molten salts, which continues to be one of the most significant challenges in molten salts systems. Based on the earlier work performed at ORNL on salt properties for heat transfer applications, a eutectic fluoride salt FLiNaK (46.5% LiF-11.5%NaF-42.0%KF, mol.%) and a eutectic chloride salt (32%MgCl2-68%KCl, mole %) were selected for this study. Several high temperature candidate Fe-Ni-Cr and Ni-Cr alloys: Hastelloy-N, Hastelloy-X, Haynes-230, Inconel-617, and Incoloy-800H, were exposed to molten FLiNaK with the goal of understanding corrosion mechanisms and ranking these alloys for their suitability for molten fluoride salt heat exchanger and thermal storage applications. The tests were performed at 850C for 500 h in sealed graphite crucibles under an argon cover gas. Corrosion was noted to occur predominantly from dealloying of Cr from the alloys, an effect that was particularly pronounced at the grain boundaries Alloy weight-loss due to molten fluoride salt exposure correlated with the initial Cr-content of the alloys, and was consistent with the Cr-content measured in the salts after corrosion tests. The alloys weight-loss was also found to correlate to the concentration of carbon present for the nominally 20% Cr containing alloys, due to the formation of chromium carbide phases at the grain boundaries. Experiments involving molten salt exposures of Incoloy-800H in Incoloy-800H crucibles under an argon cover gas showed a significantly lower corrosion for this alloy than when tested in a graphite crucible. Graphite significantly accelerated alloy corrosion due to the reduction of Cr from solution by graphite and formation

  18. High-precision gigahertz-to-terahertz spectroscopy of aqueous salt solutions as a probe of the femtosecond-to-picosecond dynamics of liquid water

    CERN Document Server

    Vinh, N Q; Allen, S James; George, D K; Rahmani, A J; Plaxco, Kevin W

    2015-01-01

    Because it is sensitive to fluctuations occurring over femtoseconds to picoseconds, gigahertz-to-terahertz dielectric relaxation spectroscopy can provide a valuable window into water's most rapid intermolecular motions. In response, we have built a vector network analyzer dielectric spectrometer capable of measuring absorbance and index of refraction in this frequency regime with unprecedented precision. Using this to determine the complex dielectric response of water and aqueous salt solutions from 5.9 GHz to 1.12 THz (which we provide in the SI), we have obtained strong new constraints on theories of water's collective dynamics. For example, while the salt-dependencies we observe for water's two slower relaxations (8 and 1 ps) are easily reconciled with suggestions that they arise due to rotations of fully and partially hydrogen bonded molecules, respectively, the salt-dependence of the fastest relaxation (180 fs) appears difficult to reconcile with its prior assignment to liberations of single hydrogen bon...

  19. 液体钙应用于硫酸钠型矿卤生产制碱用液体盐的工艺浅析%Brief Discussion on the Application of Liquid Calcium Used in Producing Liquid Salt with Sodium Sulfate Type Brine

    Institute of Scientific and Technical Information of China (English)

    黄承; 曹军; 戴克洋

    2015-01-01

    分析比较硫酸钠型矿卤生产液体盐中的脱硝和除钙镁的各种方法,探讨了液体钙应用于硫酸钠型矿卤生产液体盐的各种工艺,并与固体钙应用于生产液体盐的工艺进行了比较,突出了液体钙用于液体盐生产中的优势,展现了液体钙应用于液体盐生产中的良好经济效益和环境效益。%This paper mainly comparatively analyzes all kinds of process of removing calcium, magnesium and sulfate from sodium sulfate-type brine. It also discusses the processing liquid salt by liquid calcium chloride and make the technology and economic comparison with solid calcium chloride. This paper highlights the advantage of sulfate-removing by the liquid calcium chloride and shows the significant economic and environmental benefits in producing liquid salt.

  20. [3 + 2]-Cycloadditions of nitrile ylides after photoactivation of vinyl azides under flow conditions

    Directory of Open Access Journals (Sweden)

    Stephan Cludius-Brandt

    2013-08-01

    Full Text Available The photodenitrogenation of vinyl azides to 2H-azirines by using a photoflow reactor is reported and compared with thermal formation of 2H-azirines. Photochemically, the ring of the 2H-azirines was opened to yield the nitrile ylides, which underwent a [3 + 2]-cycloaddition with 1,3-dipolarophiles. When diisopropyl azodicarboxylate serves as the dipolarophile, 1,3,4-triazoles become directly accessible starting from the corresponding vinyl azide.

  1. A Concomitant Allylic Azide Rearrangement/Intramolecular Azide–Alkyne Cycloaddition Sequence

    Science.gov (United States)

    2015-01-01

    An intramolecular Huisgen cycloaddition of an interconverting set of isomeric allylic azides with alkynes affords substituted triazoles in high yield. The stereoisomeric vinyl-substituted triazoloxazines formed depend on the rate of cycloaddition of the different allylic azide precursors when the reaction is carried out under thermal conditions. In contrast, dimerized macrocyclic products were obtained when the reaction was done using copper(I)-catalyzed conditions, demonstrating the ability to control the reaction products through changing conditions. PMID:24635056

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

    Science.gov (United States)

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

    2010-08-01

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

  3. Preparation of chitosan quaternary ammonium salt in ionic liquid and its flocculating effect%离子液体中制备壳聚糖季铵盐及其絮凝效果研究

    Institute of Scientific and Technical Information of China (English)

    张聪璐; 胡筱敏; 祝雷; 王芳

    2013-01-01

    Ionic liquid of glycine hydrochloride has been synthesized through one-step synthesis.And chitosan quaternary ammonium salt has been made from quaternary ammonium reaction of 2,3-epoxypropyltrimethyl ammonium chloride and chitosan,with glycine hydrochloride aqueous solution as medium.Then it is applied to the treatment of traditional Chinese medicine wastewater.The effects of various reaction parameters,such as reaction temperature,reaction time,mass ratio of reactants and concentration of ionic liquid on the substitution degree of quatemary ammonium salt,as well as the effects of quaternary ammonium salt dosage,pH,stirring time on flocculating efficacy are investigated.The results show that both of the reaction efficacy of quaternary ammonium in ionic liquid and the degree of substitution of the product are higher than that of conventional non-homogeneous reaction.Chitosan quaternary ammonium salt could effectively remove the turbidity and COD from traditional Chinese medicine wastewater.%采用一步合成法制备了离子液体甘氨酸盐酸盐,以其水溶液为反应介质,壳聚糖与2,3-环氧丙基三甲基氯化铵进行季铵化反应,得到壳聚糖季铵盐,并将其用于中药废水的絮凝处理.考察了温度、时间、反应物配比及离子液体浓度对季铵盐取代度的影响,以及季铵盐加入量、pH、搅拌时间对絮凝效果的影响.实验结果表明,在离子液体中进行的季铵化反应效率及产品取代度均高于常规的非均相反应,壳聚糖季铵盐能够有效去除中药废水的浊度和COD.

  4. Photolysis and thermolysis of pyridyl carbonyl azide monolayers on single-crystal platinum.

    Science.gov (United States)

    Adkinson, Dana K; Magri, David C; Pitters, Jason L; Griffiths, Keith; Norton, Peter R; Workentin, Mark S

    2013-01-01

    The photochemical and thermal reactivity of a number of acyl azide-substituted pyridine compounds, namely nicotinyl azide, isonicotinyl azide, picolinyl azide and dinicotinyl azide with investigated as saturated monolayers on a single-crystal Pt(111) surface in an ultrahigh vacuum chamber. Multilayers of the substrates exhibited a maximum rate of desorption at 270 K, above which, stable saturated monolayers formed as characterized by reflection-absorption infrared spectroscopy by observation of C=O and N3 bands at 1700 cm(-1), and 2100 and 1300 cm(-1) respectively. The monolayers were stable up to 400 K. Photolysis of the monolayer (or heating above 400 K) results in the formation of the respective isocyanate intermediate after loss of nitrogen as evidenced by the appearance of a new infrared band at 2260 cm(-1) with concomitant loss of the azide bands. The resulting isocyanate saturated monolayer is stable in absence of nucleophiles, but can be quenched with appropriate nucleophiles. © 2013 The American Society of Photobiology.

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

    Science.gov (United States)

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

    2015-08-19

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

  6. 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.

    1975-01-01

    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.

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

    Science.gov (United States)

    Zhang, Xiaoguang; Liu, Peiye; Zhu, Lei

    2016-12-09

    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-(triazolylmethyl)propargylic 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.

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

    Directory of Open Access Journals (Sweden)

    Xiaoguang Zhang

    2016-12-01

    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.

  9. Removing vanadium from sodium chromate neutral liquid by non­calcium roasting technology with chromium salt%铬盐无钙焙烧工艺铬酸钠中性液铁盐除钒

    Institute of Scientific and Technical Information of China (English)

    杨得军; 王少娜; 陈晓芳; 郑诗礼; 李世厚

    2014-01-01

    According to the current existing problem in the vanadium precipitating process in calcium salt by non­calcium roasting technology with chromium salt, such problems as large amount of calcium salt, repeatedly adjusting the pH value, slag containing calcium chromate and other issues, iron salts were used as precipitating agent to remove vanadium. The amount of iron salt added, pH value, temperature and other major factors on the impact of vanadium removal were investigated, the optimum conditions are that the vanadium concentration in final liquid is less than 0.08 g/L, which satisfies the follow­up process requirements. Utilizing iron salt to remove vanadium can be operated in wide pH range, without repeatedly adjusting the pH value. By analyzing, the slag phase is ferric hydroxide, which adsorbs vanadium, containing no chromium. And by further exploring against adsorption mechanism, vanadium is adsorbed on the surface of the iron hydroxide by inner layer complexation.%针对铬盐无钙焙烧工艺浸出液除钒现行钙盐沉钒法钙盐加入量大、需反复调节pH值、脱钒渣含铬酸钙等问题,提出采用铁盐作为沉钒剂进行除钒。考察铁盐加入量、pH 值和温度等主要因素对钒脱除的影响,得到了最佳工艺条件,且终液钒浓度低于0.08 g/L,满足后续工艺要求。铁盐除钒可在较宽的pH值范围内操作,不需反复调节溶液pH值。渣相分析表明:脱钒渣为吸附钒酸根的氢氧化铁,其中不含铬,进一步探讨氢氧化铁对钒的吸附机理,确定钒酸根通过内层络合方式吸附在氢氧化铁表面。

  10. Phosphate salts

    Science.gov (United States)

    ... levels that are too high, and for preventing kidney stones. They are also taken for treating osteomalacia (often ... But intravenous phosphate salts should not be used. Kidney stones (nephrolithiasis). Taking potassium phosphate by mouth might help ...

  11. Salt cookbook

    CERN Document Server

    Saha, Anirban

    2015-01-01

    If you are a professional associated with system and infrastructure management, looking at automated infrastructure and deployments, then this book is for you. No prior experience of Salt is required.

  12. Flash Vacuum Pyrolysis of Azides, Triazoles, and Tetrazoles.

    Science.gov (United States)

    Wentrup, Curt

    2017-03-08

    Flash vacuum pyrolysis (FVP) of azides is an extremely valuable method of generating nitrenes and studying their thermal rearrangements. The nitrenes can in many cases be isolated in low-temperature matrices and observed spectroscopically. NH and methyl, alkyl, aralkyl, vinyl, cyano, aryl and N-heteroaryl, acyl, carbamoyl, alkoxycarbonyl, imidoyl, boryl, silyl, phosphonyl, and sulfonyl nitrenes are included. FVP of triazoloazines generates diazomethylazines and azinylcarbenes, which often rearrange to the energetically more stable arylnitrenes. N2 elimination from monocyclic 1,2,3-triazoles can generate iminocarbenes, 1H-azirines, ketenimines, and cyclization products, and 1,2,4-triazoles are precursors of nitrile ylides. Benzotriazoles are preparatively useful precursors of cyanocyclopentadienes, carbazoles, and aza-analogues. FVP of 5-aryltetrazoles can result in double N2 elimination with formation of arylcarbenes or of heteroarylcarbenes, which again rearrange to arylnitrenes. Many 5-substituted and 2,5-disubstituted tetrazoles are excellent precursors of nitrile imines (propargylic, allenic, or carbenic), which are isolable at low temperatures in some cases (e.g., aryl- and silylnitrile imines) or rearrange to carbodiimides. 1,5-Disubstituted tetrazoles are precursors of imidoylnitrenes, which also rearrange to carbodiimides or add intramolecularly to aryl substituents to yield indazoles and related compounds. Where relevant for the mechanistic understanding, pyrolysis under flow conditions or in solution or the solid state will be mentioned. Results of photolysis reactions and computational chemistry complementing the FVP results will also be mentioned in several places.

  13. Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water—Part 1: Organic compounds and water by consideration of short- and long-range effects using X-UNIFAC.1

    Science.gov (United States)

    Erdakos, Garnet B.; Asher, William E.; Seinfeld, John H.; Pankow, James F.

    The semi-empirical group contribution method (GCM) of Kikic et al. [Chem. Eng. Sci. 46 (1991) 2775-2780] for estimating activity coefficient ( ζ) values of neutral organic compounds and water in solutions composed of organic compounds, dissolved inorganic salts, and water is adapted for application to atmospheric particulate matter (PM). It is assumed that ζ values are determined by a combination of short- and long-range interactions. The ζ expression involves conventional UNIFAC terms and a Debye-Hückel term, with the former computed using group-group interaction parameters. Organic-organic interaction parameters are assigned the values from the UNIFAC-LLE model of Magnussen et al. [Ind. Eng. Chem. Process Design Develop. 20 (1981) 331-339]. Forty interaction parameters (ion-solvent group and anion-cation) were obtained from Kikic et al. [Chem. Eng. Sci. 46 (1991) 2775-2780], Achard et al. [Fluid Phase Equilibria 98 (1994) 71-89], and Ming and Russell [Am. Inst. Chem. Eng. J. 48 (2002) 1331-1348]. Twenty additional interaction parameters (ion-solvent group) are estimated based on 879 UNIQUAC-fitted ζ values for organic compounds and water. The fitted ζ values are based on liquid-liquid equilibrium (LLE) data for a range of ternary and quaternary organic/inorganic salt/water mixtures at 293-308 K. The UNIQUAC fits are analogous to those described by Fredenslund et al. [Vapor-Liquid Equilibria Using UNIFAC: A Group-Contribution Method, Elsevier Scientific Publishing, New York, 1977]. The LLE mixture compositions range from primarily organic solutions to primarily aqueous solutions with maximum ionic strengths of ˜5 mol kg -1. The groups characteristic of organic compounds found in atmospheric PM considered here include: CH 3-, -CH 2-, -CH|-, -C||-, -OH, -CH 2CO-, and -COOH. These are: single bonded carbon with three, two, one, and zero hydrogens, respectively, hydroxyl, -CH 2-carbonyl, and carboxyl, respectively. The inorganic salts represented in the mixture

  14. Mechanism study of copper-mediated one-pot reductive amination of aryl halides using trimethylsilyl azide.

    Science.gov (United States)

    Maejima, Toshihide; Ueda, Moriatsu; Nakano, Jun; Sawama, Yoshinari; Monguchi, Yasunari; Sajiki, Hironao

    2013-09-20

    Reaction mechanisms of the copper-mediated amination of aryl halides with trimethylsilyl azide (TMSN3) were analyzed on the basis of the time-course study using reaction monitoring FT-IR, trapping an intermediary aryl azide by the Huisgen reaction, and the analysis of the generated N2 gas during the reaction. This amination would proceed through multiple pathways via aryl radicals and copper(I) azide.

  15. NMR Studies on Diffusion and Molecular Motions of Imidazolium Ionic Liquids doped by Lithium Salts Related to Ionic Conductivity and Computational Interaction Energy

    Institute of Scientific and Technical Information of China (English)

    Kikuko; Hayamizua; Seiji; Tsuzuki; Shiro; Seki

    2007-01-01

    1 Results Room-temperature Ionic liquids (RTILs) are special class of compounds, where a combination of cations and anions produces neutral, stable and viscous liquids with high ionic conductivity. Widely spread applications are proposed to use conductors, electrolytes, clean solvents and others. Especially, RTILs are expected to be safe electrolytes in the ion-lithium batteries. In this study, NMR methods are used to clarify the basic properties of the individual movements of the anions and cations of ...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-09-14

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

  17. Mechanism for salt scaling

    Science.gov (United States)

    Valenza, John J., II

    Salt scaling is superficial damage caused by freezing a saline solution on the surface of a cementitious body. The damage consists of the removal of small chips or flakes of binder. The discovery of this phenomenon in the early 1950's prompted hundreds of experimental studies, which clearly elucidated the characteristics of this damage. In particular it was shown that a pessimum salt concentration exists, where a moderate salt concentration (˜3%) results in the most damage. Despite the numerous studies, the mechanism responsible for salt scaling has not been identified. In this work it is shown that salt scaling is a result of the large thermal expansion mismatch between ice and the cementitious body, and that the mechanism responsible for damage is analogous to glue-spalling. When ice forms on a cementitious body a bi-material composite is formed. The thermal expansion coefficient of the ice is ˜5 times that of the underlying body, so when the temperature of the composite is lowered below the melting point, the ice goes into tension. Once this stress exceeds the strength of the ice, cracks initiate in the ice and propagate into the surface of the cementitious body, removing a flake of material. The glue-spall mechanism accounts for all of the characteristics of salt scaling. In particular, a theoretical analysis is presented which shows that the pessimum concentration is a consequence of the effect of brine pockets on the mechanical properties of ice, and that the damage morphology is accounted for by fracture mechanics. Finally, empirical evidence is presented that proves that the glue-small mechanism is the primary cause of salt scaling. The primary experimental tool used in this study is a novel warping experiment, where a pool of liquid is formed on top of a thin (˜3 mm) plate of cement paste. Stresses in the plate, including thermal expansion mismatch, result in warping of the plate, which is easily detected. This technique revealed the existence of

  18. 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)

    2002-01-01

    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.

  19. Study and application of fast harden single cement liquid with sulfur and aluminum salt%快硬硫铝盐水泥单液浆性能研究及应用

    Institute of Scientific and Technical Information of China (English)

    邓尤东; 帅建国; 罗光财

    2012-01-01

    以重庆市轨道交通一号线中梁山隧道工程岩溶高压富水段注浆堵水为工程实例,探讨快硬硫铝盐水泥单液浆的性能和在富水隧道注浆施工中的应用.通过研究,实现了科学、文明、高效、可控的帷幕注浆施工,可供类似工程参考.%Taking the Zhongliangshan Tunnel 1st line of trace traffic in Chongqing as an example, the plugging water problem was discussed. The fast harden single cement liquid with sulfur and aluminum salt was successfully was applied in tunnel grouting. The research will provide useful reference for similar engineering.

  20. Improved method for the determination of trace quaternary ammonium salt by high performance liquid chromatography%高效液相色谱法测定微量季铵盐的改进方法

    Institute of Scientific and Technical Information of China (English)

    卢姝; 纪然

    2011-01-01

    利用季铵盐与间硝基酚反应生成溶于有机溶剂的络合物,该络合物可以用紫外检测器进行定量分析,建立了一种高效液相色谱测定微量季铵盐的改进方法.该方法的线性范围为0.60~99.40 mg/L,最低检出限可达0.4mg/L,平均回收率为94.97%~104.02%,相对标准偏差为3.41%.该方法稳定、简便且灵敏度高,适于测定锅炉循环冷却水、工业废水及水处理药剂中季铵盐类阳离子表面活性剂的含量.%Quaternary ammonium salt and 3-nitrophenol have been used for preparing the complex compound which is soluble in organic solvent. The complex compound can be determined quantitatively with UV detector. An improved method for the determination of trace quaternary ammonium salt by the high performance liquid chromatography is established. The linear range of the method is 0.60-99.40 mg/L. Its lowest detection limit 0.4 mg/L, average recovery rate 94.97%-104.02% and relative standard deviation 3.41%. The method is rapid, convenient and highly sensitive. It is suitable for the determination of the content of cationic surfactant of quaternary ammonium salts in circulating cooling water, industrial wastewater and water treatment agents.

  1. Rapid ion-exchange matrix removal for a decrease of detection limits in the analysis of salt-rich reservoir waters for fluorobenzoic acids by liquid chromatography coupled with tandem mass spectrometry.

    Science.gov (United States)

    Kubica, Paweł; Vacchina, Véronique; Wasilewski, Tomasz; Reynaud, Stéphanie; Szpunar, Joanna; Lobinski, Ryszard

    2017-02-01

    A matrix removal procedure with ion-exchange resin prior to analysis for 18 fluorinated benzoic acids (FBAs) tracers in saline (>25% salt) reservoir water was optimized. The elimination of >98% of salt and the simultaneous matrix sample cleanup allowed the direct analysis using the supernatant by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). This resulted in a gain in detection limits for most of the tracers in comparison with the reference method (direct analysis after minimum required dilution). The limits of detection (LODs) were in the range of 0.01-0.15 ng/ml and compared to other studies the developed method provided comparable limits of detection and advantage of simplified and shorter sample preparation. The presented method offers a considerable gain in simplicity and analysis time. Recoveries for all the tracers reached 80-100%, except for 2-FBA and 2,6-dFBA for which they were ca. 60%. The low recoveries were corrected by the use of five isotopically labeled internal standards. The method was validated by the analysis of spiked samples and by an independent comparison of the results with those obtained by solid-phase extraction LC-MS/MS method.

  2. Conventional high-performance liquid chromatography versus derivative spectrophotometry for the determination of 1,3,6-pyrenetrisulfonic acid trisodium salt and 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt in the color additive D&C Green No. 8 (Pyranine).

    Science.gov (United States)

    Jitian, Simion; White, Samuel R; Yang, H-H Wendy; Weisz, Adrian

    2014-01-10

    Specifications in the U.S. Code of Federal Regulations for the color additive D&C Green No. 8 (Colour Index No. 59040) limit the levels of the subsidiary colors 1,3,6-pyrenetrisulfonic acid trisodium salt (P3S) and 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt (P4S). The present paper describes a comparative study of two possible methods to replace the currently used multi-step TLC/spectrophotometry method of separating and quantifying the minor components P3S and P4S in G8. One of the new approaches uses conventional high-performance liquid chromatography (HPLC) and the other, derivative spectrophotometry. While the derivative spectrophotometric method was shown to be inadequate for the analysis of minor components overwhelmed by components of much higher concentration, the HPLC method was proven highly effective. The closely related, very polar compounds P3S and P4S were separated by the new HPLC method in less than 4 min using a conventional HPLC instrument. P3S and P4S were quantified by using five-point calibration curves with data points that ranged from 0.45 to 7.63% and from 0.13 to 1.82%, by weight, for P3S and P4S, respectively. The HPLC method was applied to the analysis of test portions from 20 batches of D&C Green No. 8 submitted to the U.S. Food and Drug Administration for certification.

  3. Labeling Live Cells by Copper-Catalyzed Alkyne-Azide Click Chemistry

    Science.gov (United States)

    Hong, Vu; Steinmetz, Nicole F.; Manchester, Marianne

    2010-01-01

    The copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, optimized for biological molecules in aqueous buffers, has been shown to rapidly label mammalian cells in culture with no loss in cell viability. Metabolic uptake and display of the azide derivative of N-acetylmannosamine developed by Bertozzi, followed by CuAAC ligation using sodium ascorbate and the ligand tris(hydroxypropyltriazolyl)methylamine (THPTA), gave rise to abundant covalent attachment of dye-alkyne reactants. THPTA serves both to accelerate the CuAAC reaction and to protect the cells from damage by oxidative agents produced by the Cu-catalyzed reduction of oxygen by ascorbate, which is required to maintain the metal in the active +1 oxidation state. This procedure extends the application of this fastest of azide-based bioorthogonal reactions to the exterior of living cells. PMID:20886827

  4. Synthesis and luminescence properties of iridium(III) azide- and triazole-bisterpyridine complexes.

    Science.gov (United States)

    Goldstein, Daniel C; Peterson, Joshua R; Cheng, Yuen Yap; Clady, Raphael G C; Schmidt, Timothy W; Thordarson, Pall

    2013-07-26

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

  5. Labeling live cells by copper-catalyzed alkyne--azide click chemistry.

    Science.gov (United States)

    Hong, Vu; Steinmetz, Nicole F; Manchester, Marianne; Finn, M G

    2010-10-20

    The copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, optimized for biological molecules in aqueous buffers, has been shown to rapidly label mammalian cells in culture with no loss in cell viability. Metabolic uptake and display of the azide derivative of N-acetylmannosamine developed by Bertozzi, followed by CuAAC ligation using sodium ascorbate and the ligand tris(hydroxypropyltriazolyl)methylamine (THPTA), gave rise to abundant covalent attachment of dye-alkyne reactants. THPTA serves both to accelerate the CuAAC reaction and to protect the cells from damage by oxidative agents produced by the Cu-catalyzed reduction of oxygen by ascorbate, which is required to maintain the metal in the active +1 oxidation state. This procedure extends the application of this fastest of azide-based bioorthogonal reactions to the exterior of living cells.

  6. Azide as a competitor of chloride in oxygen evolution by Photosystem II.

    Science.gov (United States)

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

    1999-05-11

    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.

  7. On the Mechanism of Copper(I)-Catalyzed Azide-Alkyne Cycloaddition.

    Science.gov (United States)

    Zhu, Lei; Brassard, Christopher J; Zhang, Xiaoguang; Guha, P M; Clark, Ronald J

    2016-06-01

    The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction regiospecifically produces 1,4-disubstituted-1,2,3-triazole molecules. This heterocycle formation chemistry has high tolerance to reaction conditions and substrate structures. Therefore, it has been practiced not only within, but also far beyond the area of heterocyclic chemistry. Herein, the mechanistic understanding of CuAAC is summarized, with a particular emphasis on the significance of copper/azide interactions. Our analysis concludes that the formation of the azide/copper(I) acetylide complex in the early stage of the reaction dictates the reaction rate. The subsequent triazole ring-formation step is fast and consequently possibly kinetically invisible. Therefore, structures of substrates and copper catalysts, as well as other reaction variables that are conducive to the formation of the copper/alkyne/azide ternary complex predisposed for cycloaddition would result in highly efficient CuAAC reactions. Specifically, terminal alkynes with relatively low pKa values and an inclination to engage in π-backbonding with copper(I), azides with ancillary copper-binding ligands (aka chelating azides), and copper catalysts that resist aggregation, balance redox activity with Lewis acidity, and allow for dinuclear cooperative catalysis are favored in CuAAC reactions. Brief discussions on the mechanistic aspects of internal alkyne-involved CuAAC reactions are also included, based on the relatively limited data that are available at this point. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Protein enrichment by capture-release based on strain-promoted cycloaddition of azide with bicyclononyne (BCN).

    NARCIS (Netherlands)

    Temming, R.P.; Scherpenzeel, M. van; Brinke, E. te; Schoffelen, S.; Gloerich, J.; Lefeber, D.J.; Delft, F.L. van

    2012-01-01

    An enrichment strategy was devised for azide derivatized macromolecules, based on strain-promoted alkyne-azide cycloaddition (SPAAC) and a cleavable linker. A ring-strained alkyne, bicyclo[6.1.0]non-4-yne (BCN), was covalently attached to agarose beads via a hydrazine-sensitive linker. Benchmark

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

    OpenAIRE

    Ciesielski, Witold; Jędrzejewski, Włodzimierz

    1993-01-01

    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...

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

    Science.gov (United States)

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

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

  11. Chelation-assisted, copper(II)-acetate-accelerated azide-alkyne cycloaddition.

    Science.gov (United States)

    Kuang, Gui-Chao; Michaels, Heather A; Simmons, J Tyler; Clark, Ronald J; Zhu, Lei

    2010-10-01

    We described in a previous communication a variant of the popular Cu(I)-catalyzed azide-alkyne cycloaddition (AAC) process where 5 mol % of Cu(OAc)(2) in the absence of any added reducing agent is sufficient to enable the reaction. 2-Picolylazide (1) and 2-azidomethylquinoline (2) were found to be by far the most reactive carbon azide substrates that convert to 1,2,3-triazoles in as short as a few minutes under the discovered conditions. We hypothesized that the abilities of 1 and 2 to chelate Cu(II) contribute significantly to the observed high reaction rates. The current work examines the effect of auxiliary ligands near the azido group other than pyridyl for Cu(II) on the efficiency of the Cu(OAc)(2)-accelerated AAC reaction. The carbon azides capable of binding to the catalytic copper center at the alkylated azido nitrogen in a chelatable fashion were indeed shown to be superior substrates under the reported conditions. The chelation between carbon azide 11 and Cu(II) was demonstrated in an X-ray single-crystal structure. In a limited set of examples, the ligand tris(benzyltriazolylmethyl)amine (TBTA), developed by Fokin et al. for assisting the original Cu(I)-catalyzed AAC reactions, also dramatically enhances the Cu(OAc)(2)-accelerated AAC reactions involving nonchelating azides. This observation leads to the hypothesis of an additional effect of chelating azides on the efficiencies of Cu(OAc)(2)-accelerated AAC reactions, which is to facilitate the rapid reduction of Cu(II) to highly catalytic Cu(I) species. Mechanistic studies on the AAC reactions with particular emphasis on the role of carbon azide/copper interactions will be conducted based on the observations reported in this work. Finally, the immediate utility of the product 1,2,3-triazole molecules derived from chelating azides as multidentate metal coordination ligands is demonstrated. The resulting triazolyl-containing ligands are expected to bind with transition metal ions via the N(2) nitrogen of

  12. Visible-light sensitization of vinyl azides by transition-metal photocatalysis.

    Science.gov (United States)

    Farney, Elliot P; Yoon, Tehshik P

    2014-01-13

    Irradiation of vinyl and aryl azides with visible light in the presence of Ru photocatalysts results in the formation of reactive nitrenes, which can undergo a variety of C-N bond-forming reactions. The ability to use low-energy visible light instead of UV in the photochemical activation of azides avoids competitive photodecomposition processes that have long been a significant limitation on the synthetic use of these reactions. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Dataset on characterization of hemin-azide derivative and DNA oligonucleotide-hemin conjugate

    Directory of Open Access Journals (Sweden)

    J. Kosman

    2017-08-01

    Full Text Available In this article newly synthesized azide derivative of hemin and DNA-hemin conjugate are characterized. Hemin-azide was purified using HPLC and characterized using elemental analysis, IR and NMR. The DNA-hemin conjugate was obtained via click chemistry [1] and click reaction was carried out using traditional Cu-catalyzed and Cu-free approaches. The final product was successfully obtained using Cu-free cycloaddition. The identity of product was confirmed using Maldi TOF spectrometry. Obtained hemin-DNA conjugate exhibited peroxidase-like activity.

  14. Actinide-Lanthanide separation by an electrolytic method in molten salt media: feasibility assessment of a renewed liquid cathode; Un nouveau concept de separation actinides-lanthanides en milieu sel fondu: mise en oeuvre d'une cathode liquide a surface renouvelee

    Energy Technology Data Exchange (ETDEWEB)

    Huguet, A.

    2009-12-15

    This study is part of a research program concerning the assessment of pyrochemical methods for the nuclear waste processing. The An-Ln partitioning could be achieved by an electrolytic selective extraction in molten salt media. It has been decided to focus on liquid reactive cathode which better suits to a group actinides co-recycling. The aim of the study is to propose, define and initiate the development of an electrolytic pyro-process dedicated to the quantitative and selective recovery of the actinides. Quantitativeness is related to technology, whereas selectivity is governed by chemistry. The first step consisted in selecting the adequate operating conditions, which enables a sufficient An-Ln separation. The first step consisted, by means of thermodynamic calculi and electrochemical investigations, in selecting a promising combination between molten electrolyte and cathodic material, regarding the process constraints. To improve the recovery yield, it is necessary to develop a disruptive technology: here comes the concept of a dynamic electrodeposition carried out onto liquid metallic drops. The next step consisted in designing and manufacturing a lab-scale device which enables dropping flow studies. Since interfacial phenomena are of primary meaning in such a concept, it has been decided to focus on high temperature liquid-liquid interfacial measurements. (author)

  15. In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis.

    Science.gov (United States)

    Hu, Lu; Liu, Yahu A; Liao, Xuebin

    2017-08-01

    Although azides have been widely used in nitrene transfer reactions, in situ generation of N-H imines from azides for downstream transformations has rarely been explored. We report copper-mediated formation of N-unsubstituted aliphatic imines from easily available aliphatic azides using a customized phenanthroline-based ligand (L1*). Through trapping in situ-generated N-H imines, multisubstituted pyridines or indoles were readily synthesized. (13)C-labeled azide was used as part of an isotope labeling study, which suggests that the construction of pyridine derivatives involves a three-component dehydrogenative condensation. The construction of 2,3,5-triaryl pyridines using this method provided evidence supporting a proposed pathway involving both imine formation and abnormal Chichibabin pyridine synthesis. The generation of N-unsubstituted imine intermediates was also confirmed by formation of indole derivatives from alkyl azides.

  16. In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis

    Science.gov (United States)

    Hu, Lu; Liu, Yahu A.; Liao, Xuebin

    2017-01-01

    Although azides have been widely used in nitrene transfer reactions, in situ generation of N-H imines from azides for downstream transformations has rarely been explored. We report copper-mediated formation of N-unsubstituted aliphatic imines from easily available aliphatic azides using a customized phenanthroline-based ligand (L1*). Through trapping in situ–generated N-H imines, multisubstituted pyridines or indoles were readily synthesized. 13C-labeled azide was used as part of an isotope labeling study, which suggests that the construction of pyridine derivatives involves a three-component dehydrogenative condensation. The construction of 2,3,5-triaryl pyridines using this method provided evidence supporting a proposed pathway involving both imine formation and abnormal Chichibabin pyridine synthesis. The generation of N-unsubstituted imine intermediates was also confirmed by formation of indole derivatives from alkyl azides. PMID:28808683

  17. Influence of Proton and Salt Concentration on the Chromonic Liquid Crystal Phase Diagram of Disodium Cromoglycate Solutions: Prospects and Limitations of a Host for DNA Nanostructures.

    Science.gov (United States)

    Zhang, Bingru; Kitzerow, Heinz-S

    2016-03-31

    Lyotropic chromonic liquid crystals have recently been suggested for use as a self-organized host for dispersing and aligning self-organized DNA origami nanostructures. However, an appropriate pH value and a suitable cation concentration are necessary to stabilize such nanostructures and to avoid unfolding of the DNA. The present study shows that the nematic and columnar liquid crystal phases appearing in aqueous solutions of disodium cromoglycate are robust against the replacement of deionized water by a neutral or alkaline buffer solution. However, disodium cromoglycate precipitates when an acidic buffer is used or when the concentration of magnesium cations exceeds a critical concentration of about 0.6-0.7 mmol/L.

  18. Partition behavior of surfactants, butanol, and salt during application of density-modified displacement of dense non-aqueous phase liquids

    Energy Technology Data Exchange (ETDEWEB)

    Damrongsiri, S. [Center of Excellence on Hazardous Substance Management (HSM), Chulalongkorn University, Phaya-Thai Rd., Bangkok (Thailand); Tongcumpou, C., E-mail: tchantra@chula.ac.th [Center of Excellence on Hazardous Substance Management (HSM), Chulalongkorn University, Phaya-Thai Rd., Bangkok (Thailand); Environmental Research Institute, Chulalongkorn University (Thailand); Sabatini, D.A. [School of Civil Engineering and Environmental Science, The University of Oklahoma, Oklahoma (United States)

    2013-03-15

    Highlights: ► Aqueous surfactant increases the partition of butanol aqueous phase. ► Water partition to NAPL phase via butanol and surfactant in NAPL phase. ► PCE partition to aqueous phase by solubilization into micelles. ► Surfactants cause the dramatically partition of water to NAPL phase. ► Aqueous salt dispels surfactant to NAPL phase. -- Abstract: Density-modified displacement (DMD) is a recent approach for removal of trapped dense NAPL (DNAPL). In this study, butanol and surfactant are contacted with the DNAPL to both reduce the density as well as release the trapped DNAPL (perchloroethylene: PCE). The objective of the study was to determine the distribution of each component (e.g., butanol, surfactant, water, PCE) between the original aqueous and PCE phases during the application of DMD. The results indicated that the presence of the surfactant increased the amount of n-butanol required to make the NAPL phase reach its desired density. In addition, water and anionic surfactant were found to partition along with the BuOH into the PCE phase. The water also found partitioned to reverse micelles in the modified phase. Addition of salt was seen to increase partitioning of surfactant to BuOH containing PCE phase. Subsequently, a large amount of water was solubilized into reverse micelles which lead to significantly increase in volume of the PCE phase. This work thus demonstrates the role of each component and the implications for the operation design of an aquifer treatment using the DMD technique.

  19. Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water—Part 2: Consideration of phase separation effects by an X-UNIFAC model

    Science.gov (United States)

    Chang, Elsa I.; Pankow, James F.

    A thermodynamic model is presented for predicting the formation of particulate matter (PM) within an aerosol that contains organic compounds, inorganic salts, and water. Neutral components are allowed to partition from the gas phase to the PM, with the latter potentially composed of both a primarily aqueous ( α) liquid phase and a primarily organic ( β) liquid phase. Partitioning is allowed to occur without any artificial restraints: when both α and β PM phases are present, ionic constituents are allowed to partition to both. X-UNIFAC.2, an extended UNIFAC method based on Yan et al. (1999. Prediction of vapor-liquid equilibria in mixed-solvent electrolyte systems using the group contribution concept. Fluid Phase Equilibria 162, 97-113), was developed for activity coefficient estimation. X-UNIFAC.2 utilizes the standard UNIFAC terms, a Debye-Hückel term, and a virial equation term that represents the middle-range (MR) contribution to activity coefficient effects. A large number (234) of MR parameters are already available from Yan et al. (1999). Six additional MR parameters were optimized here to enable X-UNIFAC.2 to account for interactions between the carboxylic acid group and Na +, Cl -, and Ca 2+. Predictions of PM formation were made for a hypothetical sabinene/O 3 system with varying amounts of NaCl in the PM. Predictions were also made for the chamber experiments with α-pinene/O 3 (and CaCl 2 seed) carried out by Cocker et al. (2001. The effect of water on gas-particle partitioning of secondary organic aerosol. Part I. α-pinene/ozone system. Atmospheric Environment 35, 6049-6072); good agreement between the predicted and chamber-measured PM mass concentrations was achieved.

  20. Experiment on the Application of Ionic Liquid as Green Medium for Extraction of Boric Acid from Salt Lake Brine%离子液体作为绿色介质从盐湖卤水中萃取硼酸

    Institute of Scientific and Technical Information of China (English)

    宋贤菊; 李在均

    2011-01-01

    Ionic liquid is a green solvent for extraction of boron from salt lake beine as extraction medium, 1-octyl-3-methylimidazolium hexafluorophosphate ionic liquid was prepared and the ionic liquid, isooctyl alcohol and kerosene were used as extraction medium, synergic reagent and diluent respectively. The influence of ionic liquid dosage and extraction conditions on the boron extraction were investigated. The optimal experimental parameters were obtained as follows: ionic liquid dosage 10% ,the extractant 50% ,the ratio of organic phase to brine 1:1, the extraction time 10 min, and pH 2.4. The concentration of Mg2+ 4.268 mollL. Under optimal conditions, the boron can be fully extracted to the organic phase with three step extractions and a recovey of 99.54% was obtained.%制备了1-辛烷基-3-甲基咪唑六氟磷酸盐离子液体,再以离子液体(IL)为萃取介质、异辛醇为萃取剂及煤油为稀释剂建立盐湖卤水硼萃取研究模型,考察了离子液体用量和萃取条件对硼萃取的影响.异辛醇从卤水中萃取提硼的最佳实验条件:离子液体体积分数为10%,萃取剂体积分数为50%,相比(O/A)为1:1,萃取时间10 min,pH 2.4,Mg2+浓度为4.268 mol/L.在此条件下,当萃取级数为3级时,萃取率为99.54%,卤水中的硼可被完全萃取到有机相中.

  1. 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

    1997-01-01

    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.

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

    Science.gov (United States)

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

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

    Science.gov (United States)

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

  4. Catalytic Intermolecular Cross-Couplings of Azides and LUMO-Activated Unsaturated Acyl Azoliums

    KAUST Repository

    Li, Wenjun

    2017-02-15

    An example for the catalytic synthesis of densely functionalized 1,2,3-triazoles through a LUMO activation mode has been developed. The protocol is enabled by intermolecular cross coupling reactions of azides with in situ-generated alpha,beta-unsaturated acyl azoliums. High yields and broad scope as well as the investigation of reaction mechanism are reported.

  5. Inhibitory effects of sodium azide on microbial growth in experimental resuspension of marine sediment.

    Science.gov (United States)

    Cabrol, Léa; Quéméneur, Marianne; Misson, Benjamin

    2017-02-01

    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.

  6. Influence of azide incorporation on binding affinity by small papain inhibitors

    NARCIS (Netherlands)

    Wammes, A.E.; Hendriks, T.G.; Amatdjais-Groenen, H.I.; Wijdeven, M.A.; Hest, J.C.M. van; Delft, F.L. van; Ritschel, T.; Rutjes, F.P.J.T.

    2014-01-01

    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

  7. Kinetic resolution of alkyne-substituted quaternary oxindoles via copper catalysed azide-alkyne cycloadditions.

    Science.gov (United States)

    Brittain, William D G; Buckley, Benjamin R; Fossey, John S

    2015-12-18

    The synthesis and kinetic resolution of quaternary oxindoles through copper catalysed azide-alkyne cycloadditions is presented. Selectivity factors (s) up to 22.1 ± 0.5 are reported. Enantioenriched alkynes and triazoles were obtained in ≥80% enantiomeric excess (e.e.).

  8. Nucleobase azide-ethynylribose click chemistry contributes to stabilizing oligonucleotide duplexes and stem-loop structures.

    Science.gov (United States)

    Kitamura, Yoshiaki; Asakura, Ryo; Terazawa, Koki; Shibata, Aya; Ikeda, Masato; Kitade, Yukio

    2017-06-15

    The formation of 1,4-disubstituted 1,2,3-triazoles through copper-catalyzed azide-alkyne cycloaddition (CuAAC) in oligonucleotides bearing 1-deoxy-1-ethynyl-β-d-ribofuranose (R(E)) can have a positive impact on the stability of oligonucleotide duplexes and stem-loop structures. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Ligand-assisted, copper(II) acetate-accelerated azide-alkyne cycloaddition.

    Science.gov (United States)

    Michaels, Heather A; Zhu, Lei

    2011-10-04

    Polytriazole ligands such as the widely used tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), are shown to assist copper(II) acetate-mediated azide-alkyne cycloaddition (AAC) reactions that involve nonchelating azides. Tris(2-{4-[(dimethylamino)methyl]-1H-1,2,3-traizol-1-yl}ethyl)amine (DTEA) outperforms TBTA in a number of reactions. The satisfactory solubility of DTEA in a wide range of polar and nonpolar solvents, including water and toluene, renders it advantageous under copper(II) acetate-mediated conditions. The copper(II) acetate-mediated formation of the three triazolyl groups in a tris(triazolyl)-based ligand occurs sequentially with an inhibitory effect in the last step. The kinetic investigations of the ligand-assisted reactions reveal an interesting mechanistic dependence on the relative affinity of azide and alkyne to copper (II). In addition to expanding the scope of the copper(II) acetate-mediated AAC reactions to include nonchelating azides, this work offers evidence for the mechanistic synergy between the title reaction and the alkyne oxidative homocoupling reaction. The elucidation of the structural details of the polytriazole-ligand-bound reactive species in copper(I/II)-mediated AAC reactions, however, awaits further characterization of the metal coordination chemistry of polytriazole ligands. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Quick and highly efficient copper-catalyzed cycloaddition of organic azides with terminal alkynes.

    Science.gov (United States)

    Wang, Dong; Zhao, Mingming; Liu, Xiang; Chen, Yongxin; Li, Na; Chen, Baohua

    2012-01-14

    Good to excellent yields of 1,4-disubstituted 1,2,3-triazoles were obtained within 2-25 min when the Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction was carried out under solvent-free conditions, with [Cu(phen)(PPh(3))(2)]NO(3) (1mol%) as the catalyst.

  11. Copper-catalyzed Chan-Lam coupling between sulfonyl azides and boronic acids at room temperature.

    Science.gov (United States)

    Moon, Soo-Yeon; Nam, Jungsoo; Rathwell, Kris; Kim, Won-Suk

    2014-01-17

    A mild and efficient method for the synthesis of N-arylsulfonamides in the presence of 10 mol % of CuCl is demonstrated. The reaction proceeds readily at room temperature in an open flask using a variety of sulfonyl azides and boronic acids without any base, ligand, or additive.

  12. Continuous flow photolysis of aryl azides: Preparation of 3H-azepinones.

    Science.gov (United States)

    Bou-Hamdan, Farhan R; Lévesque, François; O'Brien, Alexander G; Seeberger, Peter H

    2011-01-01

    Photolysis of aryl azides to give nitrenes, and their subsequent rearrangement in the presence of water to give 3H-azepinones, is performed in continuous flow in a photoreactor constructed of fluorinated ethylene polymer (FEP) tubing. Fine tuning of the reaction conditions using the flow reactor allowed minimization of secondary photochemical reactions.

  13. Continuous flow photolysis of aryl azides: Preparation of 3H-azepinones

    Directory of Open Access Journals (Sweden)

    Farhan R. Bou-Hamdan

    2011-08-01

    Full Text Available Photolysis of aryl azides to give nitrenes, and their subsequent rearrangement in the presence of water to give 3H-azepinones, is performed in continuous flow in a photoreactor constructed of fluorinated ethylene polymer (FEP tubing. Fine tuning of the reaction conditions using the flow reactor allowed minimization of secondary photochemical reactions.

  14. 1,3-DIPOLAR CYCLOADDITION OF PHENYL AZIDE TO NORBORNENE IN AQUEOUS-SOLUTIONS

    NARCIS (Netherlands)

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

    1995-01-01

    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

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

    DEFF Research Database (Denmark)

    Jepsen, Tue Heesgaard; Kristensen, Jesper Langgaard

    2014-01-01

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

  16. 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.

    2008-01-01

    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

  17. 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.

    2008-01-01

    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

  18. Phospha-scorpionate complexes by click chemistry using phenyl azide and ethynylphosphine oxides

    NARCIS (Netherlands)

    van Assema, S.G.A.; Tazelaar, C.G.J.; de Jong, G.B.; van Maarseveen, J.H.; Schakel, M.; Lutz, M.; Spek, A.L.; Slootweg, J.C.; Lammertsma, K.

    2008-01-01

    The copper-catalyzed Click reaction of phenyl azide with ethynylphosphine oxides provides new P-substituted triazoles. With tris(ethynyl)phosphine oxide this route affords a versatile scorpionate ligand that coordinates to RhCl3 as a tripodal N ligand. Upon reduction, the same ligand can act as a P

  19. Core flow distribution design of molten salt reactor with liquid fuel%一种液态燃料熔盐堆堆芯流量分配设计

    Institute of Scientific and Technical Information of China (English)

    周振华; 潘登; 陈玉爽; 黄建平; 余笑寒; 王纳秀

    2016-01-01

    Background: In the thermal-hydraulic design of molten salt reactor (MSR) with liquid fuel, the structure and the flow field distribution of lower plenum play a decisive role for the core flow distribution.Purpose: The mass flow distribution of core inlet is designed to match with the release heat distribution, so that the core power distribution will be flattened in radical.Methods: To realize the reasonable distribution of core flow, the flow field of lower plenum is optimized through adjusting the geometry of core lower plenum and flow distribution device using FLUENT software to simulate three-dimensional flow field of core.Results: The simulation results showed that the mass flow rate standard deviation of salt channels of trumpet-shape lower plenum is reduced by 4.2% compared with that of the ellipsoid-shape. The mass flow rate standard deviation of salt channel is reduced by 29.2% by setting the flow distribution plate.Conclusion:Changing the structure of lower plenum andsetting the flow distribution plate are useful measures to adjust the mass flow distribution and power matching. The results can provide the basis for the optimization design of MSR with liquid fuel.%在液态燃料熔盐堆(Molten salt reactor, MSR)热工水力设计中,为实现堆芯径向功率展平需对堆芯流量分配进行设计,使得堆芯进口流量分布正比于释热量分布,而下腔室结构和流场分布对堆芯流量分配起决定性作用。利用FLUENT软件对堆芯三维流场进行模拟,通过调节下腔室结构和流量分配装置,对下腔室流场分布进行优化,最终实现堆芯流量合理分配。数值模拟结果表明,喇叭状下腔室比椭球形下腔室熔盐通道流量标准差降低4.2%,设置流量分配板熔盐通道流量标准差降低29.2%;改变下腔室结构和设置流量分配装置能够较好调节流量分配和功率分布匹配性,该结果可为液态熔盐堆堆芯优化设计提供依据。

  20. Lithium and magnesium separation from salt lake brine by ionic liquids containing tributyl phosphate%离子液体-磷酸三丁酯体系分离盐湖卤水镁锂

    Institute of Scientific and Technical Information of China (English)

    石成龙; 贾永忠; 景燕

    2015-01-01

    In the present work, a typical room temperature ionic liquids (RTILs), 1-octyl-3-methyl-imidazolium hexafluorophosphate ([C8mim][PF6]), was used as an alternative solvent to study liquid/liquid extraction of lithium from salt lake brine. In this system, the ionic liquids and tributyl phosphate (TBP) were used as extraction medium and extractant respectively. The effects of solution pH value, phase ratio and other factors on lithium extraction efficiency had been investigated. The preliminary experimental results had demonstrated that, compared with using conventional extraction system, the extraction efficiency had been increased greatly in this ionic liquid system. Optimal extraction conditions of this system include the ratio of TBP/ILs at 9/1(vol), O/A at 2:1 and unadjusted pH. Under the optimal conditions, the single extraction efficiency of lithium ion and magnesium ion were 80.64% and 5.30%, respectively. And total extraction efficiency of 99.42% was obtained by triple-stage countercurrent extraction. The single stripping rate of lithium ion and magnesium ion were 98.78% and 99.15%, respectively, at 80℃ when the A/O phase ratio was 2. The Mg/Li ratio was 3.03 in the aqueous phase after stripping, which have dropped 93.41% when compared with the initial value.To evaluate the potential use of RTILs to replace traditional volatile organic compounds (VOCs) in liquid/liquid extraction of lithium, the extractions of lithium ion with VOCs and ionic liquid were compared. Compared with using conventional extraction system, the extraction efficiency had been increased greatly in this ionic liquid system. In addition, the equipment corrosion and the environmental pollution had been avoided in this new extraction system. The extraction mechanism was deduced based on the ultraviolet-visible(UV) absorption. Cation exchange was proposed to be the mechanism of extraction followed in ionic liquid. So the ionic liquid was not only regarded as the solvent but also the co

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

    Energy Technology Data Exchange (ETDEWEB)

    Rosen, R.K.

    1989-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Rosen, R.K.

    1989-12-01

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

  3. clickECM: Development of a cell-derived extracellular matrix with azide functionalities.

    Science.gov (United States)

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

    2016-12-10

    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.

  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

    2005-01-01

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

  5. Injectable hyaluronic acid/poly(ethylene glycol) hydrogels crosslinked via strain-promoted azide-alkyne cycloaddition click reaction.

    Science.gov (United States)

    Fu, Shuangli; Dong, Hui; Deng, Xueyi; Zhuo, Renxi; Zhong, Zhenlin

    2017-08-01

    This paper reports injectable hyaluronic acid (HA)-based hydrogels crosslinked with azide-modified poly(ethylene glycol) (PEG) via the strain-promoted azide-alkyne cycloaddition (SPAAC) between cyclooctyne and azide groups. Cyclooctyne-modified HA (Cyclooctyne-HA) is prepared by the reaction of HA with 2-(aminoethoxy)cyclooctyne. To crosslink the modified HA, quadruply azide-terminated poly(ethylene glycol) (Azide-PEG) is designed and prepared. The mixture of Cyclooctyne-HA and Azide-PEG gelates in a few minutes to form a strong HA-PEG hydrogel. The hydrogel has fast gelation time, good strength, and slow degradation rate, because of the high reactivity of SPAAC, high crosslinking density originated from the quadruply-substituted Azide-PEG, and the good stability of the crosslinking amide bonds. In vitro cell culturing within the hydrogel demonstrated an excellent cell-compatibility. The bioorthogonality of SPAAC makes the hydrogel injectable. With good mechanical properties and biocompatibility, the hydrogel would be useful in a wide range of applications such as injection filling materials for plastic surgery. Copyright © 2017. Published by Elsevier Ltd.

  6. Salt splitting with ceramic membranes

    Energy Technology Data Exchange (ETDEWEB)

    Kurath, D. [Pacific Northwest National Lab., Richland, WA (United States)

    1996-10-01

    The purpose of this task is to develop ceramic membrane technologies for salt splitting of radioactively contaminated sodium salt solutions. This technology has the potential to reduce the low-level waste (LLW) disposal volume, the pH and sodium hydroxide content for subsequent processing steps, the sodium content of interstitial liquid in high-level waste (HLW) sludges, and provide sodium hydroxide free of aluminum for recycle within processing plants at the DOE complex. Potential deployment sites include Hanford, Savannah River, and Idaho National Engineering Laboratory (INEL). The technical approach consists of electrochemical separation of sodium ions from the salt solution using sodium (Na) Super Ion Conductors (NaSICON). As the name implies, sodium ions are transported rapidly through these ceramic crystals even at room temperatures.

  7. Protein aggregation in salt solutions

    Science.gov (United States)

    Kastelic, Miha; Kalyuzhnyi, Yurij V.; Hribar-Lee, Barbara; Dill, Ken A.; Vlachy, Vojko

    2015-01-01

    Protein aggregation is broadly important in diseases and in formulations of biological drugs. Here, we develop a theoretical model for reversible protein–protein aggregation in salt solutions. We treat proteins as hard spheres having square-well-energy binding sites, using Wertheim’s thermodynamic perturbation theory. The necessary condition required for such modeling to be realistic is that proteins in solution during the experiment remain in their compact form. Within this limitation our model gives accurate liquid–liquid coexistence curves for lysozyme and γ IIIa-crystallin solutions in respective buffers. It provides good fits to the cloud-point curves of lysozyme in buffer–salt mixtures as a function of the type and concentration of salt. It than predicts full coexistence curves, osmotic compressibilities, and second virial coefficients under such conditions. This treatment may also be relevant to protein crystallization. PMID:25964322

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

    Indian Academy of Sciences (India)

    Firouzeh Nesmati; Ali Elhampour

    2012-07-01

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

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

    KAUST Repository

    Johansson, Johan R.

    2011-04-01

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

  10. Quaternary ammonium room-temperature ionic liquid including an oxygen atom in side chain/lithium salt binary electrolytes: ab initio molecular orbital calculations of interactions between ions.

    Science.gov (United States)

    Tsuzuki, Seiji; Hayamizu, Kikuko; Seki, Shiro; Ohno, Yasutaka; Kobayashi, Yo; Miyashiro, Hajime

    2008-08-14

    Interactions of the lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) complex with N, N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium (DEME), 1-ethyl-3-methylimidazolium (EMIM) cations, neutral diethylether (DEE), and the DEMETFSA complex were studied by ab initio molecular orbital calculations. An interaction energy potential calculated for the DEME cation with the LiTFSA complex has a minimum when the Li atom has contact with the oxygen atom of DEME cation, while potentials for the EMIM cation with the LiTFSA complex are always repulsive. The MP2/6-311G**//HF/6-311G** level interaction energy calculated for the DEME cation with the LiTFSA complex was -18.4 kcal/mol. The interaction energy for the neutral DEE with the LiTFSA complex was larger (-21.1 kcal/mol). The interaction energy for the DEMETFSA complex with LiTFSA complex is greater (-23.2 kcal/mol). The electrostatic and induction interactions are the major source of the attraction in the two systems. The substantial attraction between the DEME cation and the LiTFSA complex suggests that the interaction between the Li cation and the oxygen atom of DEME cation plays important roles in determining the mobility of the Li cation in DEME-based room temperature ionic liquids.

  11. Differentiation of cyclosporin A from isocyclosporin A by liquid chromatography/electrospray ionization mass spectrometry with post-column addition of divalent metal salt.

    Science.gov (United States)

    Cirigliano, Adriana M; Cabrera, Gabriela M

    2014-03-15

    Cyclosporin A (CsA) rearranges to its isomer isocyclosporin A (isoCsA) upon acid hydrolysis and also during ionization in the ion source of the mass spectrometer. It has been reported that both compounds could not be differentiated by tandem mass spectrometry (MS/MS) using atmospheric pressure ionization (API) sources and ambiguously differentiated by using other sources. In order to analyze these compounds which are common fungal metabolites, it is relevant to develop a simple method for their differentiation. CsA and isoCsA were analyzed by liquid chromatography/mass spectrometry (LC/MS) with post-column addition of metal ion solutions in a quadrupole time-of-flight instrument equipped with an electrospray ionization (ESI) source. Mass spectra of CsA obtained upon post-column addition of solutions of Ca(II), Cu(II) and Zn(II) showed complexes between cyclosporin and the metal, including [2CsA + Me](2+) and [CsA-H + Me](+). These complexes were not observed in the spectra of isoCsA. The same results were observed at different metal concentrations. Differentiation via metal complexation in positive ion mode LC/ESI-MS was performed to simultaneously distinguish CsA and its isomer isoCsA. Copyright © 2014 John Wiley & Sons, Ltd.

  12. Investigation of possibility to fabricate Si3N4-TiN ceramic nanocomposite powder by azide SHS method

    Science.gov (United States)

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

    2016-11-01

    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.

  13. An efficient approach to fused indolines via a copper(I)-catalyzed reaction of sulfonyl azide with 2-ethynylaryl methylenecyclopropane.

    Science.gov (United States)

    Li, Shaoyu; Luo, Yong; Wu, Jie

    2011-06-17

    A cascade reaction of 2-ethynylaryl methylenecyclopropane with sulfonyl azide catalyzed by copper(I) iodide under mild conditions is described, which provides a novel and efficient route for the generation of fused indolines. © 2011 American Chemical Society

  14. Analysis of Phenolic Acids of Jerusalem Artichoke (Helianthus tuberosus L. Responding to Salt-Stress by Liquid Chromatography/Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Fujia Chen

    2014-01-01

    Full Text Available Plant phenolics can have applications in pharmaceutical and other industries. To identify and quantify the phenolic compounds in Helianthus tuberosus leaves, qualitative analysis was performed by a reversed phase high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS and quantitative analysis by HPLC. Ten chlorogenic acids (CGAs were identified (3-o-caffeoylquinic acid, two isomers of caffeoylquinic acid, caffeic acid, p-coumaroyl-quinic acid, feruloylquinic acid, 3,4-dicaffeoyquinic acid, 3,5-dicaffeoylquinic acid, 1,5-dicaffeoylquinic acid, and 4,5-dicaffeoylquinic acid by comparing their retention times, UV-Vis absorption spectra, and MS/MS spectra with standards. In addition, four other phenolic compounds, including caffeoyl glucopyranose, isorhamnetin glucoside, kaempferol glucuronide, and kaempferol-3-o-glucoside, were tentatively identified in Helianthus tuberosus leaves for the first time. The 3-o-caffeoylquinic acid (7.752 mg/g DW, 4,5-dicaffeoylquinic acid (5.633 mg/g DW, and 3,5-dicaffeoylquinic acid (4.900 mg/g DW were the major phenolic compounds in leaves of Helianthus tuberosus cultivar NanYu in maturity. The variations in phenolic concentrations and proportions in Helianthus tuberosus leaves were influenced by genotype and plant growth stage. Cultivar NanYu had the highest concentration of phenolic compounds, in particular 3-o-caffeoylquinic acid and 4,5-dicaffeoylquinic acid compared with the other genotypes (wild accession and QingYu. Considering various growth stages, the concentration of total phenolics in cultivar NanYu was higher at flowering stage (5.270 mg/g DW than at budding and tuber swelling stages. Cultivar NanYu of Helianthus tuberosus is a potential source of natural phenolics that may play an important role in the development of pharmaceuticals.

  15. Investigation of Analytical Techniques for the Rapid Determination of the Moisture Content of NOL 130 Primer Mix and Lead Azide

    Science.gov (United States)

    1986-05-01

    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

  16. Transition metal-free generation of N-unsubstituted imines from benzyl azides: synthesis of N-unsubstituted homoallylic amines.

    Science.gov (United States)

    Pramanik, Suman; Reddy, Reddy Rajasekhar; Ghorai, Prasanta

    2015-04-03

    An efficient transition metal-free approach for the generation of N-unsubstituted imines from azides followed by trapping with allyl nucleophile to provide N-unsubstituted homoallylic amines has been described. Although catalytic KO(t)Bu in DMSO is sufficient to allow imine generation, stoichiometric KO(t)Bu is essential in THF. Further, an enantio- and diastereoselective synthesis of homoallylic amines from benzyl azide has also been exemplified.

  17. Percolation and Physical Properties of Rock Salt

    Science.gov (United States)

    Ghanbarzadeh, S.; Hesse, M. A.; Prodanovic, M.

    2015-12-01

    Textural equilibrium controls the distribution of the liquid phase in many naturally occurring porous materials such as partially molten rocks and alloys, salt-brine and ice-water systems. In these materials, pore geometry evolves to minimize the solid-liquid interfacial energy while maintaining a constant dihedral angle, θ, at solid-liquid contact lines. A characteristic of texturally equilibrated porous media, in the absence of deformation, is that the pore network percolates at any porosity for θ60°. However, in ductile polycrystalline materials including rock salt, the balance between surface tension and ductile deformation controls the percolation of fluid pockets along grain corners and edges. Here we show sufficiently rapid deformation can overcome this threshold by elongating and connecting isolated pores by examining a large number of accessible salt samples from deep water Gulf of Mexico. We first confirm the percolation threshold in static laboratory experiments on synthetic salt samples with X-ray microtomography. We then provide field evidence on existence of interconnected pore space in rock salt in extremely low porosities, significantly below the static percolation threshold. Scaling arguments suggest that strain rates in salt are sufficient to overcome surface tension and may allow percolation. We also present the first level-set computations of three-dimensional texturally equilibrated melt networks in realistic rock fabrics. The resulting pore space is used to obtain the effective physical properties of rock, effective electrical conductivity and mechanical properties, with a novel numerical model.

  18. 4-Azidomethyl-7-methyl-2-oxo-2H-chromene-6-sulfonyl azide

    Directory of Open Access Journals (Sweden)

    Mahantesha Basanagouda

    2010-11-01

    Full Text Available In the title compound, C11H8N6O4S, the plane of the coumarin aromatic ring is twisted by 17.2 (2° with respect to the plane of the azide group bound to the methylene substituent, whereas it is twisted by 83.2 (2° to the plane of the azide attached to the sulfonyl group. The crystal structure is stabilized by weak C—H...O interactions, leading to the formation of dimers with R22(12 graph-set motifs. These dimers are further linked by weak S—O...π and π–π contacts [centroid–centroid distance = 3.765 (2 Å], leading to the formation of a layered structure.

  19. Efficient and Site-specific Antibody Labeling by Strain-promoted Azide-alkyne Cycloaddition.

    Science.gov (United States)

    Kim, Sanggil; Ko, Wooseok; Park, Hyunji; Lee, Hyun Soo

    2016-12-23

    There are currently many chemical tools available to introduce chemical probes into proteins to study their structure and function. A useful method is protein conjugation by genetically introducing an unnatural amino acid containing a bioorthogonal functional group. This report describes a detailed protocol for site-specific antibody conjugation. The protocol includes experimental details for the genetic incorporation of an azide-containing amino acid, and the conjugation reaction by strain-promoted azide-alkyne cycloaddition (SPAAC). This strain-promoted reaction proceeds by simple mixing of the reacting molecules at physiological pH and temperature, and does not require additional reagents such as copper(I) ions and copper-chelating ligands. Therefore, this method would be useful for general protein conjugation and development of antibody drug conjugates (ADCs).

  20. Alkyne-Azide “Click” Chemistry in Designing Nanocarriers for Applications in Biology

    Directory of Open Access Journals (Sweden)

    Pramod K. Avti

    2013-08-01

    Full Text Available The alkyne-azide cycloaddition, popularly known as the “click” reaction, has been extensively exploited in molecule/macromolecule build-up, and has offered tremendous potential in the design of nanomaterials for applications in a diverse range of disciplines, including biology. Some advantageous characteristics of this coupling include high efficiency, and adaptability to the environment in which the desired covalent linking of the alkyne and azide terminated moieties needs to be carried out. The efficient delivery of active pharmaceutical agents to specific organelles, employing nanocarriers developed through the use of “click” chemistry, constitutes a continuing topical area of research. In this review, we highlight important contributions click chemistry has made in the design of macromolecule-based nanomaterials for therapeutic intervention in mitochondria and lipid droplets.

  1. Evaluation of bicinchoninic acid as a ligand for copper(I)-catalyzed azide-alkyne bioconjugations.

    Science.gov (United States)

    Christen, Erik H; Gübeli, Raphael J; Kaufmann, Beate; Merkel, Lars; Schoenmakers, Ronald; Budisa, Nediljko; Fussenegger, Martin; Weber, Wilfried; Wiltschi, Birgit

    2012-09-07

    The Cu(I)-catalyzed cycloaddition of terminal azides and alkynes (click chemistry) represents a highly specific reaction for the functionalization of biomolecules with chemical moieties such as dyes or polymer matrices. In this study we evaluate the use of bicinchoninic acid (BCA) as a ligand for Cu(I) under physiological reaction conditions. We demonstrate that the BCA-Cu(I)-complex represents an efficient catalyst for the conjugation of fluorophores or biotin to alkyne- or azide-functionalized proteins resulting in increased or at least equal reaction yields compared to commonly used catalysts like Cu(I) in complex with TBTA (tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine) or BPAA (bathophenanthroline disulfonic acid). The stabilization of Cu(I) with BCA represents a new strategy for achieving highly efficient bioconjugation reactions under physiological conditions in many application fields.

  2. Relative performance of alkynes in copper-catalyzed azide-alkyne cycloaddition.

    Science.gov (United States)

    Kislukhin, Alexander A; Hong, Vu P; Breitenkamp, Kurt E; Finn, M G

    2013-04-17

    Copper-catalyzed azide-alkyne cycloaddition (CuAAC) has found numerous applications in a variety of fields. We report here only modest differences in the reactivity of various classes of terminal alkynes under typical bioconjugative and preparative organic conditions. Propargyl compounds represent an excellent combination of azide reactivity, ease of installation, and cost. Electronically activated propiolamides are slightly more reactive, at the expense of increased propensity for Michael addition. Certain alkynes, including tertiary propargyl carbamates, are not suitable for bioconjugation due to copper-induced fragmentation. A fluorogenic probe based on such reactivity is available in one step from rhodamine 110 and can be useful for optimization of CuAAC conditions.

  3. Chelation-Assisted, Copper(II) Acetate-Accelerated Azide-Alkyne Cycloaddition

    Science.gov (United States)

    Kuang, Gui-Chao; Michaels, Heather A.; Simmons, J. Tyler; Clark, Ronald J.; Zhu, Lei

    2010-01-01

    We described in a previous communication (ref. 13) a variant of the popular CuI-catalyzed azide-alkyne cycloaddition (AAC) process where 5 mol% Cu(OAc)2 in the absence of any added reducing agent is sufficient to enable the reaction. 2-Picolylazide (1) and 2-azidomethylquinoline (2) were found to be by far the most reactive carbon azide substrates that convert to 1,2,3-triazoles in as short as a few minutes under the discovered conditions. We hypothesized that the abilities of 1 and 2 to chelate CuII contribute significantly to the observed high reaction rates. The current work examines the effect of auxiliary ligands near the azido group other than pyridyl for CuII on the efficiency of the Cu(OAc)2-accelerated AAC reaction. The carbon azides capable of binding to the catalytic copper center at the alkylated azido nitrogen in a chelatable fashion were indeed shown to be superior substrates under the reported conditions. The chelation between carbon azide 11 and CuII was demonstrated in an X-ray single crystal structure. In a limited set of examples, the ligand tris(benzyltriazolylmethyl)amine (TBTA), developed by Fokin et al. for assisting the original CuI-catalyzed AAC reactions (ref. 8), also dramatically enhances the Cu(OAc)2-accelerated AAC reactions involving non-chelating azides. This observation leads to the hypothesis of an additional effect of chelating azides on the efficiencies of Cu(OAc)2-accelerated AAC reactions, which is to facilitate the rapid reduction of CuII to highly catalytic CuI species. Mechanistic studies on the AAC reactions with particular emphasis on the role of carbon azide/copper interactions will be conducted based on the observations reported in this work. Finally, the immediate utility of the product 1,2,3-triazole molecules derived from chelating azides as multidentate metal coordination ligands is demonstrated. The resulting triazolyl-containing ligands are expected to bind with transition metal ions via the N(2) nitrogen of the 1

  4. The "Clickable" Method for Oligonucleotide Immobilization Onto Azide-Functionalized Microarrays.

    Science.gov (United States)

    Ratajczak, Tomasz; Uszczyńska, Barbara; Frydrych-Tomczak, Emilia; Chmielewski, Marcin K

    2016-01-01

    The DNA microarray technique was supposed to help identifying and analyzing the expression level of tens of thousands of genes in the whole genome. But there is a serious problem concerning fabrication of the microarrays by chemical synthesis, such as specific and efficient linking of probes to a solid support. Therefore, we reckon that applying "click" chemistry to covalently anchor oligonucleotides on chemically modified supports may help construct microarrays in applications such as gene identification. Silanization of the glass support with organofunctional silane makes it possible to link azide groups on glass surface and the nucleic acid probe that is equipped with a pentynyl group. This is followed by direct spotting of the nucleic acid on the azide-modified glass support in the presence of copper ions, and this is a frequently applied method of "click" chemistry.

  5. 14N NMR Spectroscopy Study of Binding Interaction between Sodium Azide and Hydrated Fullerene

    Directory of Open Access Journals (Sweden)

    Tamar Chachibaia

    2017-04-01

    Full Text Available Our study is the first attempt to study the interaction between NaN3 and hydrated fullerenes C60 by means of a non-chemical reaction-based approach. The aim is to study deviations of signals obtained by 14N NMR spectroscopy to detect the binding interaction between sodium azide and hydrated fullerene. We considered 14N NMR spectroscopy as one of the most suitable methods for the characterization of azides to show resonance signals corresponding to the three non-equivalent nitrogen atoms. The results demonstrate that there are changes in the chemical shift positions and line-broadening, which are related to the different molar ratios of NaN3:C60 in the samples.

  6. Azide-derivatized gold nanosphere "clicked" to indium and zinc phthalocyanines for improved nonlinear optical limiting

    Science.gov (United States)

    Bankole, Owolabi M.; Nyokong, Tebello

    2017-05-01

    We report on the conjugation of azide-derivatized gold nanoparticles (AuNPs) to alkyne moieties of ZnPc and InPc via azide-alkyne Huisgen cycloaddition reaction to form phthalocyanines-AuNPs (MPc-AuNPs) conjugates. The detailed structural characterizations of the composites were in good agreement with the expected results. The nonlinear absorption coefficients and other nonlinear optical limiting parameters were almost two times larger for the conjugates compared to free phthalocyanines. We established direct relationship between improved photophysical characterizations and enhanced nonlinear effects of reverse saturable absorption mechanisms favoured by excited triplet absorption of the phthalocyanines in the presence of AuNPs. The combination of InPc with AuNPs resulted in the lowest limiting intensity value of 0.06 J/cm2, hence the best performance in terms of optical limiting.

  7. Modeling of Salt Solubilities in Mixed Solvents

    DEFF Research Database (Denmark)

    Chiavone-Filho, O.; Rasmussen, Peter

    2000-01-01

    A method to correlate and predict salt solubilities in mixed solvents using a UNIQUAC+Debye-Huckel model is developed. The UNIQUAC equation is applied in a form with temperature-dependent parameters. The Debye-Huckel model is extended to mixed solvents by properly evaluating the dielectric...... constants and the liquid densities of the solvent media. To normalize the activity coefficients, the symmetric convention is adopted. Thermochemical properties of the salt are used to estimate the solubility product. It is shown that the proposed procedure can describe with good accuracy a series of salt...

  8. Modeling of Salt Solubilities in Mixed Solvents

    DEFF Research Database (Denmark)

    Chiavone-Filho, O.; Rasmussen, Peter

    2000-01-01

    A method to correlate and predict salt solubilities in mixed solvents using a UNIQUAC+Debye-Huckel model is developed. The UNIQUAC equation is applied in a form with temperature-dependent parameters. The Debye-Huckel model is extended to mixed solvents by properly evaluating the dielectric...... constants and the liquid densities of the solvent media. To normalize the activity coefficients, the symmetric convention is adopted. Thermochemical properties of the salt are used to estimate the solubility product. It is shown that the proposed procedure can describe with good accuracy a series of salt...

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

    Directory of Open Access Journals (Sweden)

    Sebastian Rojek

    2016-03-01

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

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

    Science.gov (United States)

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

    2016-01-01

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

  11. Intramolecular azide to alkene cycloadditions for the construction of pyrrolobenzodiazepines and azetidino-benzodiazepines.

    Science.gov (United States)

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

    2014-10-17

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

    Directory of Open Access Journals (Sweden)

    Karl Hemming

    2014-10-01

    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.

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

    Science.gov (United States)

    1974-08-01

    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

  14. Copper-catalyzed [3 + 2] cycloaddition of (phenylethynyldi-p-tolylstibane with organic azides

    Directory of Open Access Journals (Sweden)

    Mizuki Yamada

    2016-06-01

    Full Text Available 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.

  15. Copper-catalyzed C(sp2)-H amidation with azides as amino sources.

    Science.gov (United States)

    Peng, Jiangling; Xie, Zeqiang; Chen, Ming; Wang, Jian; Zhu, Qiang

    2014-09-19

    A copper-catalyzed C-H amidation process, with azides as amino sources under oxidant-free conditions, has been developed. When N-heterocycles were employed as directing groups, sulfonylazide and benzoylazide could be used as amidating reagents to provide corresponding N-arylamides. When amidines or imine were used, tandem C-N/N-N bond formation occurred to afford indazole derivatives in one pot.

  16. Ultrafast infrared and UV-vis studies of the photochemistry of methoxycarbonylphenyl azides in solution.

    Science.gov (United States)

    Xue, Jiadan; Luk, Hoi Ling; Eswaran, S V; Hadad, Christopher M; Platz, Matthew S

    2012-06-07

    The photochemistry of 4-methoxycarbonylphenyl azide (2a), 2-methoxycarbonylphenyl azide (3a), and 2-methoxy-6-methoxycarbonylphenyl azide (4a) were studied by ultrafast time-resolved infrared (IR) and UV-vis spectroscopies in solution. Singlet nitrenes and ketenimines were observed and characterized for all three azides. Isoxazole species 3g and 4g are generated after photolysis of 3a and 4a, respectively, in acetonitrile. Triplet nitrene 4e formation correlated with the decay of singlet nitrene 4b. The presence of water does not change the chemistry or kinetics of singlet nitrenes 2b and 3b, but leads to protonation of 4b to produce nitrenium ion 4f. Singlet nitrenes 2b and 3b have lifetimes of 2 ns and 400 ps, respectively, in solution at ambient temperature. The singlet nitrene 4b in acetonitrile has a lifetime of about 800 ps, and reacts with water with a rate constant of 1.9 × 10(8) L·mol(-1)·s(-1) at room temperature. These results indicate that a methoxycarbonyl group at either the para or ortho positions has little influence on the ISC rate, but that the presence of a 2-methoxy group dramatically accelerates the ISC rate relative to the unsubstituted phenylnitrene. An ortho-methoxy group highly stabilizes the corresponding nitrenium ion and favors its formation in aqueous solvents. This substituent has little influence on the ring-expansion rate. These results are consistent with theoretical calculations for the various intermediates and their transition states. Cyclization from the nitrene to the azirine intermediate is favored to proceed toward the electron-deficient ester group; however, the higher energy barrier is the ring-opening process, that is, azirine to ketenimine formation, rendering the formation of the ester-ketenimine (4d') to be less favorable than the isomeric MeO-ketenimine (4d).

  17. Functionalization of Graphene Nanoplatelets Using Sugar Azide for Graphene/Epoxy Nanocomposites

    Science.gov (United States)

    2014-06-20

    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

  18. The decomposition of benzenesulfonyl azide: a matrix isolation and computational study.

    Science.gov (United States)

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

    2017-02-01

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

    Directory of Open Access Journals (Sweden)

    Ting Huang

    2015-05-01

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

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

    Directory of Open Access Journals (Sweden)

    Stefanie Wolfram

    2014-10-01

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

  1. Sulfated ligands for the copper(I)-catalyzed azide-alkyne cycloaddition.

    Science.gov (United States)

    Wang, Wei; Hong, Senglian; Tran, Andrew; Jiang, Hao; Triano, Rebecca; Liu, Yi; Chen, Xing; Wu, Peng

    2011-10-04

    The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC), the prototypical reaction of click chemistry, is accelerated by tris(triazolylmethyl)amine-based ligands. Herein, we compare two new ligands in this family--3-[4-({bis[(1-tert-butyl-1H-1,2,3-triazol-4-yl)methyl]amino}methyl)-1H-1,2,3-triazol-1-yl]propanol (BTTP) and the corresponding sulfated ligand 3-[4-({bis[(1-tert-butyl-1H-1,2,3-triazol-4-yl)methyl]amino}methyl)-1H-1,2,3-triazol-1-yl]propyl hydrogen sulfate (BTTPS)--for three bioconjugation applications: 1) labeling of alkyne-tagged glycoproteins in crude cell lysates, 2) labeling of alkyne- or azide-tagged glycoproteins on the surface of live mammalian cells, and 3) labeling of azides in surface proteins of live Escherichia coli. Although BTTPS exhibits faster kinetics than BTTP in accelerating the CuAAC reaction in in vitro kinetic measurements, its labeling efficiency is slightly lower than BTTP in modifying biomolecules with a significant amount of negative charges due to electrostatic repulsion. Nevertheless, the negative charge conferred by the sulfate at physiological conditions significantly reduced the cellular internalization of the coordinated copper(I), thus making BTTPS-Cu(I) a better choice for live-cell labeling. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. The mechanism of copper-catalyzed azide-alkyne cycloaddition reaction: a quantum mechanical investigation.

    Science.gov (United States)

    Ozen, Cihan; Tüzün, Nurcan Ş

    2012-04-01

    In this study, the mechanism of CuAAC reaction and the structure of copper acetylides have been investigated with quantum mechanical methods, namely B3LYP/6-311+G(d,p). A series of possible copper-acetylide species which contain up to four copper atoms and solvent molecules as ligand has been evaluated and a four-copper containing copper-acetylide, M1A, was proposed more likely to form based on its thermodynamic stability. The reaction has been modeled with a representative simple alkyne and a simple azide to concentrate solely on the electronic effects of the mechanism. Later, the devised mechanism has been applied to a real system, namely to the reaction of 2-azido-1,1,1-trifluoroethane and ethynylbenzene in the presence of copper. The copper catalyst transforms the concerted uncatalyzed reaction to a stepwise process and lowers the activation barrier. The pre-reactive complexation of the negatively charged secondary nitrogen of azide and the positively charged copper of copper-acetylide brings the azide and the alkyne to a suitable geometry for cycloaddition to take place. The calculated activation barrier difference between the catalyzed and the uncatalyzed reactions is consistent with faster and the regioselective synthesis of triazole product. Copyright © 2012 Elsevier Inc. All rights reserved.

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

    Science.gov (United States)

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

    2016-05-03

    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.

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

    Science.gov (United States)

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

    2012-07-07

    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.

  5. Pressure-accelerated azide-alkyne cycloaddition: micro capillary versus autoclave reactor performance.

    Science.gov (United States)

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

    2015-02-01

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Metal Free Azide-Alkyne Click Reaction: Role of Substituents and Heavy Atom Tunneling.

    Science.gov (United States)

    Karmakar, Sharmistha; Datta, Ayan

    2015-09-03

    Metal free click reactions provide an excellent noninvasive tool to modify and understand the processes in biological systems. Release of ring strain in cyclooctynes on reaction with azides on the formation of triazoles results in small activation energies for various intermolecular Huisgen reactions (1-9). Substitution of difluoro groups at the α, α' position of the cyclooctyne ring enhances the rates of cycloadditions by 10 and 20 times for methyl azide and benzyl azide respectively at room temperature. The computed rate enhancement on difluoro substitution using direct dynamical calculations using the canonical variational transition state theory (CVT/CAG) with small curvature tunneling (SCT) corrections are in excellent agreement with the experimental results. For the intramolecular click reaction (10) notwithstanding its much higher activation energy, quantum mechanical tunneling (QMT) enhances the rate of cycloaddition significantly and increases the N(14)/N(15) primary kinetic isotope effect at 298 K. QMT is shown to be rather efficient in 10 due to a thin barrier of ∼2.4 Å. The present study shows that tunneling effects can be significant for intramolecular click reactions.

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

    Directory of Open Access Journals (Sweden)

    Timothy W. Schmidt

    2013-07-01

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

  8. Modeling of ionic liquids

    Science.gov (United States)

    Tatlipinar, Hasan

    2017-02-01

    Ionic liquids are very important entry to industry and technology. Because of their unique properties they may classified as a new class of materials. IL usually classified as a high temperature ionic liquids (HTIL) and room temperature ionic liquids (RTIL). HTIL are molten salts. There are many research studies on molten salts such as recycling, new energy sources, rare elements mining. RTIL recently become very important in daily life industry because of their "green chemistry" properties. As a simple view ionic liquids consist of one positively charged and one negatively charged components. Because of their Coulombic or dispersive interactions the local structure of ionic liquids emerges. In this presentation the local structural properties of the HTIL are discussed via correlation functions and integral equation theories. RTIL are much more difficult to do modeling, but still general consideration for the modeling of the HTIL is valid also for the RTIL.

  9. Separation and Identification of Volatile Flavor Compounds in High-Salt Liquid State-Fermented Soy Sauce%高盐稀态酱油挥发性风味物质的分离与鉴定

    Institute of Scientific and Technical Information of China (English)

    高献礼; 赵谋明; 崔春; 曹鸣凯; 李丹

    2009-01-01

    分别采用固相微萃取(SPME)、同时蒸馏萃取(VSDE)和直接溶剂萃取(DSE)法对高盐稀态酱油挥发性风味物质进行分离、浓缩,并利用气质联用色谱(GC-MS)对其挥发性风味物质进行鉴定.试验共鉴定出147种风味化合物,其中酸类17种、醇类12种、醛类16种、酯类36种、呋喃(酮)类12种、酮类13种、杂环化合物14种、酚类8种、吡喃(酮)类6种、吡嗪类4种、吡咯(酮)类3种、含硫化合物6种.研究结果表明,主要挥发性风味化合物为酯、酸、醛、杂环化合物和醇类,其中酯类化合物的数量和相对含量最多;此外,有16种日式和韩式酱油中的关键风味化合物在国产高盐稀态酱油中被检出.%In this paper, such technologies as solid-phase micro-extraction (SPME), simultaneous steam distillation-extraction (VSDE) and direct solvent extraction (DSE) were employed to separate and concentrate the volatile flavor compounds in high-salt liquid state-fermented soy sauce, and the extracts were identified by means of gas chromatography-mass spectrometry (GC-MS). 147 flavor compounds, including 17 kinds of acids, 12 kinds of alcohols, 16 kinds of aldehydes, 36 kinds of esters, 12 kinds of furan(one)s, 13 kinds of ketones, 14 kinds of he-〖JP2〗 terocyclic compounds, 8 kinds of phenols, 6 kinds of pyran(one)s, 4 kinds of pyrazines, 3 kinds of pyrrol(idon)es〖JP〗 and 6 kinds of sulfur-containing compounds, were then identified. The results indicate that, in the dominant volatile flavor compounds in the soy sauce, namely, esters, acids, alcohols, aldehydes and heterocyclic compounds, esters are of the most species and of the highest relative content; and that 16 aroma-impact compounds of Japanese and Korean soy sauces were detected from Chinese high-salt liquid state-fermented soy sauce.

  10. Molten Salts for High Temperature Reactors: University of Wisconsin Molten Salt Corrosion and Flow Loop Experiments -- Issues Identified and Path Forward

    Energy Technology Data Exchange (ETDEWEB)

    Piyush Sabharwall; Matt Ebner; Manohar Sohal; Phil Sharpe; Thermal Hydraulics Group

    2010-03-01

    Considerable amount of work is going on regarding the development of high temperature liquid salts technology to meet future process needs of Next Generation Nuclear Plant. This report identifies the important characteristics and concerns of high temperature molten salts (with lesson learned at University of Wisconsin-Madison, Molten Salt Program) and provides some possible recommendation for future work

  11. Synthesis of 5-substituted 1H-tetrazoles by the copper-catalyzed [3+2] cycloaddition of nitriles and trimethylsilyl azide.

    Science.gov (United States)

    Jin, Tienan; Kitahara, Fukuzou; Kamijo, Shin; Yamamoto, Yoshinori

    2008-09-01

    The copper-catalyzed [3+2] cycloaddition between various nitriles and trimethylsilyl azide in DMF/MeOH produced the corresponding 5-substituted 1H-tetrazoles in good to high yields. It was proposed that the reaction proceeds through the formation in situ of a copper azide species and subsequent [3+2] cycloaddition with the nitriles. Furthermore, we found that a copper and triethylamine combined catalyst also promoted the cycloaddition of nitriles and trimethylsilyl azide to afford the 5-substituted 1H-tetrazoles at relatively low reaction temperatures. The copper azide species would be formed by reaction of the copper catalyst with Et(3)NHN(3) generated in situ.

  12. Immobilization of IFR salt wastes in mortar

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, D.F.; Johnson, T.R.

    1988-01-01

    Portland cement-base mortars are being considered for immobilizing chloride salt wastes produced by the fuel cycles of Integral Fast Reactors (IFR). The IFR is a sodium-cooled fast reactor with metal alloy fuels. It has a close-coupled fuel cycle in which fission products are separated from the actinides in an electrochemical cell operating at 500/degree/C. This cell has a liquid cadmium anode in which the fuels are dissolved and a liquid salt electrolyte. The salt will be a mixture of either lithium, potassium, and sodium chlorides or lithium, calcium, barium, and sodium chlorides. One method being considered for immobilizing the treated nontransuranic salt waste is to disperse the salt in a portland cement-base mortar that will be sealed in corrosion-resistant containers. For this application, the grout must be sufficiently fluid that it can be pumped into canister-molds where it will solidify into a strong, leach-resistant material. The set times must be longer than a few hours to allow sufficient time for processing, and the mortar must reach a reasonable compressive strength (/approximately/7 MPa) within three days to permit handling. Because fission product heating will be high, about 0.6 W/kg for a mortar containing 10% waste salt, the effects of elevated temperatures during curing and storage on mortar properties must be considered.

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

    Science.gov (United States)

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

    2017-01-01

    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.

  14. Bone marrow cells stained by azide-conjugated Alexa fluors in the absence of an alkyne label.

    Science.gov (United States)

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

    2012-09-01

    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.

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

    Directory of Open Access Journals (Sweden)

    María Teresa Ramírez-Palma

    2016-01-01

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

  16. 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

    OpenAIRE

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

    2016-01-01

    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.

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

    Institute of Scientific and Technical Information of China (English)

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

    2008-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Yoshihiro Kojima

    2010-02-01

    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.

  19. The behaviour of salt and salt caverns

    NARCIS (Netherlands)

    Fokker, P.A.

    1995-01-01

    Salts are mined for both storage and extraction purposes, either via dry or solution mining techniques. For operational, environmental and geological purposes, it is important to understand and predict the in situ behaviour of salt, in particular the creep and strength characteristics. A micro-mecha

  20. Ring opening of donor-acceptor cyclopropanes with the azide ion: a tool for construction of N-heterocycles.

    Science.gov (United States)

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

    2015-03-23

    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.

  1. Cooking without salt

    Science.gov (United States)

    DASH diet; High blood pressure - DASH; Hypertension - DASH; Low-salt diet - DASH ... Explore cooking with salt substitutes. Add a splash of lemon and other citrus fruits, or wine, to soups and other dishes. Or use them ...

  2. Toxicidade retiniana do gás hexafluoreto de enxofre, líquido perfluorocarbono, ar e solução salina balanceada em olhos de coelhos Sulfur hexafluoride gas, perfluorocarbon liquid, air and balanced salt solution retinal toxicity in rabbit eyes

    Directory of Open Access Journals (Sweden)

    Eduardo Vieira de Souza

    2005-08-01

    Full Text Available OBJETIVOS: Determinar a toxicidade retiniana do gás hexafluoreto de enxofre, líquido perfluorocarbono e solução salina balanceada em olhos de coelhos. MÉTODOS: Foram analisados 22 olhos de 16 coelhos albinos da raça Nova Zelândia divididos em grupos: solução salina balanceada (7 olhos; hexafluoreto de enxofre (4 olhos, líquido perfluorocarbono (5 olhos e controle (6 olhos. Após aspiração de 0,3 ml de humor vítreo, foi injetado a mesma quantidade de solução salina balanceada ou hexafluoreto de enxofre a 100% ou líquido perfluorocarbono na cavidade vítrea. O grupo controle não foi submetido a nenhum procedimento. Três semanas depois o humor vítreo foi coletado para análise bioquímica e o olho enucleado para análise histológica. RESULTADOS: Os olhos dos animais que receberam injeção de hexafluoreto de enxofre e líquido perfluorocarbono mostraram significativo aumento da concentração vítrea de glutamato quando comparado aos grupos solução salina balanceada e controle (pPURPOSE: To determine retinal toxicity after intravitreous balanced salt solution, sulfur hexafluoride gas, and perfluorocarbon liquid injection in rabbit eyes. METHODS: Twenty-two eyes of sixteen New Zealand albino rabbits were divided into groups: balanced salt solution (7 eyes; sulfur hexafluoride gas (4 eyes; and perfluorocarbon liquid (5 eyes. After the introduction of a needle through the sclera the vitreous was aspirated (0.3 ml, balanced salt solution, sulfur hexafluoride gas 100% and perfluorocarbon liquid (0.3 ml were injected into rabbit vitreous cavity. The control group (6 eyes was not submitted to any procedure. After three weeks the vitreous was aspirated and submitted to biochemical analysis and the eyes prepared for histological analysis. RESULTS: The eyes submitted to perfluorocarbon liquid and sulfur hexafluoride gas injection showed a greater L-glutamate increase in the vitreous compared to balanced salt solution and control groups

  3. Wetting and evaporation of salt-water nanodroplets: A molecular dynamics investigation

    Science.gov (United States)

    Zhang, Jun; Borg, Matthew K.; Sefiane, Khellil; Reese, Jason M.

    2015-11-01

    We employ molecular dynamics simulations to study the wetting and evaporation of salt-water nanodroplets on platinum surfaces. Our results show that the contact angle of the droplets increases with the salt concentration. To verify this, a second simulation system of a thin salt-water film on a platinum surface is used to calculate the various surface tensions. We find that both the solid-liquid and liquid-vapor surface tensions increase with salt concentration and as a result these cause an increase in the contact angle. However, the evaporation rate of salt-water droplets decreases as the salt concentration increases, due to the hydration of salt ions. When the water molecules have all evaporated from the droplet, two forms of salt crystals are deposited, clump and ringlike, depending on the solid-liquid interaction strength and the evaporation rate. To form salt crystals in a ring, it is crucial that there is a pinned stage in the evaporation process, during which salt ions can move from the center to the rim of the droplets. With a stronger solid-liquid interaction strength, a slower evaporation rate, and a higher salt concentration, a complete salt crystal ring can be deposited on the surface.

  4. Wetting and evaporation of salt-water nanodroplets: A molecular dynamics investigation.

    Science.gov (United States)

    Zhang, Jun; Borg, Matthew K; Sefiane, Khellil; Reese, Jason M

    2015-11-01

    We employ molecular dynamics simulations to study the wetting and evaporation of salt-water nanodroplets on platinum surfaces. Our results show that the contact angle of the droplets increases with the salt concentration. To verify this, a second simulation system of a thin salt-water film on a platinum surface is used to calculate the various surface tensions. We find that both the solid-liquid and liquid-vapor surface tensions increase with salt concentration and as a result these cause an increase in the contact angle. However, the evaporation rate of salt-water droplets decreases as the salt concentration increases, due to the hydration of salt ions. When the water molecules have all evaporated from the droplet, two forms of salt crystals are deposited, clump and ringlike, depending on the solid-liquid interaction strength and the evaporation rate. To form salt crystals in a ring, it is crucial that there is a pinned stage in the evaporation process, during which salt ions can move from the center to the rim of the droplets. With a stronger solid-liquid interaction strength, a slower evaporation rate, and a higher salt concentration, a complete salt crystal ring can be deposited on the surface.

  5. Experimental Study on Liquid-Liquid Equilibria of Alcohol-Ester-Water-CaCl2 System

    Institute of Scientific and Technical Information of China (English)

    Fu Jiquan; Fu Die

    2014-01-01

    The binary liquid-liquid equilibrium (LLE) data for salt-containing systems of 1-butanol+water+CaCl2, n-butyl acetate+water+CaCl2 and ethyl acetate+acetic acid+water+CaCl2 were determined and the salt effect was analyzed. The results showed that an obvious salt effect could be identified for the systems of 1-butanol+water+CaCl2 and ethyl acetate+acetic acid+water.

  6. Improved Synthesis of 5-Substituted 1H-Tetrazoles via the [3+2] Cycloaddition of Nitriles and Sodium Azide Catalyzed by Silica Sulfuric Acid

    Science.gov (United States)

    Du, Zhenting; Si, Changmei; Li, Youqiang; Wang, Yin; Lu, Jing

    2012-01-01

    A silica supported sulfuric acid catalyzed [3+2] cycloaddition of nitriles and sodium azide to form 5-substituted 1H-tetrazoles is described. The protocol can provide a series of 5-substituted 1H-tetrazoles using silica sulfuric acid from nitriles and sodium azide in DMF in 72%–95% yield. PMID:22606004

  7. Improved Synthesis of 5-Substituted 1H-Tetrazoles via the [3+2] Cycloaddition of Nitriles and Sodium Azide Catalyzed by Silica Sulfuric Acid

    Directory of Open Access Journals (Sweden)

    Jing Lu

    2012-04-01

    Full Text Available A silica supported sulfuric acid catalyzed [3+2] cycloaddition of nitriles and sodium azide to form 5-substituted 1H-tetrazoles is described. The protocol can provide a series of 5-substituted 1H-tetrazoles using silica sulfuric acid from nitriles and sodium azide in DMF in 72%–95% yield.

  8. Conjugation of transferrin to azide-modified CdSe/ZnS core-shell quantum dots using cyclooctyne click chemistry.

    Science.gov (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

    2012-10-15

    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.

  9. White emitting polyfluorene functionalized with azide hybridized on near-UV light emitting diode for high color rendering index.

    Science.gov (United States)

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

    2008-01-21

    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.

  10. LC-TOF/MS determination of phthalates in edible salts from food markets in Korea.

    Science.gov (United States)

    Dirwono, Warnadi; Nam, Yun Sik; Park, Hyun-Mee; Lee, Kang-Bong

    2013-01-01

    Residual quantities of 12 phthalates have been monitored in edible salts (raw salts, refined salts, refined salts with additives and baked salts) available in Korean food markets. Liquid-liquid extraction followed by liquid chromatography time-of-flight mass spectrometry (LC-TOF/MS) was used to analyse the samples. The method was validated and showed linear correlation (R² > 0.996) in the range 0.5-100 ng g⁻¹ for all target analytes. Recoveries were 85.9-108.4%, except for diethyl phthalate (DEP). Relative standard deviations (RSDs) were 2.7-6.0% and the limits of detection (LODs) were 1.2-2.8 ng g⁻¹. Although the contamination of phthalates in salt would be trivial in comparison to those of other main foods and below the reference dose of the Chronic Oral Exposure recommended by US-EPA, the availability of reference data could be valuable for food chemists and salt manufacturers.

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

    Science.gov (United States)

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

    2010-07-01

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

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

    Indian Academy of Sciences (India)

    G Vaitheeswaran; K Ramesh Babu

    2012-11-01

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

  13. Alkyne-azide click reaction catalyzed by metallic copper under ultrasound.

    Science.gov (United States)

    Cintas, Pedro; Barge, Alessandro; Tagliapietra, Silvia; Boffa, Luisa; Cravotto, Giancarlo

    2010-03-01

    This protocol is for the ultrasound (US)-assisted 1,3-dipolar cycloaddition reaction of azides and alkynes using metallic copper (Cu) as the catalyst. The azido group is a willing participant in this kind of organic reaction and its coupling with alkynes is substantially improved in the presence of Cu(I). This protocol does not require additional ligands and proceeds with excellent yields. The Cu-catalyzed azide-alkyne cycloaddition (CuAAC) is generally recognized as the most striking example of 'click chemistry'. Reactions involving metals represent the favorite domain of sonochemistry because US favors mechanical depassivation and enhances both mass transfer and electron transfer from the metal to the organic acceptor. The reaction rate increases still further when simultaneous US and microwave irradiation are applied. The US-assisted click synthesis has been applied for the preparation of a wide range of 1,4-disubstituted 1,2,3-triazole derivatives starting both from small molecules and oligomers such as cyclodextrins (CDs). Using this efficient and greener protocol, all the adducts can be synthesized in 2-4 h (including work-up and excluding characterization). Click chemistry has been shown to be able to directly link chemistry to biology, thus becoming a true interdisciplinary reaction with extremely wide applicability.

  14. The salts of Mars

    Science.gov (United States)

    Clark, B. C.; Van Hart, D. C.

    1981-01-01

    Salt compounds are apparently an important component of the fine-grained regolith on Mars. Salt enrichment may be explained either as a secondary concentration of chemical weathering products or as direct incorporation of planetary released volatiles. Geochemical measurements and chemical relationships constrain the salt species and resultant physicochemical consequences. A likely assemblage is dominated by (Mg,Na)SO4, NaCl, and (Mg,Ca)CO3. Formation of brine in equilibrium with such a salt mixture is unlikely under the temperature and water-vapor restrictions prevalent over most, if not all, of the Martian surface. Acidic conditions, accompanying salt formation, favor the preferential destruction of susceptible igneous minerals.

  15. Salt-specific effects in lysozyme solutions

    Directory of Open Access Journals (Sweden)

    T. Janc

    2016-03-01

    Full Text Available The effects of additions of low-molecular-mass salts on the properties of aqueous lysozyme solutions are examined by using the cloud-point temperature, T_{cloud}, measurements. Mixtures of protein, buffer, and simple salt in water are studied at pH=6.8 (phosphate buffer and pH=4.6 (acetate buffer. We show that an addition of buffer in the amount above I_{buffer} = 0.6 mol dm^{-3} does not affect the T_{cloud} values. However, by replacing a certain amount of the buffer electrolyte by another salt, keeping the total ionic strength constant, we can significantly change the cloud-point temperature. All the salts de-stabilize the solution and the magnitude of the effect depends on the nature of the salt. Experimental results are analyzed within the framework of the one-component model, which treats the protein-protein interaction as highly directional and of short-range. We use this approach to predict the second virial coefficients, and liquid-liquid phase diagrams under conditions, where T_{cloud} is determined experimentally.

  16. Sodium Azide

    Science.gov (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 ...

  17. Thermal Characterization of Molten Salt Systems

    Energy Technology Data Exchange (ETDEWEB)

    Toni Y. Gutknecht; Guy L. Fredrickson

    2011-09-01

    The phase stability of molten salts in an electrorefiner (ER) may be adversely affected by the buildup of sodium, fission products, and transuranics in the electrolyte. Potential situations that need to be avoided are the following: (1) salt freezing due to an unexpected change in the liquidus temperature, (2) phase separation or non-homogeneity of the molten salt due to the precipitation of solids or formation of immiscible liquids, and (3) any mechanism that can result in the separation and concentration of fissile elements from the molten salt. Any of these situations would result in an off-normal condition outside the established safety basis for electrorefiner (ER) operations. The stability (and homogeneity) of the phases can potentially be monitored through the thermal characterization of the salts, which can be a function of impurity concentration. This report describes the experimental results of typical salts compositions, which consist of chlorides of potassium, lithium, strontium, samarium, praseodymium, lanthanum, barium, cerium, cesium, neodymium, sodium and gadolinium chlorides as a surrogate for both uranium and plutonium, used for the processing of used nuclear fuels.

  18. Molten salts and nuclear energy production

    Science.gov (United States)

    Le Brun, Christian

    2007-01-01

    Molten salts (fluorides or chlorides) were considered near the beginning of research into nuclear energy production. This was initially due to their advantageous physical and chemical properties: good heat transfer capacity, radiation insensitivity, high boiling point, wide range solubility for actinides. In addition it was realised that molten salts could be used in numerous situations: high temperature heat transfer, core coolants with solid fuels, liquid fuel in a molten salt reactor, solvents for spent nuclear solid fuel in the case of pyro-reprocessing and coolant and tritium production in the case of fusion. Molten salt reactors, one of the six innovative concepts chosen by the Generation IV international forum, are particularly interesting for use as either waste incinerators or thorium cycle systems. As the neutron balance in the thorium cycle is very tight, the possibility to perform online extraction of some fission product poisons from the salt is very attractive. In this article the most important questions that must be addressed to demonstrate the feasibility of molten salt reactor will be reviewed.

  19. Molten salts and nuclear energy production

    Energy Technology Data Exchange (ETDEWEB)

    Le Brun, Christian [Laboratoire de Physique Subatomique et de Cosmologie, 53 Avenue des Martyrs, 38026 Grenoble cedex (France)]. E-mail: christian.lebrun@lpsc.in2p3.fr

    2007-01-15

    Molten salts (fluorides or chlorides) were considered near the beginning of research into nuclear energy production. This was initially due to their advantageous physical and chemical properties: good heat transfer capacity, radiation insensitivity, high boiling point, wide range solubility for actinides. In addition it was realised that molten salts could be used in numerous situations: high temperature heat transfer, core coolants with solid fuels, liquid fuel in a molten salt reactor, solvents for spent nuclear solid fuel in the case of pyro-reprocessing and coolant and tritium production in the case of fusion. Molten salt reactors, one of the six innovative concepts chosen by the Generation IV international forum, are particularly interesting for use as either waste incinerators or thorium cycle systems. As the neutron balance in the thorium cycle is very tight, the possibility to perform online extraction of some fission product poisons from the salt is very attractive. In this article the most important questions that must be addressed to demonstrate the feasibility of molten salt reactor will be reviewed.

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

    Directory of Open Access Journals (Sweden)

    I Gusti Agung Eka Saraswati

    2013-04-01

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

  1. Theoretical studies on the regioselectivity of iridium-catalyzed 1,3-dipolar azide-alkyne cycloaddition reactions.

    Science.gov (United States)

    Luo, Qiong; Jia, Guochen; Sun, Jianwei; Lin, Zhenyang

    2014-12-19

    Iridium-catalyzed cycloaddition of thioalkynes and bromoalkynes with azides have been investigated with the aid of density functional theory (DFT) calculations at the M06 level of theory. Our investigation focused on the different regioselectivity observed for the reactions of the two classes of alkynes. The DFT results have shown that the mechanisms of cycloaddition reactions using thioalkynes and bromoalkynes as substrates are similar yet different. The reactions of thioalkynes occur via a metallabicyclic Ir-carbene intermediate formed through alkyne-azide oxidative coupling via attack of the azide terminal nitrogen toward the β alkyne carbon, whose carbene ligand is stabilized by an alkylthio/arylthio substituent. Reductive elimination from the intermediate leads to the formation of the experimentally observed 5-sulfenyltriazole. In the reactions of bromoalkynes RC≡CBr, the reaction mechanism involves the initial formation of a six-membered-ring metallacycle intermediate in the oxidative coupling step. The six-membered-ring intermediate then undergoes isomerization via migrating the terminal azide nitrogen from the β carbon to the α carbon to form a much less stable metallabicyclic Ir-carbene species from which reductive elimination gives 4-bromotriazole.

  2. Highly efficient coupling of beta-substituted aminoethane sulfonyl azides with thio acids, toward a new chemical ligation reaction.

    Science.gov (United States)

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

    2005-03-17

    [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.

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

    Science.gov (United States)

    Shabanpoor, Fazel; Gait, Michael J

    2013-11-11

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

  4. Copper-Catalyzed Multicomponent Domino Reaction of 2-Bromoaldehydes, Benzylamines, and Sodium Azide for the Assembly of Quinazoline Derivatives.

    Science.gov (United States)

    Xu, Cheng; Jia, Feng-Cheng; Zhou, Zhi-Wen; Zheng, Si-Jie; Li, Han; Wu, An-Xin

    2016-04-01

    An efficient three-component domino reaction of 2-bromoaldehydes, benzylamines, and sodium azide has been developed for the synthesis of quinazoline derivatives. This domino process involves copper-catalyzed SNAr, oxidation/cyclization, and denitrogenation sequences. The mild catalytic system enabled the effective construction of three C-N bonds in one operation.

  5. 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

    2016-01-01

    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

  6. A copper(I)-catalyzed reaction of 2-(2-ethynylphenyl)oxirane, sulfonyl azide, with 2-isocyanoacetate.

    Science.gov (United States)

    Li, Shaoyu; Wu, Jie

    2012-09-14

    A novel and straightforward synthetic protocol for the efficient construction of 3',5'-dihydro-1H-spiro[benzo[d]oxepine-2,4'-imidazoles] through a copper(I)-catalyzed reaction between 2-(2-ethynylphenyl)oxirane, sulfonyl azide, and 2-isocyanoacetate is described.

  7. Copper-Catalyzed Intermolecular Trifluoromethylazidation and Trifluoromethylthiocyanation of Allenes: Efficient Access to CF3-Containing Allyl Azides and Thiocyanates.

    Science.gov (United States)

    Zhu, Na; Wang, Fei; Chen, Pinhong; Ye, Jinxing; Liu, Guosheng

    2015-07-17

    A mild and efficient method for copper-catalyzed trifluoromethylazidation and trifluoromethylthiocyanation of allenes was explored. A series of CF3-containing allyl azides and thiocyanates were obtained with high yields and good stereoselectivities, which can be used for further transformation to some valuable compounds.

  8. Multifunctional Giant Amphiphiles via simultaneous copper(I)-catalyzed azide-alkyne cycloaddition and living radical polymerization.

    Science.gov (United States)

    Daskalaki, Eleftheria; Le Droumaguet, Benjamin; Gérard, David; Velonia, Kelly

    2012-02-01

    A novel class of chemically addressable, multifunctional Giant Amphiphiles was synthesized in excellent yields and polydispersity following simultaneous or sequential living radical polymerization and the click, copper(I)-catalysed azide-alkyne cycloaddition (CuAAC). This new approach allows chemical tailoring of the biomacromolecules and in situ formation of nanocontainers. This journal is © The Royal Society of Chemistry 2012

  9. Fast copper-free click DNA ligation by the ring-strain promoted alkyne-azide cycloaddition reaction.

    Science.gov (United States)

    Shelbourne, Montserrat; Chen, Xiong; Brown, Tom; El-Sagheer, Afaf H

    2011-06-14

    Templated DNA strand ligation by the ring-strain promoted alkyne-azide [3+2] cycloaddition reaction is very fast; with dibenzocyclooctyne, the reaction is essentially complete in 1 min. It is inhibited by the presence of a single mismatched base pair suggesting applications in genetic analysis. This journal is © The Royal Society of Chemistry 2011

  10. Asymmetric nitrene transfer reactions: sulfimidation, aziridination and C-H amination using azide compounds as nitrene precursors.

    Science.gov (United States)

    Uchida, Tatsuya; Katsuki, Tsutomu

    2014-02-01

    Nitrogen functional groups are found in many biologically active compounds and their stereochemistry has a profound effect on biological activity. Nitrene transfer reactions such as aziridination, C-H bond amination, and sulfimidation are useful methods for introducing nitrogen functional groups, and the enantiocontrol of the reactions has been extensively investigated. Although high enantioselectivity has been achieved, most of the reactions use (N-arylsulfonylimino)phenyliodinane, which co-produces iodobenzene, as a nitrene precursor and have a low atom economy. Azide compounds, which give nitrene species by releasing nitrogen, are ideal precursors but rather stable. Their decomposition needs UV irradiation, heating in the presence of a metal complex, or Lewis acid treatment. The examples of previous azide decomposition prompted us to examine Lewis acid and low-valent transition-metal complexes as catalysts for azide decomposition. Thus, we designed new ruthenium complexes that are composed of a low-valent Ru(II) ion, apical CO ligand, and an asymmetry-inducing salen ligand. With these ruthenium complexes and azides, we have achieved highly enantioselective nitrene transfer reactions under mild conditions. Recently, iridium-salen complexes were added to our toolbox. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2011-02-01

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

  12. Highly sensitive fluorescence and SERS detection of azide through a simple click reaction of 8-chloroquinoline and phenylacetylene.

    Science.gov (United States)

    Zeng, Qing; Ye, Lingling; Ma, Lu; Yin, Wenqing; Li, Tingsheng; Liang, Aihui; Jiang, Zhiliang

    2015-05-01

    In 0.19 mol/L acetic acid (HAc), a click reaction of 8-chloroquinoline/azide/phenylacetylene take places in aqueous solution without Cu(I) as a catalyst. 8-Chloroquinoline (CQN) exhibited a strong fluorescence peak at 430 nm that was quenched linearly as the concentration of azide increased from 20 to 1000 ng/mL. This quenching was due to consumption of CQN in the click reaction and a decrease in the number of efficiently excited photons due to the presence of triazole-quinoline ramification molecules with strong hydrophobicity. Using blue nanosilver sol as the substrate, CQN absorbed onto the surface of nanosilver particles, showing a strong surface-enhanced Raman scattering (SERS) peak at 1585 cm(-1) that decreased linearly as the azide concentration increased from 8 to 500 ng/mL; the detection limit was 4 ng/mL. Thus, two new, simple and sensitive fluorescence and SERS methods have been developed for the determination of azide via the click reaction. Copyright © 2014 John Wiley & Sons, Ltd.

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

    DEFF Research Database (Denmark)

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

    2014-01-01

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

  14. Liquids and liquid mixtures

    CERN Document Server

    Rowlinson, J S; Baldwin, J E; Buckingham, A D; Danishefsky, S

    2013-01-01

    Liquids and Liquid Mixtures, Third Edition explores the equilibrium properties of liquids and liquid mixtures and relates them to the properties of the constituent molecules using the methods of statistical thermodynamics. Topics covered include the critical state, fluid mixtures at high pressures, and the statistical thermodynamics of fluids and mixtures. This book consists of eight chapters and begins with an overview of the liquid state and the thermodynamic properties of liquids and liquid mixtures, including vapor pressure and heat capacities. The discussion then turns to the thermodynami

  15. Experimental investigation on the mechanism of chelation-assisted, copper(II) acetate-accelerated azide-alkyne cycloaddition.

    Science.gov (United States)

    Kuang, Gui-Chao; Guha, Pampa M; Brotherton, Wendy S; Simmons, J Tyler; Stankee, Lisa A; Nguyen, Brian T; Clark, Ronald J; Zhu, Lei

    2011-09-07

    A mechanistic model is formulated to account for the high reactivity of chelating azides (organic azides capable of chelation-assisted metal coordination at the alkylated azido nitrogen position) and copper(II) acetate (Cu(OAc)(2)) in copper(II)-mediated azide-alkyne cycloaddition (AAC) reactions. Fluorescence and (1)H NMR assays are developed for monitoring the reaction progress in two different solvents, methanol and acetonitrile. Solvent kinetic isotopic effect and premixing experiments give credence to the proposed different induction reactions for converting copper(II) to catalytic copper(I) species in methanol (methanol oxidation) and acetonitrile (alkyne oxidative homocoupling), respectively. The kinetic orders of individual components in a chelation-assisted, copper(II)-accelerated AAC reaction are determined in both methanol and acetonitrile. Key conclusions resulting from the kinetic studies include (1) the interaction between copper ion (either in +1 or +2 oxidation state) and a chelating azide occurs in a fast, pre-equilibrium step prior to the formation of the in-cycle copper(I)-acetylide, (2) alkyne deprotonation is involved in several kinetically significant steps, and (3) consistent with prior experimental and computational results by other groups, two copper centers are involved in the catalysis. The X-ray crystal structures of chelating azides with Cu(OAc)(2) suggest a mechanistic synergy between alkyne oxidative homocoupling and copper(II)-accelerated AAC reactions, in which both a bimetallic catalytic pathway and a base are involved. The different roles of the two copper centers (a Lewis acid to enhance the electrophilicity of the azido group and a two-electron reducing agent in oxidative metallacycle formation, respectively) in the proposed catalytic cycle suggest that a mixed valency (+2 and +1) dinuclear copper species be a highly efficient catalyst. This proposition is supported by the higher activity of the partially reduced Cu(OAc)(2) in

  16. PENENTUAN KADAR IODIDA DAN IODAT DALAM GARAM BERIODIUM DENGAN METODE KROMATOGRAFI CAIR KENERJA TINGGI PASANGAN ION [Determination of Iodate and Iodide Content in Iodized Salt By Ion Pair High Performance Liquid Chromatography Method

    Directory of Open Access Journals (Sweden)

    Wisnu Cahyadi1

    2004-04-01

    Full Text Available Two species of iodine, i.e. iodide and iodate in commercial iodized salt were determined using ion pair HPLC. From 15 samples analysed, the iodide and iodate content ranged from 24,05 ± 2,51 to 70,25 ± 3,78 ppm and from 31,43 ± 8,10 to 87,59 ± 0,44 ppm, respectively. The method used was found satisfactory in terms of precission, accuracy, sensitivity and selectivity, therefore the method seem acceptable for the determination of iodide and iodate content in iodized salt samples.

  17. Submarine Salt Karst Terrains

    Directory of Open Access Journals (Sweden)

    Nico Augustin

    2016-06-01

    Full Text Available Karst terrains that develop in bodies of rock salt (taken as mainly of halite, NaCl are special not only for developing in one of the most soluble of all rocks, but also for developing in one of the weakest rocks. Salt is so weak that many surface-piercing salt diapirs extrude slow fountains of salt that that gravity spread downslope over deserts on land and over sea floors. Salt fountains in the deserts of Iran are usually so dry that they flow at only a few cm/yr but the few rain storms a decade so soak and weaken them that they surge at dm/day for a few days. We illustrate the only case where the rates at which different parts of one of the many tens of subaerial salt karst terrains in Iran flows downslope constrains the rates at which its subaerial salt karst terrains form. Normal seawater is only 10% saturated in NaCl. It should therefore be sufficiently aggressive to erode karst terrains into exposures of salt on the thousands of known submarine salt extrusions that have flowed or are still flowing over the floors of hundreds of submarine basins worldwide. However, we know of no attempt to constrain the processes that form submarine salt karst terrains on any of these of submarine salt extrusions. As on land, many potential submarine karst terrains are cloaked by clastic and pelagic sediments that are often hundreds of m thick. Nevertheless, detailed geophysical and bathymetric surveys have already mapped likely submarine salt karst terrains in at least the Gulf of Mexico, and the Red Sea. New images of these two areas are offered as clear evidence of submarine salt dissolution due to sinking or rising aggressive fluids. We suggest that repeated 3D surveys of distinctive features (± fixed seismic reflectors of such terrains could measure any downslope salt flow and thus offer an exceptional opportunity to constrain the rates at which submarine salt karst terrains develop. Such rates are of interest to all salt tectonicians and the many

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

    KAUST Repository

    Hou, Duenren

    2010-11-01

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

  19. Synthesis, solid-state structure, and bonding analysis of a homoleptic beryllium azide

    Energy Technology Data Exchange (ETDEWEB)

    Naglav, Dominik; Tobey, Briac; Lyhs, Benjamin; Roemer, Beate; Blaeser, Dieter; Woelper, Christoph; Jansen, Georg; Schulz, Stephan [Faculty of Chemistry and Center for Nanointegration Duisburg-Essen (Cenide), Duisburg-Essen Univ., Essen (Germany)

    2017-07-10

    [Ph{sub 4}P]{sub 2}[Be(N{sub 3}){sub 4}] (1) and [PNP]{sub 2}[Be(N{sub 3}){sub 4}] (2; PNP=Ph{sub 3}PNPPh{sub 3}) were synthesized by reacting Be(N{sub 3}){sub 2} with [Ph{sub 4}P]N{sub 3} and [PNP]N{sub 3}. Compound 1 represents the first structurally characterized homoleptic beryllium azide. The electronic structure and bonding situation in the tetraazidoberyllate dianion [Be(N{sub 3}){sub 4}]{sup 2-} were investigated by quantum-chemical calculations (NPA, ELF, LOL). (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. N[Formula: see text] azide anion confined inside finite-size carbon nanotubes.

    Science.gov (United States)

    Battaglia, Stefano; Evangelisti, Stefano; Faginas-Lago, Noelia; Leininger, Thierry

    2017-09-26

    In this work, the confinement of an N[Formula: see text] azide anion inside finite-size single-wall zigzag and armchair carbon nanotubes of different diameters has been studied by wave function and density functional theory. Unrelaxed and relaxed interaction energies have been computed, resulting in a favorable interaction between the guest and host system. In particular, the largest interaction has been observed for the confinement in an armchair (5,5) carbon nanotube, for which a natural population analysis as well as an investigation based on the molecular electrostatic potential has been carried out. The nature of the interaction between the two fragments appears to be mainly electrostatic, favored by the enhanced polarizability of the nanotube wall treated as a finite system and passivated by hydrogen atoms. The results obtained are promising for possible applications of this complex as a starting point for the stabilization of larger polynitrogen compounds, suitable as a high-energy density material.

  1. Selection of Natural Peptide Ligands for Copper-Catalyzed Azide-Alkyne Cycloaddition Catalysis.

    Science.gov (United States)

    Aioub, Allison G; Dahora, Lindsay; Gamble, Kelly; Finn, M G

    2017-06-21

    The copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction is a powerful tool for making connections in both organic reactions and biological systems. However, the use of this ligation process in living cells is limited by the toxicity associated with unbound copper ions. As an initial attempt to create peptide-based accelerating ligands capable of cellular expression, we performed synthesis and selection for such species on solid-phase synthesis beads bearing both candidate ligand and alkyne substrate. A simple histidine-containing motif (HXXH) was identified, and found after solution-phase optimization to produce single-turnover systems showing moderate rate acceleration over the ligand-free reaction. CuAAC reaction rates and yields for different alkynes were found to respond to the peptide ligands, demonstrating a substrate scope beyond what was used for the selection steps, but also illustrating the potential difficulty in evolving a general CuAAC catalyst.

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

    Science.gov (United States)

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

    2013-08-21

    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. Azide-Alkyne Huisgen [3+2] Cycloaddition Using CuO Nanoparticles

    Directory of Open Access Journals (Sweden)

    Hyunjoon Song

    2012-11-01

    Full Text Available Recent developments in the synthesis of CuO nanoparticles (NPs and their application to the [3+2] cycloaddition of azides with terminal alkynes are reviewed. With respect to the importance of click chemistry, CuO hollow NPs, CuO hollow NPs on acetylene black, water-soluble double-hydrophilic block copolymer (DHBC nanoreactors and ZnO–CuO hybrid NPs were synthesized. Non-conventional energy sources such as microwaves and ultrasound were also applied to these click reactions, and good catalytic activity with high regioselectivity was observed. CuO hollow NPs on acetylene black can be recycled nine times without any loss of activity, and water-soluble DHBC nanoreactors have been developed for an environmentally friendly process.

  4. Solvent-free copper-catalyzed azide-alkyne cycloaddition under mechanochemical activation.

    Science.gov (United States)

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

    2015-02-09

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

    Directory of Open Access Journals (Sweden)

    Laura Rinaldi

    2015-02-01

    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.

  6. Cycloaddition reactivity studies of first-row transition metal-azide complexes and alkynes: an inorganic click reaction for metalloenzyme inhibitor synthesis.

    Science.gov (United States)

    Evangelio, Emi; Rath, Nigam P; Mirica, Liviu M

    2012-07-14

    The studies described herein focus on the 1,3-dipolar cycloaddition reaction between first-row transition metal-azide complexes and alkyne reagents, i.e. an inorganic variant of the extensively used "click reaction". The reaction between the azide complexes of biologically-relevant metals (e.g., Fe, Co and Ni) found in metalloenzyme active sites and alkyne reagents has been investigated as a proof-of-principle for a novel method of developing metalloenzyme triazole-based inhibitors. Six Fe, Co and Ni mono-azide complexes employing salen- and cyclam-type ligands have been synthesized and characterized. The scope of the targeted inorganic azide-alkyne click reaction was investigated using the electron-deficient alkyne dimethyl acetylenedicarboxylate. Of the six metal-azide complexes tested, the Co and Ni complexes of the 1,4,8,11-tetrametyl-1,4,8,11-tetraazacyclotetradecane (Me(4)cyclam) ligand showed a successful cycloaddition reaction and formation of the corresponding metal-triazolate products, which were crystallographically characterized. Moreover, use of less electron deficient alkynes resulted in a loss of cycloaddition reactivity. Analysis of the structural parameters of the investigated metal-azide complexes suggests that a more symmetric structure and charge distribution within the azide moiety is needed for the formation of a metal-triazolate product. Overall, these results suggest that a successful cycloaddition reaction between a metal-azide complex and an alkyne substrate is dependent both on the ligand and metal oxidation state, that determine the electronic properties of the bound azide, as well as the electron deficient nature of the alkyne employed.

  7. Exploring the flexible chemistry of 4-fluoro-3-nitrophenyl azide for biomolecule immobilization and bioconjugation.

    Science.gov (United States)

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

    2016-10-01

    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.

  8. Millimeter-Wave Spectroscopy of Formyl Azide (HC(O)N_3)

    Science.gov (United States)

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

    2015-06-01

    Formyl azide (HC(O)N_3) is a highly unstable molecule (t1/2˜2 hours at room temperature as a gas) that has only recently been studied spectroscopically by UV, IR, Raman and NMR methods. We have synthesized formyl azide and obtained its absorption spectrum at room temperature over the range 250-360 GHz. As in the case of carbonyl diazide, two conformers are expected for HC(O)N_3, with the syn-isomer 2.8 kcal/mol lower in energy than the anti-isomer (CCSD(T)/ANO1). Calculations at the same level of theory and the same basis set predict the dipole moments for the syn-isomer (μ = 1.56 D) and anti-isomer (μ = 2.56 D). These calculations also indicate that b-type transitions should dominate the syn-isomer spectrum, while a-type transitions become more significant in the case of the anti-isomer. Despite the anti-isomer having a larger dipole moment, the syn-isomer still gives rise to all the dominant features of the spectrum. Thus far, five vibrational states (νb{9}, νb{12}, 2νb{9}, νb{9} + νb{12}, νb{11}) have been studied for the syn-isomer, with the highest energy state νb{11} = 582.6 wn. Searches for the spectra of the anti-isomer are ongoing. Banert, K. et al. Angew. Chem. Int. Ed. 2012, 51, 4718-4721 Zeng, X. et al. Angew. Chem. Int. Ed. 2013, 52, 3503-3506 Amberger, B.K. et al. J. Mol. Spectrosc. 259, (2014) 15-20

  9. Thermodynamic modelling of phase equilibrium for water + poly(Ethylene glycol + salt aqueous two-phase systems

    Directory of Open Access Journals (Sweden)

    R.A.G. Sé

    2002-04-01

    Full Text Available The NRTL (nonrandom, two-liquid model, expressed in mass fraction instead of mole fraction, was used to correlate liquid-liquid equilibria for aqueous two-phase polymer-salt solutions. New interaction energy parameters for this model were determined using reported data on the water + poly(ethylene glycol + salt systems, with different molecular masses for PEG and the salts potassium phosphate, sodium sulfate, sodium carbonate and magnesium sulfate. The correlation of liquid-liquid equilibrium is quite satisfactory.

  10. A universal salt model based on under-ground precipitation of solid salts due to supercritical water `out-salting'

    Science.gov (United States)

    Rueslåtten, H.; Hovland, M. T.

    2010-12-01

    One of the common characteristics of planets Earth and Mars is that both host water (H2O) and large accumulations of salt. Whereas Earth’s surface-environment can be regarded as ‘water-friendly’ and ‘salt hostile’, the reverse can be said for the surface of Mars. This is because liquid water is stable on Earth, and the atmosphere transports humidity around the globe, whereas on planet Mars, liquid water is unstable, rendering the atmosphere dry and, therefore, ‘salt-friendly’. The riddle as to how the salt accumulated in various locations on those two planets, is one of long-lasting and great debate. The salt accumulations on Earth are traditionally termed ‘evaporites’, meaning that they formed as a consequence of the evaporation of large masses of seawater. How the accumulations on Mars formed is much harder to explain, as an ocean only existed briefly. Although water molecules and OH-groups may exist in abundance in bound form (crystal water, adsorbed water, etc.), the only place where free water is expected to be stable on Mars is within underground faults, fractures, and crevices. Here it likely occurs as brine or in the form of ice. Based on these conditions, a key to understanding the accumulation of large deposits of salt on both planets is linked to how brines behave in the subsurface when pressurized and heated beyond their supercritical point. At depths greater than about 3 km (P>300 bars) water will no longer boil in a steam phase. Rather, it becomes supercritical and will attain the phase of supercritical water vapor (SCRIW) with a specific gravity of typically 0.3 g/cm3. An important characteristic of SCRIW is its inability to dissolve the common sea salts. The salt dissolved in the brines will therefore precipitate as solid particles when brines (seawater on the Earth) move into the supercritical P&T-domain (T>400°C, P>300 bars). Numerical modeling of a hydrothermal system in the Atlantis II Deep of the Red Sea indicates that a

  11. Physical Properties Data for Rock Salt

    Science.gov (United States)

    1981-01-01

    In certain other deposits, brines may probable extension of the Louann Salt of Jurassic age have originated as magmatic or artesian ground waters...1978). (1211 Clynne, M.A. and Potter, R.W., United States Geological (871 Reference (271, p. 108. Survey, Menlo Park , CA, unpublished data (1978...Properties of Park , Calif., 79 pp. (1965). [AD 625 568] Some Organic Liquids and of Fifteen of the Alkali Halides," [601 Laboratory for Insulation

  12. SALT for Language Acquisition.

    Science.gov (United States)

    Bancroft, W. Jane

    1996-01-01

    Discusses Schuster's Suggestive-Accelerative Learning Techniques (SALT) Method, which combines Lozanov's Suggestopedia with such American methods as Asher's Total Physical Response and Galyean's Confluent Education. The article argues that students trained with the SALT Method have higher achievement scores and better attitudes than others. (14…

  13. Hydroxycarboxylic acids and salts

    Energy Technology Data Exchange (ETDEWEB)

    Kiely, Donald E; Hash, Kirk R; Kramer-Presta, Kylie; Smith, Tyler N

    2015-02-24

    Compositions which inhibit corrosion and alter the physical properties of concrete (admixtures) are prepared from salt mixtures of hydroxycarboxylic acids, carboxylic acids, and nitric acid. The salt mixtures are prepared by neutralizing acid product mixtures from the oxidation of polyols using nitric acid and oxygen as the oxidizing agents. Nitric acid is removed from the hydroxycarboxylic acids by evaporation and diffusion dialysis.

  14. SALT for Language Acquisition.

    Science.gov (United States)

    Bancroft, W. Jane

    1996-01-01

    Discusses Schuster's Suggestive-Accelerative Learning Techniques (SALT) Method, which combines Lozanov's Suggestopedia with such American methods as Asher's Total Physical Response and Galyean's Confluent Education. The article argues that students trained with the SALT Method have higher achievement scores and better attitudes than others. (14…

  15. Geomechanics of bedded salt

    Energy Technology Data Exchange (ETDEWEB)

    Serata, S.; Milnor, S.W.

    1979-06-08

    Creep data from the literature search is reinterpreted by SGI, resulting in a better understanding of the temperature and stress state dependence of the octahedral creep rate and the octahedral shear strength. The concept of a transition strength between the elastic and the plastic states is in agreement with the data. The elastic and rheological properties of salt are described, and a set of constitutive equations is presented. The dependence of material properties on parameters such as temperature is considered. Findings on the permeability of salt are summarized, and the in-situ behavior of openings in bedded salt is described based on extensive engineering experience. A stress measuring system utilizing a finite element computer code is discussed. Geological factors affecting the stability of salt openings are considered, and the Stress Control Technique for designing stable openings in bedded salt formations is explained.

  16. Salt Tolerance in Soybean

    Institute of Scientific and Technical Information of China (English)

    Tsui-Hung Phang; Guihua Shao; Hon-Ming Lam

    2008-01-01

    Soybean is an Important cash crop and its productivity is significantly hampered by salt stress. High salt Imposes negative impacts on growth, nodulation, agronomy traits, seed quality and quantity, and thus reduces the yield of soybean. To cope with salt stress, soybean has developed several tolerance mechanisms, including: (I) maintenance of ion homeostasis; (ii) adjustment in response to osmotic stress; (iii) restoration of osmotic balance; and (iv) other metabolic and structural adaptations. The regulatory network for abiotic stress responses in higher plants has been studied extensively in model plants such as Arabidopsis thaliana. Some homologous components involved in salt stress responses have been identified in soybean. In this review, we tried to integrate the relevant works on soybean and proposes a working model to descdbe Its salt stress responses at the molecular level.

  17. Salt and nephrolithiasis.

    Science.gov (United States)

    Ticinesi, Andrea; Nouvenne, Antonio; Maalouf, Naim M; Borghi, Loris; Meschi, Tiziana

    2016-01-01

    Dietary sodium chloride intake is nowadays globally known as one of the major threats for cardiovascular health. However, there is also important evidence that it may influence idiopathic calcium nephrolithiasis onset and recurrence. Higher salt intake has been associated with hypercalciuria and hypocitraturia, which are major risk factors for calcium stone formation. Dietary salt restriction can be an effective means for secondary prevention of nephrolithiasis as well. Thus in this paper, we review the complex relationship between salt and nephrolithiasis, pointing out the difference between dietary sodium and salt intake and the best methods to assess them, highlighting the main findings of epidemiologic, laboratory and intervention studies and focusing on open issues such as the role of dietary salt in secondary causes of nephrolithiasis.

  18. High Temperature Fluoride Salt Test Loop

    Energy Technology Data Exchange (ETDEWEB)

    Aaron, Adam M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Cunningham, Richard Burns [Univ. of Tennessee, Knoxville, TN (United States); Fugate, David L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Holcomb, David Eugene [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Kisner, Roger A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Peretz, Fred J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Robb, Kevin R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Wilson, Dane F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Yoder, Jr, Graydon L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-12-01

    Effective high-temperature thermal energy exchange and delivery at temperatures over 600°C has the potential of significant impact by reducing both the capital and operating cost of energy conversion and transport systems. It is one of the key technologies necessary for efficient hydrogen production and could potentially enhance efficiencies of high-temperature solar systems. Today, there are no standard commercially available high-performance heat transfer fluids above 600°C. High pressures associated with water and gaseous coolants (such as helium) at elevated temperatures impose limiting design conditions for the materials in most energy systems. Liquid salts offer high-temperature capabilities at low vapor pressures, good heat transport properties, and reasonable costs and are therefore leading candidate fluids for next-generation energy production. Liquid-fluoride-salt-cooled, graphite-moderated reactors, referred to as Fluoride Salt Reactors (FHRs), are specifically designed to exploit the excellent heat transfer properties of liquid fluoride salts while maximizing their thermal efficiency and minimizing cost. The FHR s outstanding heat transfer properties, combined with its fully passive safety, make this reactor the most technologically desirable nuclear power reactor class for next-generation energy production. Multiple FHR designs are presently being considered. These range from the Pebble Bed Advanced High Temperature Reactor (PB-AHTR) [1] design originally developed by UC-Berkeley to the Small Advanced High-Temperature Reactor (SmAHTR) and the large scale FHR both being developed at ORNL [2]. The value of high-temperature, molten-salt-cooled reactors is also recognized internationally, and Czechoslovakia, France, India, and China all have salt-cooled reactor development under way. The liquid salt experiment presently being developed uses the PB-AHTR as its focus. One core design of the PB-AHTR features multiple 20 cm diameter, 3.2 m long fuel channels

  19. Salt screening and characterization of ciprofloxacin.

    Science.gov (United States)

    Zhang, Guoshun; Zhang, Li; Yang, Dezhi; Zhang, Na; He, Lan; Du, Guanhua; Lu, Yang

    2016-02-01

    With the aim of improving the solubility of ciprofloxacin, polybasic organic acids were utilized to react with ciprofloxacin in different stoichiometric proportions. The use of the solvent drop grinding (SDG) method, as well as the solvent evaporation method, resulted in the crystalline salts ciprofloxacin/fumaric acid (1:1, 2:1), ciprofloxacin/maleic acid (1:1) and ciprofloxacin/citric acid (2:1). The solubilities of these salts in pure water (pH 7.0) were determined using high-performance liquid chromatography (HPLC) at 310 K, with the salts showing considerably greater solubility than ciprofloxacin itself and, interestingly, ciprofloxacin/fumaric acid (2:1) being more soluble than ciprofloxacin/fumaric acid (1:1). Intrigued by this phenomenon, we undertook a comparison of the crystal structures of the salts: the three-dimensional sandwich-like structure observed in the 2:1 salt indicates that the preferred stacking may be a factor in increasing the solubility of ciprofloxacin.

  20. Wetting and evaporation of salt-water nanodroplets: A molecular dynamics investigation

    OpenAIRE

    Zhang, Jun; Borg, Matthew; Sefiane, Khellil; Reese, Jason

    2015-01-01

    We employ molecular dynamics simulations to study the wetting and evaporation of salt-water nanodroplets on platinum surfaces. Our results show that the contact angle of the droplets increases with the salt concentration. To verify this, a second simulation system of a thin salt-water film on a platinum surface is used to calculate the various surface tensions. We find that both the solid-liquid and liquid-vapor surface tensions increase with salt concentration and as a result these cause an ...

  1. Process for improving the energy density of feedstocks using formate salts

    Science.gov (United States)

    Wheeler, Marshall Clayton; van Heiningen, Adriaan R.P.; Case, Paige A.

    2015-09-01

    Methods of forming liquid hydrocarbons through thermal deoxygenation of cellulosic compounds are disclosed. Aspects cover methods including the steps of mixing a levulinic acid salt-containing feedstock with a formic acid salt, exposing the mixture to a high temperature condition to form hydrocarbon vapor, and condensing the hydrocarbon vapor to form liquid hydrocarbons, where both the formic acid salt and the levulinic acid salt-containing feedstock decompose at the high temperature condition and wherein one or more of the mixing, exposing, and condensing steps is carried out a pressure between about vacuum and about 10 bar.

  2. 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.

    Science.gov (United States)

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

    2016-12-09

    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.

  3. Scientific Opinion on the safety evaluation of the active substances citric acid (E330 and sodium hydrogen carbonate (E500ii, used as carbon dioxide generators, together with liquid absorbers cellulose and polyacrylic acid sodium salt crosslinked, in active food contact materials

    Directory of Open Access Journals (Sweden)

    EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF

    2013-04-01

    Full Text Available This scientific opinion of EFSA Panel on food contact materials, enzymes, flavourings and processing aids deals with the safety evaluation of the mixture of the active substances citric acid (E330, CAS No 77-92-9, FCM Substance No 139 and sodium hydrogen carbonate (E500ii, CAS No 144-55-8, FCM Substance No 21, which is intended to be used as a carbon dioxide generator in liquid absorbent pads in the packaging of fresh or frozen meat, poultry, fish, fruits and vegetables. Depending on absorption capacity needed, pure cellulose or a mixture of cellulose and polyacrylic acid sodium salt crosslinked may be used as absorber. The Panel noted that if the active substances are used not in direct contact with food, but are placed in a pad under conditions where its absorption capacity is not exceeded, then no migration is to be expected and therefore no exposure from the consumption of the packed food is expected. Therefore the CEF Panel concluded that the use of the mixture of the active substances citric acid (E330 and sodium hydrogen carbonate (E500ii, as carbon dioxide generator in liquid absorbent pads in the packaging of food such as fresh or frozen meat, poultry, fish, fruits and vegetables, does not raise a safety concern. The absorbent pads should be used only under conditions in which the liquid absorption capacity is not exceeded and direct contact between the substance and the food is excluded.

  4. Effect of glutathione L-cystein and L-djenkolic acid in the synthesis and mutagenicity of azide metabolite in Bacillus subtilis ATCC 6633 strain.

    Science.gov (United States)

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

    1999-10-01

    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.

  5. Influence of Salts on the Partitioning of 5-Hydroxymethylfurfural in Water/MIBK.

    Science.gov (United States)

    Mohammad, Sultan; Held, Christoph; Altuntepe, Emrah; Köse, Tülay; Sadowski, Gabriele

    2016-04-28

    This study investigates the influence of electrolytes on the performance of extracting 5-hydroxymethylfurfural (HMF) from aqueous media using methyl isobutyl ketone (MIBK). For that purpose, liquid-liquid phase equilibria (LLE) of quaternary systems containing HMF, water, MIBK and salts were measured at atmospheric pressure and 298.15 K. The salts under investigation were composed of one of the anions NO(3-), SO4(2-), Cl(-), or CH3COO(-) and of one of the alkali cations Li(+), Na(+), or K(+). On the basis of these LLE data, the partition coefficient of HMF between the aqueous and the MIBK phase KHMF was determined. It could be shown that KHMF significantly depends on the kind and concentration of the added salt. Weak electrolytes (e.g., sulfates, acetates) caused salting-out, whereas nitrates caused salting-in of HMF to the aqueous phase. Unexpectedly, LiCl caused salting-out at low LiCl concentrations and salting-in at LiCl concentrations higher than 3 mol/kgH2O. The model electrolyte perturbed-chain SAFT (ePC-SAFT) was used to predict the salt influence on the LLE in the quaternary systems water/MIBK/HMF/salt in good agreement with the experimental data. On the basis of ePC-SAFT, it could be concluded that the different salting-out/salting-in behavior of the various salts is mainly caused by their different tendency to form ion pairs in aqueous solutions.

  6. Vinyl azides derived from allenes: thermolysis leading to multisubstituted 1,4-pyrazines and Mn(III)-catalyzed photochemical reaction leading to pyrroles.

    Science.gov (United States)

    Sajna, K V; Kumara Swamy, K C

    2012-10-05

    Thermolysis of phosphorus-based vinyl azides under solvent- and catalyst-free conditions furnished a new route for 1,4-pyrazines. A simple one-pot, Mn(III)-catalyzed photochemical route has been developed for multisubstituted pyrroles starting from allenes and 1,3-dicarbonyls via in situ-generated vinyl azides. The utility of new phosphorus-based pyrroles is also demonstrated in the Horner reaction. The structures of key products are unequivocally confirmed by X-ray crystallography.

  7. Efficient synthesis of α,β-unsaturated alkylimines performed with allyl cations and azides: application to the synthesis of an ant venom alkaloid.

    Science.gov (United States)

    Hayashi, Kyohei; Tanimoto, Hiroki; Zhang, Huan; Morimoto, Tsumoru; Nishiyama, Yasuhiro; Kakiuchi, Kiyomi

    2012-11-16

    An efficient synthesis of α,β-unsaturated alkylimines at low temperature using azides has been developed. Carbocations generated from allyl alcohols helped achieve a rapid conversion under mild conditions with azides to afford reactive α,β-unsaturated imines. Hydroxy or alkoxy groups are essential for these transformations, and utilizing readily accessible allyl alcohols gave a wide extension of substrates. The efficiency of this novel method is demonstrated in the total synthesis of an iminium ant venom alkaloid.

  8. The orbital ground state of the azide-substrate complex of human heme oxygenase is an indicator of distal H-bonding: Implications for the enzyme mechanism‡

    Science.gov (United States)

    Ogura, Hiroshi; Evans, John P.; Peng, Dungeng; Satterlee, James D.; de Montellano, Paul R. Ortiz; Mar, Gerd N. La

    2009-01-01

    The active site electronic structure of the azide complex of substrate-bound human heme oxygenase-1, (hHO) has been investigated by 1H NMR spectroscopy to shed light on the orbital/spin ground state as an indicator of the unique distal pocket environment of the enzyme. 2D 1H NMR assignments of the substrate and substrate-contact residue signals reveal a pattern of substrate methyl contact shifts, that places the lone iron π-spin in the dxz orbital, rather than the dyz orbital found in the cyanide complex. Comparison of iron spin relaxivity, magnetic anisotropy and magnetic susceptibilities argues for a low-spin, (dxy)2(dyz,dxz)3, ground state in both azide and cyanide complexes. The switch from singly-occupied dyz for the cyanide to dxz for the azide complex of hHO is shown to be consistent with the orbital hole determined by the azide π-plane in the latter complex, which is ∼90° in-plane rotated from that of the imidazole π-plane. The induction of the altered orbital ground state in the azide relative to the cyanide hHO complex, as well as the mean low-field bias of methyl hyperfine shifts and their paramagnetic relaxivity relative to those in globins, indicate that azide exerts a stronger ligand field in hHO than in the globins, or that the distal H-bonding to azide is weaker in hHO than in globins. The Asp140 → Ala hHO mutant that abolishes activity retains the unusual WT azide complex spin/orbital ground state. The relevance of our findings for other HO complexes and the HO mechanism is discussed. PMID:19243105

  9. The orbital ground state of the azide-substrate complex of human heme oxygenase is an indicator of distal H-bonding: implications for the enzyme mechanism.

    Science.gov (United States)

    Ogura, Hiroshi; Evans, John P; Peng, Dungeng; Satterlee, James D; Ortiz de Montellano, Paul R; La Mar, Gerd N

    2009-04-14

    The active site electronic structure of the azide complex of substrate-bound human heme oxygenase 1 (hHO) has been investigated by (1)H NMR spectroscopy to shed light on the orbital/spin ground state as an indicator of the unique distal pocket environment of the enzyme. Two-dimensional (1)H NMR assignments of the substrate and substrate-contact residue signals reveal a pattern of substrate methyl contact shifts that places the lone iron pi-spin in the d(xz) orbital, rather than the d(yz) orbital found in the cyanide complex. Comparison of iron spin relaxivity, magnetic anisotropy, and magnetic susceptibilities argues for a low-spin, (d(xy))(2)(d(yz),d(xz))(3), ground state in both azide and cyanide complexes. The switch from singly occupied d(yz) for the cyanide to d(xz) for the azide complex of hHO is shown to be consistent with the orbital hole determined by the azide pi-plane in the latter complex, which is approximately 90 degrees in-plane rotated from that of the imidazole pi-plane. The induction of the altered orbital ground state in the azide relative to the cyanide hHO complex, as well as the mean low-field bias of methyl hyperfine shifts and their paramagnetic relaxivity relative to those in globins, indicates that azide exerts a stronger ligand field in hHO than in the globins, or that the distal H-bonding to azide is weaker in hHO than in globins. The Asp140 --> Ala hHO mutant that abolishes activity retains the unusual WT azide complex spin/orbital ground state. The relevance of our findings for other HO complexes and the HO mechanism is discussed.

  10. Combinations of fluorinated solvents with imide salts or methide salts for electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan; Lei, Norman; Guerrero-Zavala, Guillermo; Kwong, Kristie W

    2015-11-10

    Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include imide salts and/or methide salts as well as fluorinated solvents capable of maintaining single phase solutions at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and improve safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Linear and cyclic imide salts, such as LiN(SO.sub.2CF.sub.2CF.sub.3).sub.2, and LiN(SO.sub.2CF.sub.3).sub.2, as well as methide salts, such as LiC(SO.sub.2CF.sub.3).sub.3 and LiC(SO.sub.2CF.sub.2CF.sub.3).sub.3, may be used in these electrolytes. Fluorinated alkyl groups enhance solubility of these salts in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene, and/or one or more ionic liquids.

  11. Finding new equilibria: Directed synthesis of lanthanide materials via sodium azide mediated pathways

    Science.gov (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

  12. Crushed Salt Constitutive Model

    Energy Technology Data Exchange (ETDEWEB)

    Callahan, G.D.

    1999-02-01

    The constitutive model used to describe the deformation of crushed salt is presented in this report. Two mechanisms -- dislocation creep and grain boundary diffusional pressure solution -- are combined to form the basis for the constitutive model governing the deformation of crushed salt. The constitutive model is generalized to represent three-dimensional states of stress. Upon complete consolidation, the crushed-salt model reproduces the Multimechanism Deformation (M-D) model typically used for the Waste Isolation Pilot Plant (WIPP) host geological formation salt. New shear consolidation tests are combined with an existing database that includes hydrostatic consolidation and shear consolidation tests conducted on WIPP and southeastern New Mexico salt. Nonlinear least-squares model fitting to the database produced two sets of material parameter values for the model -- one for the shear consolidation tests and one for a combination of the shear and hydrostatic consolidation tests. Using the parameter values determined from the fitted database, the constitutive model is validated against constant strain-rate tests. Shaft seal problems are analyzed to demonstrate model-predicted consolidation of the shaft seal crushed-salt component. Based on the fitting statistics, the ability of the model to predict the test data, and the ability of the model to predict load paths and test data outside of the fitted database, the model appears to capture the creep consolidation behavior of crushed salt reasonably well.

  13. Salt-free vesicle-phases and their template effect

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Researches on the construction, structure, and formation of vesicles formed from surfactants have attracted great attention from colloid and interface chemists. The vesicles formed from salt-free cationic-anionic surfactant systems are very different from those with excess salts, having many particular properties. In this paper, we introduce the properties of vesicles prepared from salt-free surfactant systems, according to our own results, especially the vesicles formed from surfactants with divalent metal ions as counterions in aqueous solutions and room temperature ionic liquids. Moreover, the primary results on template effect of the metal-ligand vesicles have also been summarized.

  14. A Possible Regenerative, Molten-Salt, Thermoelectric Fuel Cell

    Science.gov (United States)

    Greenberg, Jacob; Thaller, Lawrence H.; Weber, Donald E.

    1964-01-01

    Molten or fused salts have been evaluated as possible thermoelectric materials because of the relatively good values of their figures of merit, their chemical stability, their long liquid range, and their ability to operate in conjunction with a nuclear reactor to produce heat. In general, molten salts are electrolytic conductors; therefore, there will be a transport of materials and subsequent decomposition with the passage of an electric current. It is possible nonetheless to overcome this disadvantage by using the decomposition products of the molten-salt electrolyte in a fuel cell. The combination of a thermoelectric converter and a fuel cell would lead to a regenerative system that may be useful.

  15. "Bis-Click" Ligation of DNA: Template-Controlled Assembly, Circularisation and Functionalisation with Bifunctional and Trifunctional Azides.

    Science.gov (United States)

    Yang, Haozhe; Seela, Frank

    2017-03-08

    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.

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

    Institute of Scientific and Technical Information of China (English)

    PENG Yuxing; DAI Hansong; LIU Jialin; CUN Linfeng

    1995-01-01

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

  17. Novel waste printed circuit board recycling process with molten salt.

    Science.gov (United States)

    Riedewald, Frank; Sousa-Gallagher, Maria

    2015-01-01

    The objective of the method was to prove the concept of a novel waste PCBs recycling process which uses inert, stable molten salts as the direct heat transfer fluid and, simultaneously, uses this molten salt to separate the metal products in either liquid (solder, zinc, tin, lead, etc.) or solid (copper, gold, steel, palladium, etc.) form at the operating temperatures of 450-470 °C. The PCB recovery reactor is essentially a U-shaped reactor with the molten salt providing a continuous fluid, allowing molten salt access from different depths for metal recovery. A laboratory scale batch reactor was constructed using 316L as suitable construction material. For safety reasons, the inert, stable LiCl-KCl molten salts were used as direct heat transfer fluid. Recovered materials were washed with hot water to remove residual salt before metal recovery assessment. The impact of this work was to show metal separation using molten salts in one single unit, by using this novel reactor methodology. •The reactor is a U-shaped reactor filled with a continuous liquid with a sloped bottom representing a novel reactor concept.•This method uses large PCB pieces instead of shredded PCBs as the reactor volume is 2.2 L.•The treated PCBs can be removed via leg B while the process is on-going.

  18. Gases in molten salts

    CERN Document Server

    Tomkins, RPT

    1991-01-01

    This volume contains tabulated collections and critical evaluations of original data for the solubility of gases in molten salts, gathered from chemical literature through to the end of 1989. Within the volume, material is arranged according to the individual gas. The gases include hydrogen halides, inert gases, oxygen, nitrogen, hydrogen, carbon dioxide, water vapor and halogens. The molten salts consist of single salts, binary mixtures and multicomponent systems. Included also, is a special section on the solubility of gases in molten silicate systems, focussing on slags and fluxes.

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

    KAUST Repository

    Mehenni, Hakim

    2011-11-01

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

  20. Photolysis and thermolysis of bis(imino)pyridine cobalt azides: C-H activation from putative cobalt nitrido complexes.

    Science.gov (United States)

    Hojilla Atienza, Crisita Carmen; Bowman, Amanda C; Lobkovsky, Emil; Chirik, Paul J

    2010-11-24

    A series of planar aryl-substituted bis(imino)pyridine cobalt azide complexes were prepared and evaluated as synthetic precursors for the corresponding cobalt nitrido compounds. Thermolysis or photolysis of two examples resulted in intramolecular C-H activation of the benzylic positions of the aryl substituents. For the mesityl-substituted compound, C-H activation by the putative nitride resulted in formation of a neutral imine ligand and modification of the chelate by hydrogen transfer to the imine carbon.

  1. Flow synthesis of organic azides and the multistep synthesis of imines and amines using a new monolithic triphenylphosphine reagent.

    Science.gov (United States)

    Smith, Catherine J; Smith, Christopher D; Nikbin, Nikzad; Ley, Steven V; Baxendale, Ian R

    2011-03-21

    Here we describe general flow processes for the synthesis of alkyl and aryl azides, and the development of a new monolithic triphenylphosphine reagent, which provides a convenient format for the use of this versatile reagent in flow. The utility of these new tools was demonstrated by their application to a flow Staudinger aza-Wittig reaction sequence. Finally, a multistep aza-Wittig, reduction and purification flow process was designed, allowing access to amine products in an automated fashion.

  2. Ribosome-Templated Azide-Alkyne Cycloadditions: Synthesis of Potent Macrolide Antibiotics by In Situ Click Chemistry.

    Science.gov (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

    2016-03-09

    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).

  3. Copper(I)-catalyzed cycloaddition of silver acetylides and azides: incorporation of volatile acetylenes into the triazole core.

    Science.gov (United States)

    Proietti Silvestri, Ilaria; Andemarian, Fikre; Khairallah, George N; Yap, Su Wan; Quach, Tim; Tsegay, Sammi; Williams, Craig M; O'Hair, Richard A J; Donnelly, Paul S; Williams, Spencer J

    2011-09-07

    Silver acetylides and organic azides react under copper(I) catalysis to afford 1,4-disubstituted 1,2,3-triazoles. Mechanistic studies implicate a process involving transmetallation to copper acetylides prior to cycloaddition. This work demonstrates that silver acetylides serve as suitable precursors for entry into copper-mediated coupling reactions. This methodology allows the incorporation of volatile and difficult-to-handle acetylenes into the triazole core.

  4. Copper-catalyzed tandem azide-alkyne cycloaddition, Ullmann type C-N coupling, and intramolecular direct arylation.

    Science.gov (United States)

    Pericherla, Kasiviswanadharaju; Jha, Amitabh; Khungar, Bharti; Kumar, Anil

    2013-09-06

    A ligand-free copper-catalyzed tandem azide-alkyne cycloaddition (CuAAC), Ullmann-type C-N coupling, and intramolecular direct arylation has been described. The designed strategy resulted in the synthesis of a novel trazole-fused azaheterocycle framework. The reaction gave good yields (59-77%) of 1,2,3-triazole-fused imidazo[1,2-a]pyridines in a single step.

  5. Efficient approach to 4-sulfonamidoquinolines via copper(I)-catalyzed cascade reaction of sulfonyl azides with alkynyl imines.

    Science.gov (United States)

    Cheng, Guolin; Cui, Xiuling

    2013-04-05

    A novel and efficient approach to 4-sulfonamidoquinolines via copper-catalyzed cascade reaction of sulfonyl azides with alkynyl imines has been developed in which a 1,3-dipole cycloaddition/ketenimine formation/6π-electrocyclization/[1,3]-H shift cascade reaction was involved. Various 4-sulfonamidoquinolines were afforded in up to 84% yield for 19 examples. This synthetic strategy features with atom economy, concise steps, easy operation, and mild reaction conditions.

  6. Copper(I)-catalyzed cycloaddition of bismuth(III) acetylides with organic azides: synthesis of stable triazole anion equivalents.

    Science.gov (United States)

    Worrell, Brady T; Ellery, Shelby P; Fokin, Valery V

    2013-12-02

    Fully loaded: Readily accessible and shelf-stable 1-bismuth(III) acetylides react rapidly and regiospecifically with organic azides in the presence of a copper(I) catalyst. The reaction tolerates many functional groups and gives excellent yields of the previously unreported 5-bismuth triazolides. This uniquely reactive intermediate is functionalized under mild reaction conditions to give fully substituted 1,2,3-triazoles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    Mandoli, Alessandro

    2016-09-05

    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.

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

    Directory of Open Access Journals (Sweden)

    Aldo I. Ortega-Arizmendi

    2013-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Alessandro Mandoli

    2016-09-01

    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.

  10. +Facile extraction of azide in sartan drugs using magnetized anion-exchange metal-organic frameworks prior to ion chromatography.

    Science.gov (United States)

    Zhang, Sainan; Han, Peipei; Xia, Yan

    2017-09-08

    Quaternary amine functionalized metal-organic framework MIL-101(Cr) (MIL-101(Cr)-NMe3) was prepared as the sorbent for the magnetic solid-phase extraction (MSPE) of azide from sartan drugs before ion chromatography determination. Magnetization of MIL-101-NMe3 were achieved concurrently by adding MIL-101-NMe3 and Fe3O4@SiO2 to the sample solution under ultrasonication. The prepared Fe3O4@SiO2/MIL-101-NMe3 gave the adsorption capacity of 37.5mgg(-1). The developed method had a detection limit of 0.24μgL(-1) and quantitation limit of 0.79μgL(-1) for azide. The relative standard deviations for the intra-day retention time and peak area were 0.52% and 0.36% (n=5), respectively. The developed method was successfully applied for the determination of azide in sartan drugs with the recoveries from 96.5% to 100.5%. Copyright © 2017. Published by Elsevier B.V.

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

    Science.gov (United States)

    Namvari, Mina; Namazi, Hassan

    2014-09-19

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

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

    Science.gov (United States)

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

    2016-03-14

    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.

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

    Science.gov (United States)

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

    2016-09-01

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

  14. SYNTHESIS AND CHARACTERIZATION OF TRIAZOLE CONTAINING LIQUID CRYSTALLINE POLYMERS THROUGH 1,3-DIPOLAR CYCLOADDITION POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

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

    2009-01-01

    Liquid crystalline polymers containing 1,2,3-triazole units as linking groups have been synthesized from the monomers containing triad ester diazide and flexible dialkyne ester by 1,3-cycloaddition reaction and were characterized. Click reaction of azide and alkyne functionals catalyzed by Cu(I) yielded target polyesters with 1,2,3-triazole groups.The structure of the polymer was confirmed by spectral techniques.GPC analysis reveals that the polymers have moderate molecular weight with narrow distributio...

  15. Salt Pomo: An Ethnogeography

    OpenAIRE

    McCarthy, Helen

    1986-01-01

    Recent research in Salt Pomo territory has produced new ethnogeographic data to add to the named villages identified in much earlier studies (Barrett 1904, 1908; Merriam MS, 1966, 1977). This new information is of particular interest because it significantly increases our general knowledge of the Salt Pomo, about whom little is otherwise known, and because it contributes to an understanding of their settlement pattern as well as to broader, regional land-use analyses. In addition, the study a...

  16. Hydrophilic block azidation of PCL-b-PEO block copolymers from epichlorohydrin.

    Science.gov (United States)

    Liu, Junjie; Gan, Zhihua

    2014-05-01

    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.

  17. Investigation on the production of copper nitride (copper azide) thin films and their nanostructures

    Science.gov (United States)

    Lotfi-Kaljahi, Amir; Savaloni, Hadi

    2013-01-01

    Copper thin films of 80-nm thickness were deposited on glass substrate using electron beam deposition at two different deposition angles of 0° and 40°, and they were post-annealed under flow of nitrogen at different temperatures. The structure of the films was analyzed using X-ray diffraction, atomic force microscope, and scanning electron microscope. Investigation on the copper nitride phase formation showed that this phase was not formed in the samples produced at 0°, while those prepared at oblique angle of 40° clearly showed the formation of copper azide phase. This is related to the porosity of the film structure, hence increased surface area for the reaction of nitrogen with copper atoms. Therefore, this is a simple method for preparation of copper nitride films that are not usually formed due to low reactivity of copper (as transition metal) with nitrogen. The results showed that the crystallite size (coherently diffracting domains), grain size, and surface roughness increase with annealing temperature.

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

    KAUST Repository

    Du, Naiying

    2011-03-11

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

  19. Tethering antimicrobial peptides onto chitosan: Optimization of azide-alkyne "click" reaction conditions.

    Science.gov (United States)

    Barbosa, Mariana; Vale, Nuno; Costa, Fabíola M T A; Martins, M Cristina L; Gomes, Paula

    2017-06-01

    Antimicrobial peptides (AMP) are promising alternatives to classical antibiotics, due to their high specificity and potency at low concentrations, and low propensity to elicit pathogen resistance. Immobilization of AMP onto biomaterials is an emergent field of research, towards creation of novel antimicrobial materials able to avoid formation of biofilms on the surfaces of medical devices. Herein, we report the chemical route towards one such material, where chitosan was used as biocompatible carrier for the covalent grafting of Dhvar-5, a well-known potent AMP, via the chemoselective ("click") Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The material's structure, as well as peptide loading, were confirmed by Fourier-transformed infra-red (FT-IR) and X-ray photoelectron (XPS) spectroscopies, and by Amino Acid Analysis (AAA), respectively. Results herein reported demonstrate that, with proper optimization, the "click" CuAAC is an attractive approach for the tethering of AMP onto chitosan, in order to create novel antimicrobial materials potentially valuable for biomedical applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Novel bipyridinium ionic liquids as liquid electrochromic devices.

    Science.gov (United States)

    Jordão, Noémi; Cabrita, Luis; Pina, Fernando; Branco, Luís C

    2014-04-01

    Novel mono and dialkylbipyridinium (viologens) cations combined with iodide, bromide, or bis(trifluoromethanesulfonyl)imide [NTf2] as anions were developed. Selective alkylation synthetic methodologies were optimized in order to obtain the desired salts in moderate to high yields and higher purities. All prepared mono- and dialkylbipyridinium salts were completely characterized by (1)H, (13)C, and (19)F NMR spectroscopy, Fourier-transform IR spectroscopy, and elemental analysis (in the case of NTf2 salts). Melting points, glass transition temperatures by differential scanning calorimetry (DSC) studies, and decomposition temperatures were also checked for different prepared organic salts. Viscosities at specific temperatures and activation energies were determined by rheological studies (including viscosity dependence with temperature in heating and cooling processes). Electrochemical studies based on cyclic voltammetry (CV), differential pulsed voltammetry (DPV), and square-wave voltammetry (SWV) were performed in order to determine the redox potential as well as evaluate reversibility behavior of the novel bipyridinium salts. As proof of concept, we developed a reversible liquid electrochromic device in the form of a U-tube system, the most promising dialkylbipyridinium-NTf2 ionic liquid being used as the electrochromic material and the room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)-imide [EMIM][NTf2], as a stable and efficient electrolyte. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Observation of inductive effects that cause a change in the rate-determining step for the conversion of rhenium azides to imido complexes.

    Science.gov (United States)

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

    2011-10-17

    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.

  2. CURRENT STATUS OF INSTRUMENTATION FOR A FLUORIDE SALT HEAT TRANSPORT DEMONSTRATION LOOP

    Energy Technology Data Exchange (ETDEWEB)

    Kisner, Roger A [ORNL; Holcomb, David Eugene [ORNL

    2010-01-01

    A small forced convection liquid fluoride salt loop is under construction at Oak Ridge National Laboratory (ORNL) to examine the heat transfer behavior of FLiNaK in a heated pebble bed. Loop operation serves several purposes: (1) reestablishing the infrastructure necessary for fluoride salt loop testing, (2) demonstrating a wireless heating technique for simulating pebble type fuel, (3) demonstration of the integration of silicon carbide (SiC) and metallic components into a liquid salt loop, and (4) demonstration of the functionality of distinctive instrumentation required for liquid fluoride salts. Loop operation requires measurement of a broad set of process variables including temperature, flow, pressure, and level. Coolant chemistry measurements (as a corrosion indicator) and component health monitoring are also important for longer-term operation. Two dominating factors in sensor and instrument selection are the high operating temperature of the salt and its chemical environment.

  3. Exploring photochemistry of p-bromophenylsulfonyl, p-tolylsulfonyl and methylsulfonyl azides by ultrafast UV-pump-IR-probe spectroscopy and computations.

    Science.gov (United States)

    Kuzmin, A V; Neumann, C; van Wilderen, L J G W; Shainyan, B A; Bredenbeck, J

    2016-03-28

    The photochemistry of p-bromophenylsulfonyl azide (BsN3), p-tolylsulfonyl azide (TsN3) and methylsulfonyl azide (MsN3) was studied by femtosecond time-resolved infrared spectroscopy with CH2Cl2 and CCl4 as solvents along with quantum chemical calculations. The photolysis of these azides after 267 nm light excitation leads to the population of each respective azide S1 excited state. Decay of the S1 excited state gives rise to singlet nitrene formation. In the case of BsN3, the decay was found to correlate with the formation of a pseudo-Curtius photoproduct (PCP) BrC6H4NSO2. Transient electronic ground states of the three azides on their way to singlet nitrenes and PCPs were shown by locating the corresponding transition states on the potential energy surfaces. The lifetime of singlet (1)(BsN) and (1)(TsN) nitrenes is τ(S) = ∼20 ps in CH2Cl2 and ∼700 ps in CCl4. Singlet (1)(MsN) was not detected. Due to fast intersystem crossing (ISC), singlet nitrenes are converted into the triplet spin isomers lying lower in energy, the formation time constants being equal to the corresponding singlet nitrene lifetime. The formation of (3)(MsN) was shown and the formation time constant in CH2Cl2 was found to be τ(ISC) = 34 ± 3 ps. Internal conversion of the S1 excited state to the ground state of the azide was low (Φ ≈ 0.15) for BsN3 and TsN3 and was not found in the case of MsN3.

  4. Temperature effects on geotechnical and hydraulic properties of bentonite hydrated with inorganic salt solutions

    DEFF Research Database (Denmark)

    Rashid, H. M. A.; Kawamoto, K.; Saito, T.

    2015-01-01

    © 2015, International Journal of GEOMATE. This study investigated the combined effect of temperature and single-species salt solutions on geotechnical properties (swell index and liquid limit) and hydraulic conductivity of bentonite applying different cation types, concentrations, and temperature...

  5. Salt treatment Fukushima

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, Stefan [NUKEM Technologies GmbH, Alzenau (Germany)

    2013-07-01

    The Task of NUKEM Technologies GmbH is to develop a technical solution for the treatment of salt containing effluents at Fukushima Daiichi. The target of the treatment is a solidified product suitable for the safe storage on site. Therefore, NUKEM investigated several technologies (direct cementation, drying and storage, drying and subsequent cementation) in order to find a fit for purpose solution. The following tasks have been considered: (a) Mechanical strength and homogeneity of the product; (b) Cost efficient solution (cost for the drying system vs. reduced amount of storage containers); (c) Proven technology; (d) On site storage. NUKEM made some practical test in parallel with different recipes. The aim was to embed as much as possible salt quantity into the cement matrix, but still meet the requested mechanical strength and required homogeneity. As a result NUKEM recommended to apply the following technologies (a) a drying system, to produce a dry salt product (b) a cementation facility, to generate a homogeneous salt/cement matrix (c) a filling station with attached CMS (Container measuring station) to fill the resulting cement/salt matrix into containers suitable for the storage at Fukushima Daiichi. (orig.)

  6. Cryogenic suction pump mechanism for combined salt-and frost exposure

    OpenAIRE

    2012-01-01

    Freezing of water can be explained by the thermodynamic properties of the water due to the influence of temperature, pressure and special effects such as surface tension and salt solution. Gibbs free energy curves for ice and pore liquid containing different concentrations of NaCl (0-6%) are presented. These curves explain the onset of freezing in pores when the energy level for solid ice and pore liquid containing salt are equal. Upon further cooling a nonequilibrium condition develops since...

  7. Photografting of perfluoroalkanes onto polyethylene surfaces via azide/nitrene chemistry

    Science.gov (United States)

    Siegmann, Konstantin; Inauen, Jan; Villamaina, Diego; Winkler, Martin

    2017-02-01

    The purpose of this study is to render polyethylene surfaces strongly and permanently hydrophobic. Polyethylene is a common plastic and, because of its inertness, difficult to graft. We chose polyethylene as example because of its ubiquity and model character. As graft chains linear perfluoroalkyl residues (-C4F9, -C6F13, -C8F17 and -C10F21) were chosen, and photografting was selected as grafting method. Photolytically generated nitrenes can insert into carbon-hydrogen bonds and are therefore suited for binding to polyethylene. Hydrophobic photo reactive surface modifiers based on azide/nitrene chemistry are designed, synthesized in high yield and characterized. Four new molecules are described. Water contact angles exceeding 110° were achieved on grafted polyethylene. One problem is to demonstrate that the photografted surface modifiers are bound covalently to the polyethylene. Abrasion tests show that all new molecules, when photografted to polyethylene, have a higher abrasion resistance than a polyethylene surface coated with a long-chain perfluoroalkane. Relative abrasion resitances of 1.4, 2.0, 2.1 and 2.5 compared to the fluoroalkane coating were obtained for the four compounds. An abrasion model using ice is developed. Although all four compounds have the same λmax of 266 nm in acetonitrile solution, their molar extincition coefficients increase from 1.6·104 to 2.2·104 with increasing length of the fluorotelomer chain. Exitonic coupling of the chromophores of the surface modifiers is observed for specific molecules in the neat state. A linear correlation of water contact angle with fluorine surface content, as measured by photoelectron spectroscopy, in grafted polyethylene surfaces is established.

  8. Theoretical considerations on the motion of salt and fresh water

    NARCIS (Netherlands)

    Schijf, J.B.; Schönfled, J.C.

    1953-01-01

    This paper gives a survey of the theoretical investigations in Holland on the motion of salt and fresh water in estuaries, locks, etc. The insight gained is set forth, and also questions yet unsolved are mentioned. First the long wave phenomena in the interface of two sharply separated liquids are t

  9. Electrochemical studies on plutonium in molten salts

    Energy Technology Data Exchange (ETDEWEB)

    Bourges, G. [CEA-Centre d' etudes de Valduc, 21 120 Is sur Tille (France)], E-mail: gilles.bourges@cea.fr; Lambertin, D.; Rochefort, S. [CEA-Centre d' etudes de Valduc, 21 120 Is sur Tille (France); Delpech, S.; Picard, G. [Laboratoire d' Electrochimie et de Chimie Analytique (UMR7575, CNRS), ENSCP, 11 rue Pierre et Marie Curie, 75231 Paris (France)

    2007-10-11

    Electrochemical studies on plutonium have been supporting the development of pyrochemical processes involving plutonium at CEA. The electrochemical properties of plutonium have been studied in molten salts - ternary eutectic mixture NaCl-KCl-BaCl{sub 2}, equimolar mixture NaCl-KCl and pure CaCl{sub 2} - and in liquid gallium at 1073 K. The formal, or apparent, standard potential of Pu(III)/Pu redox couple in eutectic mixture of NaCl-KCl-BaCl{sub 2} at 1073 K determined by potentiometry is equal to -2.56 V (versus Cl{sub 2}, 1 atm/Cl{sup -} reference electrode). In NaCl-KCl eutectic mixture and in pure CaCl{sub 2} the formal standard potentials deduced from cyclic voltammetry are respectively -2.54 V and -2.51 V. These potentials led to the calculation of the activity coefficients of Pu(III) in the molten salts. Chronoamperometry on plutonium in liquid gallium using molten chlorides - CaCl{sub 2} and equimolar NaCl/KCl - led to the determination of the activity coefficient of Pu in liquid Ga, log {gamma} = -7.3. This new data is a key parameter to assess the thermodynamic feasibility of a process using gallium as solvent metal. By comparing gallium with other solvent metals - cadmium, bismuth, aluminum - gallium appears to be, with aluminum, more favorable for the selectivity of the separation at 1073 K of plutonium from cerium. In fact, compared with a solid tungsten electrode, none of these solvent liquid metals is a real asset for the selectivity of the separation. The role of a solvent liquid metal is mainly to trap the elements.

  10. Core-clickable PEG-branch-azide bivalent-bottle-brush polymers by ROMP: grafting-through and clicking-to

    Science.gov (United States)

    Johnson, Jeremiah A.; Lu, Ying Y.; Burts, Alan O.; Lim, Yeon-Hee; Finn, M.G.; Koberstein, Jeffrey T.; Turro, Nicholas J.; Tirrell, David A.; Grubbs, Robert H.

    2010-01-01

    The combination of highly efficient polymerizations with modular “click” coupling reactions has enabled the synthesis of wide variety of novel nanoscopic structures. Here we demonstrate the facile synthesis of a new class of clickable, branched nanostructures, polyethylene glycol (PEG)-branch-azide bivalent-brush polymers, facilitated by “graft-through” ring-opening metathesis polymerization (ROMP) of a branched norbornene-PEG-chloride macromonomer followed by halide-azide exchange. The resulting bivalent-brush polymers possess azide groups at the core near a polynorbornene backbone with PEG chains extended into solution; the structure resembles a unimolecular micelle. We demonstrate copper-catalyzed azide-alkyne cycloaddition (CuAAC) “click-to” coupling of a photocleavable doxorubicin (DOX)-alkyne derivative to the azide core. The CuAAC coupling was quantitative across a wide range of nanoscopic sizes (~6 – ~50 nm); UV photolysis of the resulting DOX-loaded materials yielded free DOX that was therapeutically effective against human cancer cells. PMID:21142161

  11. The Pressure induced by salt crystallization in confinement

    Science.gov (United States)

    Desarnaud, J.; Bonn, D.; Shahidzadeh, N.

    2016-08-01

    Salt crystallization is a major cause of weathering of rocks, artworks and monuments. Damage can only occur if crystals continue to grow in confinement, i.e. within the pore space of these materials, thus generating mechanical stress. We report the direct measurement, at the microscale, of the force exerted by growing alkali halide salt crystals while visualizing their spontaneous nucleation and growth. The experiments reveal the crucial role of the wetting films between the growing crystal and the confining walls for the development of the pressure. Our results suggest that the measured force originates from repulsion between the similarly charged confining wall and the salt crystal separated by a ~1.5 nm liquid film. Indeed, if the walls are made hydrophobic, no film is observed and no repulsive forces are detected. We also show that the magnitude of the induced pressure is system specific explaining why different salts lead to different amounts of damage to porous materials.

  12. Salt Composition Derived from Veazey Composition by Thermodynamic Modeling and Predicted Composition of Drum Contents

    Energy Technology Data Exchange (ETDEWEB)

    Weisbrod, Kirk Ryan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Veirs, Douglas Kirk [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Funk, David John [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Clark, David Lewis [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-03-11

    This report describes the derivation of the salt composition from the Veazey salt stream analysis. It also provides an estimate of the proportions of the kitty litter, nitrate salt and neutralizer that was contained in drum 68660. While the actinide content of waste streams was judiciously followed in the 1980s in TA-55, no record of the salt composition could be found. Consequently, a salt waste stream produced from 1992 to 1994 and reported by Gerry Veazey provided the basis for this study. While chemical analysis of the waste stream was highly variable, an average analysis provided input to the Stream Analyzer software to calculate a composition for a concentrated solid nitrate salt and liquid waste stream. The calculation predicted the gas / condensed phase compositions as well as solid salt / saturated liquid compositions. The derived composition provides an estimate of the nitrate feedstream to WIPP for which kinetic measurements can be made. The ratio of salt to Swheat in drum 68660 contents was estimated through an overall mass balance on the parent and sibling drums. The RTR video provided independent confirmation concerning the volume of the mixture. The solid salt layer contains the majority of the salt at a ratio with Swheat that potentially could become exothermic.

  13. TETRAALKYLPHOSPHONIUM POLYOXOMETALATES AS NOVEL IONIC LIQUIDS.

    Energy Technology Data Exchange (ETDEWEB)

    DIETZ,M.L.; RICKERT, P.G.; ANTONIO, M.R.; FIRESTONE, M.A.; WISHART, J.F.; SZREDER, T.

    2007-11-30

    The pairing of a Lindqvist or Keggin polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation, [R{sub 3}R{prime}P]{sup +}, has been shown to yield an original family of ionic liquids (POM-ILs), among them salts liquid at or near ambient temperature. The physicochemical properties of several such 'inorganic liquids', in particular their thermal properties, suggests the possible application of these compounds as robust, thermally-stable solvents for liquid-liquid extraction. A preliminary evaluation of the potential of POM-ILs in this application is presented.

  14. Quantized friction across ionic liquid thin films

    Science.gov (United States)

    Smith, Alexander M.; Lovelock, Kevin R. J.; Gosvami, Nitya Nand; Welton, Tom; Perkin, Susan

    Ionic liquids, salts in the liquid state under ambient conditions, are of great interest as precision lubricants. Ionic liquids form layered structures at surfaces, yet it is not clear how this nano-structure relates to their lubrication properties. We measured the friction force between atomically smooth solid surfaces across ionic liquid films of controlled thickness in terms of the number of ion layers. Multiple friction-load regimes emerge, each corresponding to a different number of ion layers in the film. In contrast to molecular liquids, the friction coefficients differ for each layer due to their varying composition.

  15. Quantized friction across ionic liquid thin films.

    Science.gov (United States)

    Smith, Alexander M; Lovelock, Kevin R J; Gosvami, Nitya Nand; Welton, Tom; Perkin, Susan

    2013-10-07

    Ionic liquids - salts in the liquid state under ambient conditions - are of great interest as precision lubricants. Ionic liquids form layered structures at surfaces, yet it is not clear how this nano-structure relates to their lubrication properties. We measured the friction force between atomically smooth solid surfaces across ionic liquid films of controlled thickness in terms of the number of ion layers. Multiple friction-load regimes emerge, each corresponding to a different number of ion layers in the film. In contrast to molecular liquids, the friction coefficients differ for each layer due to their varying composition.

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

    Science.gov (United States)

    Shi, Yi; Cao, Xiaosong; Gao, Haifeng

    2016-02-01

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

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

    Directory of Open Access Journals (Sweden)

    Nur Syazwani Abd Rahman

    2016-01-01

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

  18. Non-Catalyzed Click Reactions of ADIBO Derivatives with 5-Methyluridine Azides and Conformational Study of the Resulting Triazoles

    Science.gov (United States)

    Smyslova, Petra; Popa, Igor; Lyčka, Antonín; Tejral, Gracian; Hlavac, Jan

    2015-01-01

    Copper-free click reactions between a dibenzoazocine derivative and azides derived from 5-methyluridine were investigated. The non-catalyzed reaction yielded both regioisomers in an approximately equivalent ratio. The NMR spectra of each regioisomer revealed conformational isomery. The ratio of isomers was dependent on the type of regioisomer and the type of solvent. The synthesis of various analogs, a detailed NMR study and computational modeling provided evidence that the isomery was dependent on the interaction of the azocine and pyrimidine parts. PMID:26673606

  19. Photoluminescence of urine salts

    Science.gov (United States)

    Bordun, O.; Drobchak, O.

    2008-02-01

    Photoexcitation and luminescence spectra of dried urine sample under laser excitation were studied. Luminescence spectra of urine are determined by luminescence of urea which is the main component of urine. The presence of pathological salts in urine leads to the long-wave shifting of maxima of luminescence and to the decreasing of luminescence intensity.

  20. Learning SaltStack

    CERN Document Server

    Myers, Colton

    2015-01-01

    If you are a system administrator who manages multiple servers, then you know how difficult it is to keep your infrastructure in line. If you've been searching for an easier way, this book is for you. No prior experience with SaltStack is required.

  1. What Are Bath Salts?

    Science.gov (United States)

    ... in Missouri. She won the 3rd place 2013 Addiction Science Award . Read More » 0 Comments Bath Salts: An Emerging Danger February 05, 2013 / Sara Bellum ... copy Listen Drug Facts ... Nicotine, & E-Cigarettes Brain and Addiction Drug Overdoses in Youth HIV/AIDS and Drug ...

  2. Effects of Solvent Composition on Liquid Range, Glass Transition, and Conductivity of Electrolytes of a (Li, Cs)PF6 Salt in EC-PC-EMC Solvents

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Michael S.; Li, Qiuyan; Li, Xing; Xu, Wu; Xu, Kang

    2017-05-10

    Electrolytes of 1 M LiPF6 (lithium hexafluorophosphate) and 0.05 M CsPF6 (cesium hexafluorophosphate) in EC-PC-EMC (ethylene carbonate-propylene carbonate-ethyl methyl carbonate) solvents of varying solvent compositions were studied for the effects of solvent composition on the lower limit of liquid range, viscosity (as reflected by the glass transition temperature), and electrolytic conductivity. In addition, a ternary phase diagram of EC-PC-EMC was constructed and crystallization temperatures of EC and EMC were calculated to assist the interpretation and understanding of the change of liquid range with solvent composition. A function based on Vogel-Fulcher-Tammann equation was fitted to the conductivity data in their entirety and plotted as conductivity surfaces in solvent composition space for more direct and clear comparisons and discussions. Changes of viscosity and dielectric constant of the solvents with their composition, in relation to those of the solvent components, were found to be underlying many of the processes studied.

  3. Carpinteria Salt Marsh Habitat Polygons

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — We identified five common habitat types in Carpinteria Salt Marsh: channels, pans (flats), marsh, salt flat and upland. We then drew polygons around each habitat...

  4. Hydrophobic Encapsulated Phosphonium Salts-Synthesis of Weakly Coordinating Cations and their Application in Wittig Reactions.

    Science.gov (United States)

    Moritz, Ralf; Wagner, Manfred; Schollmeyer, Dieter; Baumgarten, Martin; Müllen, Klaus

    2015-06-15

    Large and rigid tetraarylphosphonium tetrafluoroborate salts have been synthesized representing weakly coordinating cations with diameters of several nanometers. Divergent dendritic growth by means of thermal Diels-Alder cycloaddition was employed for the construction of the hydrophobic polyphenylene framework up to the third generation. X-ray crystal structure analysis of first-generation phosphonium tetrafluoroborate supported the rigidity of the non-collapsible shell around the phosphorus center and gave insight into solid-state packing and cation-anion distances. Copper(I)-catalyzed azide-alkyne ligation served as reliable method for the preparation of a first-generation triazolylphenyl hybrid phosphonium cation under mild reaction conditions. Furthermore, from the synthesis of triarylbenzylphosphonium bromides, Wittig precursors with unprecedented bulky substituents in the α-position were accessible. Employment of these precursors under Wittig conditions by treatment with base and subsequent reaction with aldehydes preferentially provided (Z)-olefins with bulky polyphenylene substituents.

  5. Computer modelling of the surface tension of the gas-liquid and liquid-liquid interface.

    Science.gov (United States)

    Ghoufi, Aziz; Malfreyt, Patrice; Tildesley, Dominic J

    2016-03-07

    This review presents the state of the art in molecular simulations of interfacial systems and of the calculation of the surface tension from the underlying intermolecular potential. We provide a short account of different methodological factors (size-effects, truncation procedures, long-range corrections and potential models) that can affect the results of the simulations. Accurate calculations are presented for the calculation of the surface tension as a function of the temperature, pressure and composition by considering the planar gas-liquid interface of a range of molecular fluids. In particular, we consider the challenging problems of reproducing the interfacial tension of salt solutions as a function of the salt molality; the simulations of spherical interfaces including the calculation of the sign and size of the Tolman length for a spherical droplet; the use of coarse-grained models in the calculation of the interfacial tension of liquid-liquid surfaces and the mesoscopic simulations of oil-water-surfactant interfacial systems.

  6. Thin aligned organic polymer films for liquid crystal devices

    CERN Document Server

    Foster, K E

    1997-01-01

    This project was designed to investigate the possibility of producing alignment layers for liquid crystal devices by cross-linking thin films containing anisotropic polymer bound chromophores via irradiation with polarised ultraviolet light. Photocross-linkable polymers find use in microelectronics, liquid crystal displays, printing and UV curable lacquers and inks; so there is an increasing incentive for the development of new varieties of photopolymers in general. The synthesis and characterisation of two new photopolymers that are suitable as potential alignment layers for liquid crystal devices are reported in this thesis. The first polymer contains the anthracene chromophore attached via a spacer unit to a methacrylate backbone and the second used a similarly attached aryl azide group. Copolymers of the new monomers with methyl methacrylate were investigated to establish reactivity ratios in order to understand composition drift during polymerisation.

  7. Salt ingestion caves.

    Directory of Open Access Journals (Sweden)

    Lundquist Charles A.

    2006-01-01

    Full Text Available Large vertebrate herbivores, when they find a salt-bearing layer of rock, say in a cliff face, can produce sizable voids where, overgenerations, they have removed and consumed salty rock. The cavities formed by this natural animal process constitute a uniqueclass of caves that can be called salt ingestion caves. Several examples of such caves are described in various publications. Anexample in Mississippi U.S.A., Rock House Cave, was visited by the authors in 2000. It seems to have been formed by deer orbison. Perhaps the most spectacular example is Kitum Cave in Kenya. This cave has been excavated to a length over 100 metersby elephants. An ancient example is La Cueva del Milodon in Chile, which is reported to have been excavated by the now extinctmilodon, a giant ground sloth. Still other possible examples can be cited. This class of caves deserves a careful definition. First, thecavity in rock should meet the size and other conventions of the locally accepted definition of a cave. Of course this requirement differsin detail from country to country, particularly in the matter of size. The intent is to respect the local conventions. The characteristicthat human entry is possible is judged to be a crucial property of any recognized cave definition. Second, the cavity should besignificantly the result of vertebrate animal consumption of salt-bearing rock. The defining process is that rock removed to form thecave is carried away in the digestive track of an animal. While sodium salts are expected to be the norm, other salts for which thereis animal hunger are acceptable. Also some other speleogenesis process, such as solution, should not be excluded as long as it issecondary in formation of a cave in question.

  8. Hydrothermal synthesis, characterization, and thermal properties of alumino silicate azide sodalite, Na8[AlSiO4]6(N3)2

    Science.gov (United States)

    Borhade, A. V.; Wakchaure, S. G.; Dholi, A. G.; Kshirsagar, T. A.

    2017-07-01

    First time we report the synthesis, structural characterization and thermal behavior of an unusual N3 - containing alumino-silicate sodalite mineral. Azide sodalite, Na8[AlSiO4]6(N3)2 has been synthesized under hydrothermal conditions at 433 K in steel lined Teflon autoclave. The structural and microstructural properties of azide sodalite mineral was characterized by various methods including FT-IR, XRD, SEM, TGA, and MAS NMR. Crystal structure have been refined by Rietveld method in P\\bar 43n space group, indicating that the N3 - sodalite has cubic in lattice. High temperature study was carried out to see the effect of thermal expansion on cell dimension ( a o) of azide sodalite. Thermal behavior of sodalite was also assessed by thermogravimetric method.

  9. Synthesis of multi-hydroxyl and sulfonyl dual-functionalized room temperature ionic liquids

    Institute of Scientific and Technical Information of China (English)

    Guo Yang Zhu; Rong Wang; Guo Hua Liu; Li Qun Xu; Bei Zhang; Xia Qin Wu

    2007-01-01

    Starting from the hydroxylamine (dimethyl amino ethanol, triethanolamine) and 1,3-propane sultone, a series of hydroxyl and sulfonyl dual-functionalized zwitterionic salts and corresponding acidic room temperature ionic liquids have been synthesized.The hydroxyl groups of the synthesized substances were confirmed by the 1H NMR measurement.These zwitterionic salts and ionic liquids may be used for synthesizing other functionalized ionic liquids or ionic liquid-polymer (polyelectrolyte).

  10. Physicochemical basis for the inhibitory effects of organic and inorganic salts on the growth of Pectobacterium carotovorum subsp. carotovorum and Pectobacterium atrosepticum.

    Science.gov (United States)

    Yaganza, Elian-Simplice; Tweddell, Russell J; Arul, Joseph

    2009-03-01

    Twenty-one salts were tested for their effects on the growth of Pectobacterium carotovorum subsp. carotovorum and Pectobacterium atrosepticum. In liquid medium, 11 salts (0.2 M) exhibited strong inhibition of bacterial growth. The inhibitory action of salts relates to the water-ionizing capacity and the lipophilicity of their constituent ions.

  11. Physicochemical Basis for the Inhibitory Effects of Organic and Inorganic Salts on the Growth of Pectobacterium carotovorum subsp. carotovorum and Pectobacterium atrosepticum▿

    OpenAIRE

    Yaganza, Elian-Simplice; Tweddell, Russell J.; Arul, Joseph

    2008-01-01

    Twenty-one salts were tested for their effects on the growth of Pectobacterium carotovorum subsp. carotovorum and Pectobacterium atrosepticum. In liquid medium, 11 salts (0.2 M) exhibited strong inhibition of bacterial growth. The inhibitory action of salts relates to the water-ionizing capacity and the lipophilicity of their constituent ions.

  12. 反相高效液相色谱柱前在线衍生法测定氨基葡萄糖硫酸钾盐的含量%Determination of N-Sulfo-glucosamine potassium salt by reversed-phase high performance liquid chromatography with online pre-column derivation

    Institute of Scientific and Technical Information of China (English)

    王德伟; 叶礼红; 杨祖伟

    2015-01-01

    Objective To establish a method for the determination of N-Sulfo-glucosamine potassium salt by reversed-phase high performance liquid chromatography (RP-HPLC) with online pre-column derivation in health food. Methods Online pre-column derivation were reacted by using phthalic dicarboxaldehyde (OPA) derived reagents and amino of N-Sulfo-glucosamine potassium salt. The products were separated by C18 column with 0.68%acetic acid buffer:methanol (V:V=82:18) as mobile phase, the flow rate of 1.0 mL/min, and detection wavelength of 340 nm. Results D-glucosamine hydrochloride concentration had a good linearity in the range of 0.052~1.045 mg/mL. The average recovery rate was 97.5%, RSD%=1.2 (n=9). Conclusion The method is high, simple and accurate, and can be used to determine the content of N-Sulfo-glucosamine potassium salt in pharmaceutics and health food.%目的:建立一种反相高效液相色谱柱前在线衍生法测定保健品中氨基葡萄糖硫酸钾盐的含量。方法利用邻苯二甲醛衍生试剂与氨基葡萄糖硫酸钾盐中的氨基进行柱前在线衍生化反应,采用 C18色谱柱分离,以0.68%醋酸缓冲液:甲醇(V:V=82:18)为流动相,流速1.0 mL/min,检测波长340 nm。结果 D-盐酸氨基葡萄糖浓度在0.052~1.045 mg/mL之间呈现良好的线性,平均回收率为97.5%, RSD%=1.2(n=9)。结论该方法推广性高、简便、准确,可用于制剂及保健品中氨基葡萄糖硫酸钾盐的含量测定。

  13. Salt fluoridation and oral health

    OpenAIRE

    Thomas M. Marthaler

    2013-01-01

    The aim of this paper is to make known the potential of fluoridated salt in community oral health programs, particularly in South Eastern Europe. Since 1922, the addition of iodine to salt has been successful in Switzerland. Goiter is virtually extinct. By 1945, the cariesprotective effect of fluorides was well established. Based on the success of water fluoridation, a gynecologist started adding of fluoride to salt. The sale of fluoridated salt began in 1956 in the Swiss Canton of Zurich,...

  14. Lowering Salt in Your Diet

    Science.gov (United States)

    ... sodium, per serving. back to top Q. Are salt substitutes safe? A. Many salt substitutes contain potassium chloride and can be used by ... heart disease. Check with your doctor before using salt substitutes. back to top Q. What is FDA's role ...

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

    Directory of Open Access Journals (Sweden)

    Ricardo Montalván

    1998-03-01

    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.

  16. Bile salts of the coelacanth, Latimeria chalumnae.

    Science.gov (United States)

    Kihira, K; Akashi, Y; Kuroki, S; Yanagisawa, J; Nakayama, F; Hoshita, T

    1984-12-01

    Bile salts of the coelacanth, Latimeria chalumnae, Smith, have been analyzed and shown to have three bile alcohols, latimerol, 5 alpha-cyprinol, and 5 alpha-cholestane-3 beta, 7 alpha,-12 alpha,25,26-pentol, two C24 bile acids, chenodeoxycholic acid and cholic acid, one C26 bile acid, probably 3 beta, 7 alpha, 12 alpha-trihydroxy-27-nor-5 alpha-cholestan-26-oic acid, and two C27 bile acids, 3 alpha,7 alpha,12 alpha-trihydroxy-5 alpha-cholestan-26-oic acid and 3 beta,7 alpha,12 alpha-trihydroxy-5 alpha-cholestan-26-oic acid as determined by gas-liquid chromatography and gas-liquid chromatography-mass spectrometry.

  17. Emissions from energetic material waste during the Molten Salt Destruction process

    Energy Technology Data Exchange (ETDEWEB)

    Watkins, B.E.; Upadhye, R.S.; Pruneda, C.O.; Brummond, W.A.

    1994-07-05

    The Molten Salt Destruction (MSD) process is an alternative to open burn/open detonation for destroying energetic materials; MSD has inherently low gaseous emissions, and the salt bath can scrub both acidic gases and particulates. It was demonstrated that high explosives and a liquid propellant can be safely and completely destroyed using MSD. Gaseous emissions of NOx and CO are very low. Nitrate builds up in the salt bath when nitrate-rich materials are destroyed, but addition fuel reduces the nitrate to NO. A program has been begun to add catalytic materials to the bed to further reduce emissions; a small molten salt bath has been constructed for chemical kinetic studies.

  18. Salt supply to and significance of asymmetric salt diapirs

    DEFF Research Database (Denmark)

    Koyi, H.; Burliga, S.; Chemia, Zurab

    2012-01-01

    Salt diapirs can be asymmetric both internally and externally reflecting their evolution history. As such, this asymmetry bear a significant amount of information about the differential loading (± lateral forces) and in turn the salt supply that have shaped the diapir. In two dimensions......, In this study we compare results of analogue and numerical models of diapirs with two natural salt diapris (Klodawa and Gorleben diapirs) to explain their salt supply and asymmetric evolution. In a NW-SE section, the Gorleben salt diapir possesses an asymmetric external geometry represented by a large...... southeastern overhang due to salt extrusion during Middle Cretaceous followed by its burial in Tertiary. This external asymmetry is also reflected in the internal configuration of the diapir which shows different rates of salt flow on the two halves of the structure. The asymmetric external and internal...

  19. Salt supply to and significance of asymmetric salt diapirs

    DEFF Research Database (Denmark)

    Koyi, H.; Burliga, S.; Chemia, Zurab

    2012-01-01

    Salt diapirs can be asymmetric both internally and externally reflecting their evolution history. As such, this asymmetry bear a significant amount of information about the differential loading (± lateral forces) and in turn the salt supply that have shaped the diapir. In two dimensions......, In this study we compare results of analogue and numerical models of diapirs with two natural salt diapris (Klodawa and Gorleben diapirs) to explain their salt supply and asymmetric evolution. In a NW-SE section, the Gorleben salt diapir possesses an asymmetric external geometry represented by a large...... southeastern overhang due to salt extrusion during Middle Cretaceous followed by its burial in Tertiary. This external asymmetry is also reflected in the internal configuration of the diapir which shows different rates of salt flow on the two halves of the structure. The asymmetric external and internal...

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

    Institute of Scientific and Technical Information of China (English)

    高占先; 冯立春; 张小航; 莫自如

    2001-01-01

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