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Sample records for bf4 clo4 pf6

  1. Thermopower studies of a series of salts of tetramethyltetrathiafulvalene [(TMTTF)2X, X=Br, ClO4, NO3, SCN, BF4, AsF6, and PF6

    DEFF Research Database (Denmark)

    Mortensen, Kell; Conwell, E. M.; Fabre, J. M.

    1983-01-01

    Thermoelectric power measurements on a group of tetramethyltetrathiafulvalene (TMTTF)2X salts show a wide variety of behavior. In the range of temperatures 300≥T≳100 K several of the salts (X=BF4, ClO4, NO3, SCN) have a constant thermopower S≃35 μV/K, while the PF6 and AsF6 salts have S∝1 / T, and...... the Br salt has S increasing with T. Below ∼100 K, S shows a steep increase or decrease with decreasing temperature for each salt which, with the exception of the SCN salt, is not associated with a phase transition. These materials had been identified as semiconductors below the maximum in...

  2. The Properties of Binary Composite Ionic Liquids BMimBF4 and BMimPF6 Mixtures%BMimBF_4和BMimPF_6二元复合离子液体的特性

    Institute of Scientific and Technical Information of China (English)

    张冰; 陈松; 陈亮

    2012-01-01

    The kinematic viscosity, electrochemical window and electric conductivity of BMimBF4and BMimPF6 and their binary composite ionic liquids mixtures were studied. The results indicated that, physical and chemical properties of binary composite ionic liquids mixtures were changed by way of simply regulating volume of BMimBF4 and BMimPF6, which brought designing ionic liquids into full play and opened a new way for the application of "green solvent" - ionic liauids.%研究了BMimBF4、BMimPF6及其二者不同体积比复合离子液体的运动粘度、电化学窗口及电导率。结果表明,通过简单地调节BMimBF4和BMimPF6的复合体积比,可以改变BMimBF4和BMimPF6二元复合离子液体的物理化学性质,充分发挥离子液体的"可设计"性,为"绿色溶剂"离子液体的应用开辟了新的道路。

  3. Comparative X ray diffuse scattering studies of some superconducting and non superconducting 1 : 2 salts (TMTSF)2X and (TMTTF)2X; with x = PF6, AsF6, ClO4, NO3

    International Nuclear Information System (INIS)

    X-ray diffuse scattering experiments performed on the highly conducting (TMTSF)2X compounds (X = PF6, AsF6, ClO4, NO3) reveal no charge density wave instabilities, whether they display superconducting properties or not. Instead, another type of phase transition, not observed for the superconducting members (PF6, AsF6, ClO4), takes place in the non-superconducting (TMTSF)2NO3, and involves an ordering of the counter ions, which doubles the lattice constant in chain direction. Similar experiments performed on the less conducting (TMTSF)2X compounds (X = ClO4, PF6), which do not present a superconducting state, either reveal the ordering transition of the counter ion (ClO4) or the quasi 1-D 2ksub(F) scattering characteristic of a charge density wave instability (PF6). Consequences on the dimensionality of the Fermi surface and on the superconducting instability are discussed. (orig.)

  4. Organic metal (EDO-TTF2PF6 with multi-instability

    Directory of Open Access Journals (Sweden)

    Hideki Yamochi and Shin-ya Koshihara

    2009-01-01

    Full Text Available The multi-instability of the electronic structure of (EDO-TTF2PF6, where EDO-TTF means ethylene-dioxytetrathiafulvalene, is reviewed. This complex showed the metal–insulator transition at 280 K associated with distinct molecular deformations. The mechanism is interpreted as the cooperation of Peierls transition, charge ordering, and the order–disorder transition of the countercomponent. The charge ordering pattern in the low-temperature phase is of the novel [0, 0, 1, 1] type. The sensitivity of the electronic state to external perturbations is demonstrated applying not only static but also instantaneous stimuli. In the latter case, the photo-induced phase transition is ultrafast and highly efficient. One photon causes the transition of several hundreds of donor molecules in the low-temperature phase to relax into a highly conducting metastable state within about 1.5 ps. In the early stage of the transient state, the charge ordering of the [1, 0, 1, 0] type occurs. As for the chemical modifications of this material, the partial deuteration of this complex increases the metal–insulator transition temperature. The introduction of a methyl group greatly modulates the electronic structure of the complex, i.e. (methyl-EDO-TTF2X (X=BF4, ClO4 shows a two-dimensional electronic structure. The working hypotheses for developing the systems with multi-instability are described.

  5. Dehumidification performance of [EMIM]BF4

    International Nuclear Information System (INIS)

    Some ionic liquids have dehumidification capacity and are non-corrosive to metals. Based on the Finite Difference Method, the heat and moisture transfer model of the counter-flow dehumidifier was established. Using this model, the dehumidification capacity of one kind of ionic liquids 1-Ethyl-3-methylimidazolium Tetrafluoroborate ([EMIM]BF4) and traditional desiccant lithium bromide (LiBr) was compared in equivalent conditions. The results show that the dehumidification performances of the two solutions both improve with the increase of air flow rate, solution flow rate and air humidity. Even though the dehumidification rate of [EMIM]BF4 is a little lower than that of LiBr, such difference could be reduced by increasing the mass concentration of [EMIM]BF4. Meanwhile, compared with traditional desiccants, [EMIM]BF4 solution has significantly lower corrosion to metals and does not crystallize at high mass concentration, which render it a possible substitute of existed desiccants in liquid desiccant air conditioning systems. - Highlights: → The paper researched on using [EMIM]BF4 solution as desiccant in the liquid desiccant air conditioning system by simulation. → By comparing the dehumidification performance of [EMIM]BF4 solution with traditional desiccant LiBr solution, it confirms the feasibility of using [EMIM]BF4 as desiccant. → [EMIM]BF4 solution has significantly lower corrosion of metals and does not crystallize at high mass concentration, which make it a possible substitute of existed desiccants.

  6. Transformations of Organic Molecules with F-TEDA-BF4 in Ionic Liquid Media

    Directory of Open Access Journals (Sweden)

    Stojan Stavber

    2009-07-01

    Full Text Available The transformations of organic molecules with F-TEDA-BF4 (1 were investigated in the hydrophilic ionic liquid (IL 1-butyl-3-methyl-imidazolium tetrafluoroborate ([bmim][BF4], 2 and the hydrophobic IL 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF6], 3. The range of substrates included alkyl substituted phenols 4a-c, 9, 13, 1,1-diphenylethene (15, alkyl aryl ketones 19-22, aldehydes 23-25 and methoxy-substituted benzene derivatives 26-30. The evaluation of the outcome of reactions performed in IL media in comparison to those of the corresponding reactions in conventional organic solvents revealed that the transformations in IL are less efficient and selective. The effect of the presence of a nucleophile (MeOH, H2O, MeCN on the course of reaction was also studied.

  7. Densities and viscosities for ionic liquids mixtures containing [eOHmim][BF4], [bmim][BF4] and [bpy][BF4

    International Nuclear Information System (INIS)

    Highlights: • Targets of this research are ILs mixtures. • Densities and viscosities were measured for three ILs mixtures. • Excess molar properties were deduced from the experiments. • Viscosities were discussed by the ideal Grunberg and Nissan mixing law. - Abstract: Densities and viscosities of binary ionic liquids mixtures, 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate ([eOHmim][BF4]) + 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate ([eOHmim][BF4]) + N-butylpyridinium tetrafluoroborate ([bpy][BF4]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) + N-butylpyridinium tetrafluoroborate ([bpy][BF4]) were measured over the entire mole fraction from T = (298.15 to 343.15) K. The excess molar volumes were calculated and correlated by Redlich–Kiser polynomial expansions. The viscosities for pure ionic liquids were analyzed by means of the Vogel–Tammann–Fulcher equation and ideal mixing rules were applied for the ILs mixtures

  8. Thermal stability of LiPF 6 salt and Li-ion battery electrolytes containing LiPF 6

    Science.gov (United States)

    Yang, Hui; Zhuang, Guorong V.; Ross, Philip N.

    The thermal stability of the neat lithium hexafluorophosphate (LiPF 6) salt and of 1 molal (m) solutions of LiPF 6 in prototypical Li-ion battery solvents was studied with thermogravimetric analysis (TGA) and on-line Fourier transform infrared (FTIR). Pure LiPF 6 salt is thermally stable up to 107 °C in a dry inert atmosphere, and its decomposition path is a simple dissociation producing lithium fluoride (LiF) as solid and PF 5 as gaseous products. In the presence of water (300 ppm) in the carrier gas, its decomposition onset temperature is lowered as a result of direct thermal reaction between LiPF 6 and water vapor to form phosphorous oxyfluoride (POF 3) and hydrofluoric acid (HF). No new products were observed in 1 m solutions of LiPF 6 in ethylene carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) by on-line TGA-FTIR analysis. The storage of the same solutions in sealed containers at 85 °C for 300-420 h did not produce any significant quantity of new products as well. In particular, no alkylflurophosphates were found in the solutions after storage at elevated temperature. In the absence of either an impurity like alcohol or cathode active material that may (or may not) act as a catalyst, there is no evidence of thermally induced reaction between LiPF 6 and the prototypical Li-ion battery solvents EC, PC, DMC or EMC.

  9. Proton irradiation defects in (fluoranthene)2PF6

    International Nuclear Information System (INIS)

    Electron spin resonance and electron-proton double resonance (Overhauser shift method) are used for the comparison of proton radiation damaged and as-grown (fluoranthene)2PF6 single crystals. Chemical modification and various consequences of the nonuniform distribution of radiation induced defects in this quasi-one-dimensional organic conductor with defect dependent Peierls transition are worked out

  10. Optimization of a NH4PF6-enhanced, non-organic solvent, dual microextraction method for determination of phthalate metabolites in urine by high performance liquid chromatography.

    Science.gov (United States)

    Wu, Jia; Ye, Zhihan; Li, Xiaolong; Wang, Xuedong; Luo, Fangjun; Sheng, Bo; Li, Yiwei; Lyu, Jianxin

    2016-03-01

    In conventional ionic liquid-based dispersive liquid-liquid microextraction (IL-DLLME) procedures, most of the IL disperser remains in the aqueous phase resulting in low recovery for moderately and weakly polar analytes due to the "carry-over effect". Herein, we successfully developed a "NH4PF6-enhanced, non-organic solvent, dual microextraction" method (ANSDM) for pretreatment of phthalate (PAE) metabolites with weak to moderate polarity. This method utilized in situ reaction of NH4PF6 as an ion-exchange reagent and disperser to realize two microextractions after using [C8MIM]PF6 as an extraction solvent and [C4MIM]BF4 as a disperser for conventional DLLME. Single-factor experiments, a two-level full factorial experimental design and central composite design were applied for optimizing operational parameters using 3D response surfaces and contour lines. Under optimized conditions, the newly developed method provided high extraction recoveries (93.8-99.1%) and low LODs (ca. 0.3μgL(-1)) for three phthalate metabolites in human urine. The primary advantages of the ANSDM method include: (1) integration of in situ reaction and conventional DLLME techniques to effectively extract both weak and moderately polar pollutants simultaneously; (2) non-organic solvent use in the microextraction procedure making the process safer and more environmental friendly; and (3) a time-saving, simple operation that is fully compatibility with HPLC analysis. To the best of our knowledge, our group is the first to develop the "non-organic solvent, dual microextraction" method and it has great potential as a sample pre-treatment technique for organic pollutants with weak to moderate polarity in biological and environmental matrices. PMID:26852090

  11. Study of the Ion Channel Behavior of Didodecyldimethylammonium Bromide Formed Bilayer Lipid Membrane Stimulated by PF-6

    Institute of Scientific and Technical Information of China (English)

    TONG,Yue-Hong; HAN,Xiao-Jun; WANG,Er-Kang

    2003-01-01

    Bilayer lipid membranes ( BLM ) formed from didodecyldimethylammonium bromide were made on the freshly exposed surface ofa glassy carbon (GC) ani were demonstrated by the ac impedance spectroscopy. The ion channels of membrane properties induced by PF6- were studied by the cyclic voltammetric methods.Experimental results indicated that the ion channel of BLM was open in the presence of the PF6- due to the interaction of PF6- with the BLM, while it was switched offin the absence of PF6-. Because the ion channel behavior was affected by the concentration of PF6-,a sensor for PF6- can be developed.

  12. Structure, phase transitions, dielectric and spectroscopic studies of the 2-aminopyrimidinium salts: [(2-NH 2C 4N 2H 3) 2H][ClO 4] and [2-NH 2C 4N 2H 4][BF 4

    Science.gov (United States)

    Czupiński, O.; Wojtaś, M.; Ciunik, Z.; Jakubas, R.

    2006-01-01

    Crystal structure of the 2-aminopyrimidinium derivatives: [(2-NH 2C 4N 2H 3) 2H][ClO 4] (I) and [2-NH 2C 4N 2H 4][BF 4] (II) has been determined at 100 K (I) and 293 K (II) by means of single crystal X-ray diffraction as monoclinic space group, P2/c and P2/n, respectively. The asymmetric part of the unit cell of (I) contains two symmetry independent 2-aminopyrimidine forming one dimeric cation and one disordered perchlorate anion. The structure of (II) consists of 2-aminopyrimidinium cation, [2-NH 2C 4N 2H 4] +, protonated at a pyrimidine ring-N atom and [BF 4] - anion. Differential scanning calorimetry (DSC) on perchlorate derivative ( 1:1), [2-NH 2C 4N 2H 3][ClO 4] (III)—being isomorphic to tetrafluoroborate one (I) at room temperature, reveals two phase transitions of first order: at 250/275 K and 390/410 K (cooling-heating, respectively), whereas the analog (II) only one transition at high temperatures—343/385 K. The dielectric studies in the frequency range 75 kHz - 10 MHz disclose relaxation process at high temperatures in salt (I). Infrared spectra of polycrystalline [2-NH 2C 4N 2H 4][BF 4] have been studied in the temperature range 300-420 K. Substantial changes in the temperature evolution of frequencies of internal modes of the 2-aminopyrimidinium cations and [BF 4] - anions near 390 K are due to the variations in the motion of both moieties and hydrogen bond configuration. The experimental studies indicate that all phase transitions taking place in studied 2-aminopyrimidinium derivatives are classified as an order-disorder.

  13. Thermal stability of LiPF6/EC+DMC+EMC electrolyte for lithium ion batteries

    Institute of Scientific and Technical Information of China (English)

    WANG Qingsong; SUN Jinhua; CHEN Chunhua

    2006-01-01

    The thermal stability of lithium-ion battery electrolyte could substantially affect the safety of lithium-ion battery. In order to disclose the thermal stability of 1.0 mol·L-1 LiPF6/ethylene carbonate (EC)+dimethyl carbonate (DMC)+ethylmethyl carbonate (EMC) electrolyte, a micro calorimeter C80 micro calorimeter was used in this paper. The electrolyte samples were heated in argon atmosphere, and the heat flow and pressure performances were detected. It is found that LiPF6 influences the thermal behavior remarkably, with more heat generation and lower onset temperature. LiPF6/EC shows an exothermic peak at 212 ℃ with a heat of reaction -355.4J·g-1.DMC based LiPF6 solution shows two endothermic peak temperatures at 68.5 and 187 ℃ in argon filled vessel at elevated temperature. EMC based LiPF 6 solution shows two endothermic peak temperatures at 191 and 258 ℃ in argon filled vessel.1.0mol·L-1LiPF6/EC+DMC+ EMC electrolyte shows an endothermic and exothermic process one after the other at elevated temperature. By comparing with the thermal behavior of single solvent based LiPF6 solution, it can be speculated that LiPF6 may react with EC, DMC and EMC separately in 1.0 mol·L-1LiPF6/EC+DMC+EMC electrolyte, but the exothermic peak is lower than that of 1.0 mol·L-1LiPF6/EC solution. Furthermore, The 1.0 mol·L-1 LiPF6 /EC+DMC+EMC electrolyte decomposition reaction order was calculated based on the pressure data, its value is n =1.83, and the pressure rate constants kp=6.49×10-2k Pa·-0.83·min-1 .

  14. Cooperative phenomena in (TMTSF)2ClO4 : an NMR evidence

    OpenAIRE

    Bourbonnais, C.; Creuzet, F.; Jérome, D.; Bechgaard, K.; Moradpour, A.

    1984-01-01

    We present 1H and 77Se NMR relaxation data on oriented (TMTSF)2ClO4 single crystals in the relaxed state. The data show the existence of three distinct regimes for the nuclear relaxation rate T-11. In the high temperature part (T > 25 K) the Korringa law seems to be well satisfied whereas in the lower temperature part we have strong deviations down to 8 K or so. At T ≲ 6 K, a different and enhanced Korringa regime appears to be restored. Preliminary results on (TMTSF)2FSO3 under pressure also...

  15. Investigation of toxic effects of imidazolium ionic liquids, [bmim][BF4] and [omim][BF4], on marine mussel Mytilus galloprovincialis with or without the presence of conventional solvents, such as acetone

    International Nuclear Information System (INIS)

    Highlights: • The toxic effects of [bmim][BF4] and [omim][BF4] on mussels were investigated. • Both ILs could induce lethal and nonlethal effects on Mytilus galloprovincialis. • Different extent of IL-mediated adverse effects was observed in mussel hemocytes. • The alkyl chain length and lipophilicity of ILs are crucial for their toxicity. • Acetone influences the oxidative and genotoxic effects of [omim][BF4]. - Abstract: This study investigated the cytotoxic, oxidative and genotoxic effects of two commonly used imidazolium ionic liquids (ILs), [bmim][BF4] (1-butyl-3-methylimidazolium) and [omim][BF4] (1-methyl-3-octylimidazolium tetrafluoroborate), on the marine mussel Mytilus galloprovincialis, as well as whether acetone could mediate their toxic profile. In this context, mussels were firstly exposed to different concentrations of [bmim][BF4] or [omim][BF4], with or without the presence of acetone (at a final concentration of 0.06% v/v), for a period of 96 h, in order to determine the concentration that causes 50% mussel mortality (LC50 values) in each case. Thereafter, mussels were exposed to sub- and non-lethal concentrations of ILs for investigating their ability to cause lysosomal membrane impairment (with the use of neutral red retention assay/NRRT), superoxide anion and lipid peroxidation byproduct (malondialdehyde/MDA) formation, as well as DNA damage and formation of nuclear abnormalities in hemocytes. The results showed that [omim][BF4] was more toxic than [bmim][BF4] in all cases, while the presence of acetone resulted in a slight attenuation of its toxicity. The different toxic behavior of ILs was further revealed by the significantly lower levels of NRRT values observed in [omim][BF4]-treated mussels, compared to those occurring in [bmim][BF4] in all cases. Similarly, [bmim][BF4]-mediated oxidative and genotoxic effects were observed only in the highest concentration tested (10 mg L−1), while [omim][BF4]-mediated effects were enhanced at

  16. Structural, spectroscopic and magnetic properties of [Cu(1-meim)4].2(PF6)

    Science.gov (United States)

    Yıldırım, Ilkay; Karabulut, Bünyamin

    2016-03-01

    [Cu(1-meim)4].2(PF6) (1-meim: 1-methylimidazole) complex has been synthesized and characterized by EPR, FT-IR, and XRD techniques. The Cu(II) complex crystallizes in the monoclinic system with the space group P21/c. EPR spectrum of [Cu(1-meim)4].2(PF6) powder has been studied at room temperature. The spin Hamiltonian parameters (g and hyperfine values) have been calculated. The results indicate the axial symmetry around the paramagnetic Cu2+ center. 2 2 The ground state wave function of Cu2+ ion has been constructed. The unpaired electron spends most of its time in dx2-y2 orbital.

  17. Characterization of plasticized PMMA–LiBF4 based solid polymer electrolytes

    Indian Academy of Sciences (India)

    S Rajendran; T Uma

    2000-02-01

    Polymer electrolyte films prepared from poly(methyl methacrylate) and LiBF4 with different concentrations of plasticizer (DBP) are described. The formation of polymer–salt complex has been confirmed by FTIR spectral studies. The temperature dependence of conductivity of polymer films seems to obey the VTF relation. Values of conductivities of the polymer complexes are presented and discussed.

  18. Electrocrystallization and structures of perylene radical salts: hexaperylene perchlorate, (C20H12)6+ClO4-, triperylene perchlorate, (C20H12)3+ClO4-, and diperylene hexafluorophosphate-tetrahydrofuran (3/2), (C20H12)2+PF6-.2/3C4H8O

    OpenAIRE

    Endres, Helmut; Keller, Heimo J.; Müller, Barbara; Schweitzer, Dieter

    1985-01-01

    Crystals grown by electrocrystallization, species obtained depending on perylene concentration. Room-temperature data collect ions, Mo Kat λ = 0·71069 A. 6:1 salt: Mr= 1613·3, triclinic. pl, a = 12·57 1 (7), b = 13·699(5). c = 13.835(II)A, α = 110·43 (4), β= 107·13 (7), γ= 107·09 (4)°, V = 1913A3, Z = 1, Dx = 1.40gcm-3, μ= 1.1 cm- ', F(OOO) = 841, final R = 0·077 for 3171 observed reflections. The structure contains three independent perylene π dimers arranged ne...

  19. Positron 2D-ACAR study of the quasi-one-dimensional organic superconductor (TMTSF)2ClO4

    International Nuclear Information System (INIS)

    We have measured electron-positron momentum density in (TMTSF)2ClO4 by the positron two-dimensional angular correlation of annihilation radiation (2D-ACAR) technique. In order to interpret the experimental results, the electronic structure of (TMTSF)2ClO4 as well as the positron state therein has been investigated by ab initio theoretical calculations. 2D-ACAR spectra have been also calculated and compared with the experimental ones through their anisotropies and Lock-Crisp-West remapped spectra. The Fermi-surface-related structure is discussed. (orig.)

  20. Electrodeposition of tin from EMI⋅BF4⋅Cl room temperature molten salts

    Directory of Open Access Journals (Sweden)

    Morimitsu M.

    2003-01-01

    Full Text Available The electrochemistry of Sn(II was investigated with cyclic voltammetry and chronoamperometry in the 1-ethyl-3-methylimidazolium tetrafluoroborate molten salt containing free chloride ions (EMI ⋅BF4 ⋅Cl originated from the mixture of EMIC and NaBF4 (60:40 mol%. The well defined redox waves for the electro deposition and dissolution of tin were observed on a platinum electrode at 303 K. The deposition of tin proceeded through a quasi-reversible step with two electron transfer, and the deposited tin was sufficiently recovered during oxidation. The experimental current-time transient coincided with the theory based on one-dimensional diffusion control.

  1. Synthesis and characterization of ionic liquid (EMImBF4)/Li+ - chitosan membranes for ion battery

    International Nuclear Information System (INIS)

    Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li+ ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anion metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10−2 S cm−1 for chitosan to 1.30 × 10−2 S cm−1 for chitosan with EMImBF4/Li+, and this result was supported by analysis the surface morphology (SEM)

  2. Synthesis and characterization of ionic liquid (EMImBF4)/Li+ - chitosan membranes for ion battery

    Science.gov (United States)

    Pasaribu, Marvin H.; Arcana, I. Made; Wahyuningrum, Deana

    2015-09-01

    Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li+ ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anion metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10-2 S cm- 1 for chitosan to 1.30 × 10-2 S cm-1 for chitosan with EMImBF4/Li+, and this result was supported by analysis the surface morphology (SEM).

  3. Solvent relaxation of a room-temperature ionic liquid [bmim][PF6] confined in a ternary microemulsion

    Indian Academy of Sciences (India)

    Debabrata Seth; Palash Setua; Anjan Chakraborty; Nilmoni Sarkar

    2007-03-01

    In this paper we have reported the solvent and rotational relaxation of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) confined in tween 20/([bmim][PF6]/water microemulsion using coumarin 153 (C-153) as probe. The most interesting feature of our experiment was that we observed an increase in solvent relaxation time with increase in ( = tween 20-to-[bmim][PF6] molar ratio). This is due to the fact that with increase in [bmim][PF6] content of the microemulsions, the microviscosity of the pool of the microemulsions increases, and motion of ions of [bmim][PF6] is hindered in the pool of microemulsions. Since motion of ions is responsible for solvation in room-temperature ionic liquids (RTILs), solvent-relaxation time increases with increase in .

  4. Anisotropy of the upper critical field in ultrahigh-pressure-induced superconductor (TMTTF)2PF6

    International Nuclear Information System (INIS)

    We have measured the temperature dependence of resistivity of (TMTTF)2PF6 under high pressures up to 7 GPa by using a turnbuckle DAC (diamond anvil cell) for pressurization, also in magnetic field up to 5 T. In superconducting transition, zero-resistivity was successfully observed even there are not many cases that zero-resistivity has been observed from measurements of organics under high pressures. Superconductivity was observed at P=4.18-6.03 GPa and showed the highest TC of 2.25 K at 4.58 GPa. The temperature dependence of the upper critical magnetic field HC2(T) was determined via resistivity at P=4.58 GPa, for the intrachain (a), interchain (b'), and interlayer (c*). Also, the values of GL coherence lengths for three different axis which obtained from this work show that (TMTTF)2PF6 is anisotropic three-dimensional superconductor.

  5. Thermodynamics of Imidazolium-Based Ionic Liquids Containing PF6 Anions.

    Science.gov (United States)

    Zaitsau, Dzmitry H; Yermalayeu, Andrei V; Emel'yanenko, Vladimir N; Butler, Simon; Schubert, Thomas; Verevkin, Sergey P

    2016-08-18

    Imidazolium-based ionic liquids (ILs) with PF6(-) anions are considered as low-cost solvents for separation processes, but they exhibit restricted thermal stabilities. Reliable measurements of vaporization thermodynamics by conventional methods have failed. In this work, we applied a quartz-crystal microbalance method to determine for the first time the absolute vapor pressures for the [Cnmim][PF6] family, with n = 2, 4, 6, 8, and 10, in the temperature range 403-461 K. An absence of decomposition of ILs in experimental conditions was determined by the attenuated total reflection-infrared spectroscopy. The consistency of the experimental results within the homologous series was established through enthalpy and entropy analyses of the liquid and gas phases as well as by molecular dynamics simulations. PMID:27462931

  6. Studies on the thermal decomposition kinetics of LiPF6 and LiBC4O8

    Indian Academy of Sciences (India)

    Li Shi-You; Ma Pei-Hua; Cui Xiao-Ling; Ren Qi-Du; Li Fa-Qiang

    2008-03-01

    Thermal decomposition of LiPF6 and LiBC4O8 (lithium bis(oxalate)borate, abbreviated as LiBOB) were studied using TG (thermogravimetry)-DTG (derivative thermogravimetry) method with different heating rate of 5, 10, 20 and 40°C min-1 or at different constant temperature C (109.80, 118.79, 148.41, 176.86 °C for LiPF6 and 278.51, 298.13, 317.65, 336.13 for LiBOB). From the nonisothermal kinetics we calculate that LiPF6 is 1.01, LiBOB is 1.04, LiPF6 is 91907.61 J/mol, and LiBOB is 205179.88 J/mol; from the isothermal kinetics we calculate that n for both LiPF6 and LiBOB are 1, LiPF6 is 91907.61 J/mol, LiBOB is 205179.88 J/mol, lnALiPF6 is 16.89 s-1, and lnALiBOB is 31.96 s-1. The results obtained from the two ways have minor differences and can validate each other.

  7. Crystal structure, properties and phase transitions of morpholinium tetrafluoroborate [C 4H 10NO][BF 4

    Science.gov (United States)

    Szklarz, P.; Owczarek, M.; Bator, G.; Lis, T.; Gatner, K.; Jakubas, R.

    2009-07-01

    The crystal structure of [C 4H 10NO][BF 4] is determined in the phase I at 160, 180, 240 and 290 K. At room temperature the compound crystallizes in the orthorhombic space group: Pnam. The structure is composed of the morpholinium cations, [C 4H 10NO] +, which form one-dimensional hydrogen bonded chains, and [BF 4] - anions. [C 4H 10NO][BF 4] undergoes two structural phase transformations: second-order at 153 K and first-order at 117/118 K (cooling/heating). The phase transitions are characterized with the differential scanning calorimetry, dilatometric and dielectric techniques. The possible mechanism of the phase transitions in [C 4H 10NO][BF 4] is discussed on the basis of the presented results.

  8. Di-ureasil hybrids doped with LiBF4: Spectroscopic study of the ionic interactions and hydrogen bonding

    International Nuclear Information System (INIS)

    Highlights: → FT-IR and FT-Raman spectroscopy were used to characterize cation interactions in two LiBF4-doped di-ureasil networks incorporating POE chains with different length. → Over the range of salt content analyzed the cations bond to amorphous POE chains and form ion contact pairs with BF4-. → A crystalline POE/LiBF4 complex of unknown stoichiometry emerges at high salt concentration. - Abstract: In the present work Fourier transform infrared and Raman spectroscopy were used to characterize the cation/polymer, cation/cross-link, cation/anion and hydrogen bonding interactions in hybrid electrolytes composed of lithium tetrafluoroborate (LiBF4) and di-urea cross-linked poly(oxyethylene) (POE)/siloxane hybrid networks (di-ureasils) designated as d-U(2000) and d-U(600) and incorporating polyether chains with ca. 40.5 and 8.5 oxyethylene repeat units, respectively. Samples with ∞ > n ≥ 2.5 (where n, composition, is the molar ratio of CH2CH2O units per Li+ ion) were analyzed. In both di-ureasil systems over the whole range of salt content examined the Li+ ions bond to the ether oxygen atoms of amorphous POE chains and to BF4- ions forming ion contact pairs. Spectroscopic evidences and SEM images confirm the presence of a crystalline POE/LiBF4 complex of unknown stoichiometry at n +/urea carbonyl oxygen atom interactions.

  9. Synthesis of Aryl Allyl Ether in the Recyclable Ionic Liquid [bmim]PF6

    Institute of Scientific and Technical Information of China (English)

    Zhou Mei-Yun; Li Yi-Qun; Xu Xin-Ming

    2004-01-01

    Ionic liquids, especially imidazonium salts, have recently gained recognition as possible environmentally benign alternative chemical process solvents. This is mainly due to their nonvolatile nature, insolubility in some solvents as well as their ability to dissolve a wide range of organic and inorganic materials, allowing the ionic liquids easy recovery and recycling. Examples of their application in organic reactions have been summarized in a number of recent review articles.1Aryl allyl ether is very useful intermediate in organic synthesis. The Williamson reaction is a well knows method for the preparation ethers. However, the reaction of alkylating agents with the phenoxide ions was conventionally carried out in the organic solvents. The usual solvents for this type of reaction are DCM, 2 DMSO, 3 DMF, 4 CH3CN5 etc. With the current desire to avoid the use of organic molecular solvents in organic synthesis, we decide to investigate the use of the ionic liquid for the alternative solvent for the Williamson reaction to prepare the aryl allyl ethers. The ionic liquid employed here was the moisture stable 1-butyl-3-methylimidazolium hexafluorophosphate [bmim]PF6.6 The ionic liquid is non-volatile, thermally stable, and depending on the anion, can present low immiscible with water,alkanes and dialky ethers. We have now found that aryl allyl ethers can have been obtained from various phenols and allyl bromide in the presence of potassium hydroxide in [bmim]PF6 as a replacement for classical organic solvents in the ambient temperature. The results are shown in Scheme 1.The reaction were carried out by simple mixing the phenolwith the ally bromide and potassium hydroxide in [bmim]PF6 and stirred at room temperature for 4h. The results are summarized in Table 1.In conclusion, Williamson reaction can be successfully conducted in ionic liquid [bmim]PF6 with a number of advantages: the procedure is simple, the reaction condition is mild and the yields are excellent

  10. Optimization of performances of gelatin/LiBF4-based polymer electrolytes by plasticizing effects

    International Nuclear Information System (INIS)

    Gelatin is a cheap and abundant natural product with very good biodegradation properties and can be used to obtain acetic acid or LiClO4-based gel polymer electrolytes (GPEs) with high ionic conductivity and good stability. This article presents results of GPEs obtained by the plasticization of gelatin and addition of LiBF4, where the optimization of the system was achieved by using a factorial design type 22 with two variables: glycerol and LiBF4. From this analysis it was stated that the effect of glycerol as a plasticizer on the ionic conductivity results is much more important than the effect obtained by varying the lithium salt content or the effect of the interaction of both variables. Also all the samples were characterized by X-ray diffraction measurements, UV-vis-NIR spectroscopy and scanning electron microscopy (SEM) and impedance spectroscopy. The ionic conductivity results of all analyzed samples as a function of temperature obey predominantly an Arrhenius relationship and the samples are stable up to 160 deg. C. Good conductivity results combined with transparency and good adhesion to the electrodes have shown that gelatin-based GPEs are very promising materials to be used as solid electrolytes in electrochromic devices.

  11. Assembly of a Cyclic Dimer Silver(I) Complex Encapsulating Two BF4 - Ions

    International Nuclear Information System (INIS)

    Unusual twenty-membered cyclic dimer encapsulating two BF4- anions was obtained by the self-assembly of the tridentate N2S donor ligand and silver ion. We are currently investigating the subtle factors influencing the formation of discrete or continuous complexes using dipicolyl sulfide derivatives including. It is a challenging work to capture ionic species or small molecules as guests. Thus, the construction of self-assembled cyclic oligomer complexes composed of metal centres connected by acyclic organic ligands has been a subject of great interest together with the inclusion phenomena of macrocyclic ligands in the supramolecular chemistry. The majority of the organic-inorgaic hybrid macrocyclic structures reported so far have been based on bis-monodentate ligands such as 4,4'-bipyridine and its derivatives interconnected by rigid or flexible spacers. The same type of ligands has been also used for the formation of coordination network

  12. Pitting corrosion of Al and Al-Cu alloys by ClO4- ions in neutral sulphate solutions

    International Nuclear Information System (INIS)

    The influence of various concentrations of NaClO4, as a pitting corrosion agent, on the corrosion behaviour of pure Al, and two Al-Cu alloys, namely (Al + 2.5 wt% Cu) and (Al + 7 wt% Cu) alloys in 1.0 M Na2SO4 solution was investigated by potentiodynamic polarization and potentiostatic techniques at 25 deg. C. Measurements were conducted under the influence of various experimental conditions, complemented by ex situ energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) examinations of the electrode surface. In free perchlorate sulphate solutions, for the three Al samples, the anodic polarization exhibits an active/passive transition. The active dissolution region involves an anodic peak (peak A) which is assigned to the formation of Al2O3 passive film on the electrode surface. The passive region extends up to 1500 mV with almost constant current density (jpass) without exhibiting a critical breakdown potential or showing any evidence of pitting attack. For the three Al samples, addition of ClO4- ions to the sulphate solution stimulates their active anodic dissolution and tends to induce pitting corrosion within the oxide passive region. Pitting corrosion was confirmed by SEM examination of the electrode surface. The pitting potential decreases with increasing ClO4- ion concentration indicating a decrease in pitting corrosion resistance. The susceptibility of the three Al samples towards pitting corrosion decreases in the order: Al > (Al + 2.5 wt% Cu) alloy > (Al + 7 wt% Cu) alloy. Potentiostatic measurements showed that the rate of pitting initiation increases with increasing ClO4- ion concentration and applied step anodic potential, while it decreases with increasing %Cu in the Al samples. The inhibitive effect of SO42- ions was also discussed

  13. Electropolymerization of 3-Methylthiophene in [BMIM]PF6 Ionic Liquid, Characterization and Application

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ai-Jian; QI Xi-Min; DU Yan-Fang; LUO Yi-Wen; FANG Hui-Jue; LU Jia-Xing

    2006-01-01

    Poly-3-methylthiophene (P3MT) was synthesized in the room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) by constant potential and constant current respectively. The structure and morphology of P3MT films were characterized by FTIR spectrum and SEM. The undoped (reduction) and doped (oxidation) forms of P3MT film prepared in ionic liquid were reversible and stable. The P3MT film has strong characteristics of electrocatalytic oxidation of ascorbic acid and can separate the oxidation peaks of ascorbic acid and dopamine. Two methods of potential steps were used to observe the response time of the film and the film was found to have perfect electrochromic response.

  14. Thermal reactions of mesocarbon microbead (MCMB) particles in LiPF 6-based electrolyte

    Science.gov (United States)

    Xiao, Ang; Li, Wentao; Lucht, Brett L.

    The thermal reaction of ternary electrolyte (1.0 M LiPF 6 in 1:1:1 ethylene carbonate/dimethyl carbonate/diethyl carbonate) with mesocarbon microbeads (MCMB) particles was investigated by the combined use of NMR, GC-MS, FTIR-ATR, TGA, XPS and SEM/EDS-element map. The thermal decomposition of ternary electrolyte is not inhibited by the presence of MCMB particles. The chemical composition and morphology of the surface of MCMB particles changes significantly upon storage in the presence of ternary electrolyte. Electrolyte decomposition products including oligocarbonates, oligoethylene oxides, polyethylene oxide (PEO), lithium fluorophosphates (Li xPO yF z), and lithium fluoride are deposited on the surface of MCMB particles. The concentration of decomposition products on the surface of MCMB increases with increased storage time and temperature. The addition of dimethyl acetamide (DMAc) impedes the thermal decomposition of the electrolyte and deposition of electrolyte decomposition products on the surface of MCMB.

  15. Structure and Dynamics of [PF$_6$][P$_{1,2,2,4}$] from Molecular Dynamics Simulations

    CERN Document Server

    Carignano, Marcelo A

    2013-01-01

    Diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate, [PF$_6$][P$_{1,2,2,4}$], is an organic ionic plastic crystal with potential uses as a solid electrolyte in storage and light harvesting devices. In this work we present a molecular dynamics simulation study for this material covering an extended temperature range, from 175 K to 500 K. The simulations predicts a transition from the crystalline to a {\\em semi} plastic phase at 197 K, the onset of cation jump-like rotations at 280 K, a third transition at 340 K to a {\\em full} plastic phase and melting to 450 K. Overall, the simulations show a good agreement with the experimental findings providing a wealth of detail in the structural and dynamic properties of the system.

  16. Enhanced Performance of Li|LiFePO4 Cells Using CsPF6 as an Electrolyte Additive

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Liang; Chen, Xilin; Cao, Ruiguo; Qian, Jiangfeng; Xiang, Hongfa; Zheng, Jianming; Zhang, Jiguang; Xu, Wu

    2015-10-20

    The practical application of lithium (Li) metal anode in rechargeable Li batteries is hindered by both the growth of Li dendrites and the low Coulombic efficiency (CE) during repeated charge/discharge cycles. Recently, we have discovered that CsPF6 as an electrolyte additive can significantly suppress Li dendrite growth and lead to highly compacted and well aligned Li nanorod structure during Li deposition on copper substrates. In this paper, the effect of CsPF6 additive on the performance of rechargeable Li metal batteries with lithium iron phosphate (LFP) cathode was further studied. Li|LFP coin cells with CsPF6 additive in electrolytes show well protected Li anode surface, decreased resistance, enhanced rate capability and extended cycling stability. In Li|LFP cells, the electrolyte with CsPF6 additive shows excellent long-term cycling stability (at least 500 cycles) at a charge current density of 0.5 mA cm-2 without internal short circuit. At high charge current densities, the effect of CsPF6 additive becomes less significant. Future work needs to be done to protect Li metal anode, especially at high charge current densities and for long cycle life.

  17. Enhanced performance of Li|LiFePO4 cells using CsPF6 as an electrolyte additive

    Science.gov (United States)

    Xiao, Liang; Chen, Xilin; Cao, Ruiguo; Qian, Jiangfeng; Xiang, Hongfa; Zheng, Jianming; Zhang, Ji-Guang; Xu, Wu

    2015-10-01

    The practical application of lithium (Li) metal anode in rechargeable Li batteries is hindered by both the growth of Li dendrites and the low Coulombic efficiency (CE) during repeated charge/discharge cycles. Recently, we have discovered that CsPF6 as an electrolyte additive can significantly suppress Li dendrite growth and lead to highly compacted and well aligned Li nanorod structures during Li deposition on copper substrates. In this paper, the effect of CsPF6 additive on the performance of rechargeable Li metal batteries with lithium iron phosphate (LFP) cathode is further studied. Li|LFP coin cells with CsPF6 additive in electrolytes show well protected Li anode surface, decreased resistance, enhanced rate capability and extended cycling stability. In Li|LFP cells, the electrolyte with CsPF6 additive shows excellent long-term cycling stability (at least 500 cycles) at a charge current density of 0.5 mA cm-2 without internal short circuit. At high charge current densities, the effect of CsPF6 additive becomes less significant. Future work needs to be done to protect Li metal anode, especially at high charge current densities and for long cycle life.

  18. Biosorption of BF-4B Reactive Red Dye by using Leaves of Macrophytes Eichhornia crassipes

    Directory of Open Access Journals (Sweden)

    Aparecido Nivaldo Módenes

    2013-04-01

    Full Text Available The removal potential on BF-4B reactive red dye by Eichhornia crassipes dried leaves has been investigated. Furthermore, the influence of process parameters such as solution pH, agitation, and particle size on the dye adsorption efficiency was assessed. Both kinetic and equilibrium experiments were performed in batch operation of the system. Kinetic results demonstrated that the equilibrium state was achieved after 45 min process time. The kinetic experimental data were best described by applying a pseudo-second order model that evaluated the value of rate constant 0.22 g/mg/min and an equilibrium dye concentration 8.20 mg/g. A set of isotherm models, taken from knowledge database, was tested in order to represent the equilibrium adsorption data. The Langmuir model performed the best when fitting experimental data where the maximum adsorption capacity of 20.38 mg/g was achieved. The results demonstrated that the E. crassipes has good potential to be used as a biosorbent in industrial treatment systems to remove reactive dyes from textile effluents.

  19. Time-dependent effects of [apyr]BF4 and key contributors to their mixture stimulation on Vibrio qinghaiensis sp.-Q67 at apical and biochemical levels.

    Science.gov (United States)

    Yu, ZhenYang; Zhang, Jing

    2016-07-15

    Earlier reports studied the time-dependent effects of imidazolium-based ionic liquids ([amim]X) in the aspect of biochemical explanation and that of key contributor in mixture effects. Presently, the effects of N-alkylpyridinium-based ILs ([apyr]BF4) were studied combining the above two aspects, i.e., the time-dependent effects of [bpyr]BF4, [hpyr]BF4 and [opyr]BF4 on luminescence and biochemical indicators in Vibrio qinghaiensis sp.-Q67, and those of the mixtures. In individual results, the inhibition on luminescence increased over concentrations and the side chain length, showing concentration- and side chain-dependence. Moreover, the inhibition of [apyr]BF4 decreased from 0.25 to 24h, showing a time-dependence. Notably, [hpyr]BF4 stimulated the luminescence at 24h. The biochemical effects, including inhibition and stimulation, were well correlated to those on luminescence. In mixture results, the inhibition on luminescence was lower than the predicted effects by concentration addition model which was based on individual results. Moreover, the mixture stimulation on luminescence was significantly higher than individual ones, and the mixture stimulation on biochemical indicators was even greater than that on luminescence. In mixture effects, [bpyr]BF4 was the positive contributor, and [hpyr]BF4 was the negative contributor. Similarities and differences between [amim]X and [apyr]BF4 indicated underlying mechanisms of the commonly observed hormetic effects of ionic liquids. PMID:27017397

  20. Direct measurement of the chemical reactivity of silicon electrodes with LiPF6-based battery electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Veith, Gabriel M [ORNL; Baggetto, Loic [ORNL; Sacci, Robert L [ORNL; Unocic, Raymond R [ORNL; Tenhaeff, Wyatt E [ORNL; Browning, Jim [ORNL

    2014-01-01

    We report the first direct measurement of the chemistry and extent of reactivity between a lithium ion battery electrode surface (Si) and a liquid electrolyte (1.2M LiPF6-3:7 wt% ethylene carbonate:dimethyl carbonate). This layer is estimated to be 3.6 nm thick and partially originates from the consumption of the silicon surface.

  1. Graphene-Polypyrrole Nanocomposite as a Highly Efficient and Low Cost Electrically Switched Ion Exchanger for Removing ClO4- from Wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Sheng; Shao, Yuyan; Liu, Jun; Aksay, Iihan A.; Lin, Yuehe

    2011-10-10

    Perchlorate (ClO4-) contamination is now recognized as a widespread concern affecting many water utilities. In this report, graphene is employed as the scaffold to synthesize novel graphene-polypyrrole nanocomposite, which is demonstrated as excellent electrically switched ion exchanger for perchlorate removal. Scanning electron microscopy (SEM) and electrochemical measurements showed that the 3D nanostructured graphene/Ppy nanocomposite exhibited the significantly improved uptake capacity for ClO4- compared with Ppy film. X-ray photoelectron spectroscopy (XPS) confirmed the uptake and release process of ClO4- in graphene/Ppy nanocomposite. In addition, the presence of graphene substrate resulted in high stability of graphene/Ppy nanocomposite during potential cycling. The present work provides a promising method for large scale water treatment.

  2. Comparison of the local binding motifs in the imidazolium-based ionic liquids [EMIM][BF4] and [EMMIM][BF4] through cryogenic ion vibrational predissociation spectroscopy: Unraveling the roles of anharmonicity and intermolecular interactions

    International Nuclear Information System (INIS)

    We clarify the role of the critical imidazolium C(2)H position (the central C between N atoms in the heterocycle) in the assembly motif of the [EMIM][BF4] ionic liquid by analyzing the vibrational spectra of the bare EMIM+ ion as well as that of the cationic [EMIM]2[BF4]+ (EMIM+ = 1-ethyl-3-methylimidazolium, C6H11N2+) cluster. Vibrational spectra of the cold, mass-selected ions are obtained using cryogenic ion vibrational predissociation of weakly bound D2 molecules formed in a 10 K ion trap. The C(2)H behavior is isolated by following the evolution of key vibrational features when the C(2) hydrogen, the proposed binding location of the anion to the imidazolium ring, is replaced by either deuterium or a methyl group (i.e., in the EMMIM+ analogue). Strong features in the ring CH stretching region of the bare ion are traced to Fermi resonances with overtones of lower frequency modes. Upon incorporation into the EMIM+ ⋅ ⋅ ⋅ BF4− ⋅ ⋅ ⋅ EMIM+ ternary complex, the C(2)H oscillator strength is dramatically increased, accounting for the much more complicated patterns derived from the EMIM+ ring CH stretches in the light isotopomer, which are strongly suppressed in the deuterated analogue. Further changes in the spectra that occur when the C(2)H is replaced by a methyl group are consistent with BF4− attachment directly to the imidazolium ring in an arrangement that maximizes the electrostatic interaction between the molecular ions

  3. 锂离子电池电解质盐LiPF6中微量水的测定%MEASUREMENT OF TRACE WATER IN LiPF6 ELECTROLYTE SALT OF LITHIUM ION BATTERY

    Institute of Scientific and Technical Information of China (English)

    王成俊; 郭爱红; 王凤花; 韩晓丽; 张宝贵

    2003-01-01

    采用把库仑法和卡尔-菲休法有效结合的库仑滴定法测定锂电池电解质中微量水份,对电解质盐六氟磷酸锂(LiPF6)样品的测定表明,该方法灵敏度为1μg,精密度高,结果比较理想.

  4. Photoinduced electron and energy transfer from coumarin 153 to perylenetetracarboxylic diimide in bmimPF6/TX-100/water microemulsions.

    Science.gov (United States)

    Wu, Haixia; Wang, Haixia; Xue, Lin; Li, Xiyou

    2011-01-15

    A perylenetetracarboxylic diimide (PDI) compound with an attached hydrophilic polyoxyethylene group at the imide nitrogen position was designed and synthesized. Photoinduced electron and energy transfer between coumarin 153 (C-153) and PDI in a ternary microemulsion with an ionic liquid (bmimPF(6)/TX-100/H(2)O) were investigated by steady state electronic absorption and fluorescence spectroscopy. The results revealed that both PDI and C-153 resided at the interface between the surfactant TX-100 and the ionic liquid bmimPF(6) in the ternary microemulsions. The absorption spectra suggested no interactions between C-153 and PDI in the ground states, but the fluorescence spectra revealed the presence of an efficient electron transfer and a less efficient energy transfer from C-153 to PDI. Moreover, the electron transfer was much more efficient in microemulsions than that in homogeneous conventional organic solvents due to the unique micro-environment of the microemulsion. PMID:20965513

  5. Overhauser effect experiments on the one-dimensional conductor (perylene)2+PF6-·2/3THF

    OpenAIRE

    Brunner, Hermann; Hausser, Karl H.; Keller, Heimo J.; Schweitzer, Dieter

    1984-01-01

    We have measured the Overhauser enhancement of the protons and the 19F-nuclei of the one-dimensional conductor (perylene)2+PF6-·2/3THF in its metallic phase at room temperature. The enhancement factor V was found to be VP=+320±20 for the protons and VF=+175±40 for the 19F-nuclei indicating a predominantly scalar interaction with the conduction electrons in both cases.

  6. Direct measurement of the chemical reactivity of silicon electrodes with LiPF6-based battery electrolytes.

    Science.gov (United States)

    Veith, Gabriel M; Baggetto, Loïc; Sacci, Robert L; Unocic, Raymond R; Tenhaeff, Wyatt E; Browning, James F

    2014-03-21

    We report the first direct measurement of the extent of the spontaneous non-electrochemically driven reaction between a lithium ion battery electrode surface (Si) and a liquid electrolyte (1.2 M LiPF6-3 : 7 wt% ethylene carbonate : dimethyl carbonate). This layer is estimated to be 35 Å thick with a SLD of ∼ 4 × 10(-6) Å(-2) and likely originates from the consumption of the silicon surface. PMID:24513965

  7. TEMPO-catalyzed aerobic oxidation of alcohols to aldehydes and ketones in ionic liquid [bmim][PF6].

    Science.gov (United States)

    Ansari, Imtiaz A; Gree, Rene

    2002-05-01

    [reaction: see text]. A simple and mild TEMPO-CuCl catalyzed aerobic oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones in ionic liquid [bmim][PF6] with no trace of overoxidation to carboxylic acids has been developed. The product can be isolated by a simple extraction with organic solvent, and the ionic liquid can be recycled or reused. PMID:11975615

  8. Dielectric spectroscopy study on ionic liquid microemulsion composed of water, TX-100, and BmimPF6

    Science.gov (United States)

    Chen, Zhen; Nozaki, Ryusuke

    2012-06-01

    We report here a broadband dielectric spectroscopy study on an ionic liquid microemulsion (ILM) composed of water, Triton X-100 (TX-100), and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6). It is found that the phase behavior of this ILM can be easily identified by its dielectric response. The dielectric behavior of the ILM in the GHz range is consistent with that of TX-100/water mixtures with comparable water-to-TX-100 weight ratio. It consists of the relaxations due to ethylene oxide (EO) unit relaxation, hydration water dynamics, and/or free water dynamics. The water content dependence of the EO unit relaxation suggests that this relaxation involves dynamics of hydration water molecules. In the IL-in-water microemulsion phase, it is found that bmimPF6 molecules are preferentially dissolved in water when their concentration in water is lower than the solubility. An additional dielectric relaxation that is absent in the TX-100/water mixtures is observed in the frequency range of 107-108 Hz for this ILM. This low-frequency relaxation is found closely related to the bmimPF6 molecule and could be attributed to the hopping of its cations/anions between the anionic/cationic sites.

  9. Electrochemical investigation of Li-Al anodes in oligo(ethylene glycol) dimethyl ether/LiPF6

    International Nuclear Information System (INIS)

    LiPF6 dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight 5 g mol-1 was investigated as a new electrolyte (OEGDME5, 1 M LiPF6) for metal deposition and battery applications. At 25 C a conductivity of .48 x 1-3 S cm-1 was obtained and at 85 C, 3.78 x 1-3 S cm-1. The apparent activation barrier for ionic transport was evaluated to be 3.7 kJ mol-1. OEGDME5, 1 M LiPF6 allows operating temperature above 1 C with very attractive conductivity. The electrolyte shows excellent performance at negative and positive potentials. With this investigation, we report experimental results obtained with aluminum electrodes using this electrolyte. At low current densities lithium ion reduction and re-oxidation can be achieved on aluminum electrodes at potentials about 28 mV more positive than on lithium electrodes. In situ X-ray diffraction measurements collected during electrochemical lithium deposition on aluminum electrodes show that the shift to positive potentials is due to the negative Gibbs free energy change of the Li-Al alloy formation reaction.

  10. A laser flash photolysis study on duroquinone in binary mixtures of ionic liquid [bmim]+[PF6]- and acetonitrile

    International Nuclear Information System (INIS)

    Room temperature ionic liquids (RTILs) are entirely composed of special organic cations and anions, which are liquid near room temperature. Owing to their desirable properties including nonvolatility, high polarity, high selectivity and ease of recycling, RTILs are regarded as suitable solvents for green chemistry,which have been used as reaction media for a number of organic synthesis reactions, catalysis, separation processes and polymerization. As a prototype of RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] has been used as medium in which some representative photochemical reactions have been previously studied in comparison with volatile organic compounds. It was found that molecular diffusion of solute was significantly retarded and lifetime of transient species was longer in the neat [bmim][PF6]. Laser flash photolysis experiments were carried out using a Nd:YAG laser that provides 266 and 355 nm laser pulse with a duration of 5 ns and a maximum energy of 80 mJ per pulse. Using duroquinone (DQ) as a probe molecule photochemical properties of the ionic liquid [bmim][PF6] and its binary mixed solutions with acetonitrile (MeCN) were investigated at an excitation wavelength of 355 nm by laser flash photolysis technique. Along with the increasing of the fraction of [bmim][PF6] in the mixture, the characteristic absorption peak of triplet excited state 3DQ* showed a blue shift of ca. 20 nm. It was found that the decay of 3DQ* under N2 atmosphere followed a mono-exponential kinetics. Its rate constant increased with xRTIL (VRTIL/VMeCN) before the critical point at xRTIL = 0.3; however, it decreased obviously with xRTIL after the critical point. The experimental results indicate that RTIL didn't react with 3DQ*, which is different from our previous study on anthraquinone in binary solutions of [bmim][PF6] and acetonitrile. In view of the experimental data, it can be concluded that the viscosity and phase transformation are dominant for the effects

  11. Moessbauer study and magnetic properties of bis (ethanol) tetraphenylporphinatoiron (III) tetrafluoroborate [Fe(EtOH)2(tpp)]+BF4-

    International Nuclear Information System (INIS)

    Moessbauer experiments and magnetic measurements have been performed at various temperatures between 1.8 and 300 K on a six-coordinated iron porphyrin [Fe(EtOH)2(tpp)]+BF4-. All the results are consistent with the presence of high-spin iron (III) with an unambiguous S = 5/2 ground state. A marked reversal of the asymmetric broadening of the quadrupole doublet lines has been observed between 1.8 and 300 K. This asymmetric broadening of the lines arising from relaxation effects depends on the directions along which the hyperfine magnetic field fluctuates relative to the principal axes of the e.f.g. tensor. (Auth.)

  12. Theoretical study on reaction of [(Ind ∗)Rh(CO) 2Me]BF 4 with nbd

    Science.gov (United States)

    Bi, Siwei; Wang, Bin; Zhao, Yi; Zhang, Zhenwei; Zhu, Shufen

    2006-07-01

    The mechanisms on the model reaction of [(Ind)Rh(CO) 2Me]BF 4 with nbd have been studied using density functional theory. Two pathways are proposed due to the rotation of indenyl group. Our results of calculations predict that the methyl migration is the rate-determining step, and that the rotation of indenyl group around the Rh-indenyl axis plays an important role in lowering the reaction barrier. Theoretical studies also reveal that this kind of reaction is favorable thermodynamically as a result of the relief of ring strain as nbd coordinating to the metal center and the chelation effect arisen from the cyclometallation.

  13. Effect of ZrO2 on conductivity of PVC–PMMA–LiBF4–DBP polymer electrolytes

    Indian Academy of Sciences (India)

    S Rajendran; T Uma

    2000-02-01

    The preparation and characterization of composite polymer electrolytes of PVC–PMMA–LiBF4–DBP for different concentrations of ZrO2 have been investigated. FTIR studies indicate complex formation between the polymers, salt and plasticizer. The electrical conductivity values measured by a.c. impedance spectroscopy is found to depend upon the ZrO2 concentration. The temperature dependence of the conductivity of the polymer films seems to obey the VTF relation. The conductivity values are presented and results discussed.

  14. Dielectric spectroscopy study on ionic liquid microemulsion composed of water, TX-100, and BmimPF6

    OpenAIRE

    Chen, Zhen; Nozaki, Ryusuke

    2012-01-01

    We report here a broadband dielectric spectroscopy study on an ionic liquid microemulsion (ILM) composed of water, Triton X-100 (TX-100), and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6). It is found that the phase behavior of this ILM can be easily identified by its dielectric response. The dielectric behavior of the ILM in the GHz range is consistent with that of TX-100/water mixtures with comparable water-to-TX-100 weight ratio. It consists of the relaxations due to ethylene o...

  15. Nonlinear Hall effect in the field-induced spin-density wave states of (TMTSF)2PF6

    International Nuclear Information System (INIS)

    The resistivity along the conducting chains, ρxx, and the Hall resistivity ρxy are investigated as a function of the electric field in the magnetic-field-induced spin-density wave (FISDW) states of (TMTSF)2PF6 under hydrostatic pressure. Both resistivities decrease with increasing electric field above the same well-defined threshold electric field in the order of 100 μV/cm. We interpret the nonlinearity by the depinning and sliding of the FISDW. The nonlinearity in ρxy is much stronger than in ρxx what we attribute to an unusually strong coupling between the FISDW and single-particle excitations. (orig.)

  16. Glass transition in the spin density wave phase of (TMTSF)2PF6 investigated by calorimetric measurements

    International Nuclear Information System (INIS)

    We report on detailed kinetic investigation of the specific heat anomaly of the spin density wave phase of (TMTSF)2PF6 in the temperature range 2.5-5K. We point out the crucial role of kinetic conditions and of previous thermal history, such as isothermal annealing, which causes large hysteretic phenomena. This gives strong support to the origin of the anomaly in a glass transition which can be described in the general framework of freezing of supercooled liquids. For the unannealed system, Tg = 3.45 K. (orig.)

  17. Experiments and model for the surface tension of (MDEA + [Bmim][BF4]) and (MDEA + [Bmim][Br]) aqueous solutions

    International Nuclear Information System (INIS)

    Highlights: • The surface tensions of (MDEA + ionic liquids) aqueous solutions were measured. • The experiments were modeled satisfactorily by using a thermodynamic equation. • The temperature dependence of the surface tension was illustrated. • The effects of the mass fractions of MDEA and ionic liquids were demonstrated. -- Abstract: The surface tension (γ) of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]), 1-butyl-3-methylimidazolium bromide ([Bmim][Br]), (N-methyldiethanolamine(MDEA) + [Bmim][BF4]) and (MDEA + [Bmim][Br]) aqueous solutions were measured by using the BZY-1 surface tension meter. The temperature ranged from (293.2 to 323.2) K. The mass fraction of MDEA ranged from 0.35 to 0.45. A thermodynamic equation was proposed to model the surface tension of (MDEA + ionic liquids) (ILS) aqueous solutions and the calculated results agreed well with the experiments. The effects of temperature, mass fractions of MDEA and ILS on the surface tension were demonstrated on the basis of experiments and calculations

  18. Thermal properties of [Cr(NH3)6](BF4)3 studied by adiabatic and relaxation calorimetry

    International Nuclear Information System (INIS)

    Highlights: • Four solid phase transitions are observed between T = (9 and 300) K for [Cr(NH3)6](BF4)3. • Low temperature properties were investigated with relaxation calorimetry below T = 20 K. • For nonzero values of applied magnetic field well-defined Schottky anomaly appears. • Isothermal magnetization curve recorded up to 5 T was measured at T = 1.8 K. - Abstract: Four (solid–solid) phase transitions were detected in the temperature range of (9 to 300) K in polycrystalline [Cr(NH3)6](BF4)3 at TC1 = 240.7 K, TC2 = 108.0 K, TC3 = 91.9 K, and TC4 = 61.3 K by adiabatic calorimetry. The measurements by relaxation calorimetry were followed on lowering temperature from 20 K down to 0.35 K under six different external magnetic field values (9, 7, 5, 3, 1 and 0) T. For non-zero values of applied magnetic field well-defined Schottky anomaly appears. Magnetic heat capacity was calculated assuming the zero-field splitting for the decoupled Cr(III) ions. There is no discrepancy between the observed and calculated values. Isothermal magnetization curve recorded up to 5 T was measured at temperature of 1.8 K

  19. The Chlamydomonas PF6 Locus Encodes a Large Alanine/Proline-Rich Polypeptide That Is Required for Assembly of a Central Pair Projection and Regulates Flagellar Motility

    OpenAIRE

    Rupp, Gerald; O'Toole, Eileen; Porter, Mary E.

    2001-01-01

    Efficient motility of the eukaryotic flagellum requires precise temporal and spatial control of its constituent dynein motors. The central pair and its associated structures have been implicated as important members of a signal transduction cascade that ultimately regulates dynein arm activity. To identify central pair components involved in this process, we characterized a Chlamydomonas motility mutant (pf6-2) obtained by insertional mutagenesis. pf6-2 flagella ...

  20. First-principle investigation of the interactions between PtxRu55−x (x = 0, 13, 42, 55) nanoparticles and [BMIM][PF6] ionic liquid

    International Nuclear Information System (INIS)

    Highlights: • Interaction between PtRu nanoparticle and [BMIM][PF6] is performed by DFT calculations. • The structure of Pt13Ru42 nanoparticle is distorted induced by [BMIM][PF6]. • The d-band center show that catalytic activities of Pt13Ru42 and Ru55 are enhanced. • Two C atoms of [BMIM][PF6] form the bond with Pt13Ru42 nanoparticles. - Abstract: Density functional theory calculations have been performed to characterize the interactions between [BMIM][PF6] ionic liquid and icosahedral PtxRu55−x (x = 0, 13, 42, 55) nanoparticles. In Ru13Pt42–[BMIM][PF6], only one F atom of the anion form the bond with nanoparticle, resulting in the smallest interaction energy (−0.56 eV). While in Pt13Ru42–[BMIM][PF6], two F atoms of the anion together with two C atoms of cation form the bonds with nanoparticle, resulting in the biggest interaction energy (−10.65 eV). The interaction between [BMIM][PF6] and Pt13Ru42 is so strong that it induces a significant distortion in the original core–shell structure of Pt13Ru42. Moreover, after interacting with [BMIM][PF6], the Pt55, Pt13Ru42 and Ru55 nanoparticles become more stable based on the negative relaxation energy. The d-band centers of Pt13Ru42 and Ru55 shift from −1.90, −1.78 eV up to −1.78, −1.56 eV, suggesting that the catalytic activities of Pt13Ru42 and Ru55 are enhanced

  1. Preparation and Molten Salt as Performances of Room Electrolyte carbon Capacitor Based on Trifluoroacetamide n CarbonLiPF6 and

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    A novel room moRen salt with an eutectic temperature of about -62℃ is prepared using LiPF6 and trifluoroacetamide as precursors. And then its performance is evaluated in carbon-carbon electrochemical double layerdifferent molar ratios are characterized and then the liquid-solid phase diagram is presented. The electrochemical performance tests show that the as-prepared LiPF6/trifluoroacetamide molten salt is a promising electrolyte candidate for carboncarbon EDLCs.

  2. Studies on structural, thermal and AC conductivity scaling of PEO-LiPF6 polymer electrolyte with added ionic liquid [BMIMPF6

    Science.gov (United States)

    Chaurasia, S. K.; Saroj, A. L.; Shalu, Singh, V. K.; Tripathi, A. K.; Gupta, A. K.; Verma, Y. L.; Singh, R. K.

    2015-07-01

    Preparation and characterization of polymer electrolyte films of PEO+10wt.% LiPF6 + xwt.% BMIMPF6 (1-butyl-3-methylimidazolium hexafluorophosphate) containing dopant salt lithium hexafluorophosphate (LiPF6) and ionic liquid (BMIMPF6) having common anion PF6 - are reported. The ionic conductivity of the polymer electrolyte films has been found to increase with increasing concentration of BMIMPF6 in PEO+10 wt.% LiPF6 due to the plasticization effect of ionic liquid. DSC and XRD results show that the crystallinity of polymer electrolyte decreases with BMIMPF6 concentration which, in turn, is responsible for the increase in ionic conductivity. FTIR spectroscopic study shows the complexation of salt and/or ionic liquid cations with the polymer backbone. Ion dynamics behavior of PEO+LiPF6 as well as PEO+LiPF6 + BMIMPF6 polymer electrolytes was studied by frequency dependent conductivity, σ(f) measurements. The values σ(f) at various temperatures have been analyzed in terms of Jonscher power law (JPL) and scaled with respect to frequency which shows universal power law characteristics at all temperatures.

  3. Ab initio studies on [bmim][PF6]–CO2 mixture and CO2 clusters

    Indian Academy of Sciences (India)

    B L Bhargava; M Saharay; S Balasubramanian

    2008-06-01

    Ab initio molecular dynamics studies have been carried out on the room temperature ionic liquid, 1,n-butyl,3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and supercritical carbon dioxide mixture at room temperature and experimental density. Partial radial distribution functions (RDF) for different sites have been computed to see the organization of CO2 molecules around the ionic liquid. Several partial RDFs around the carbon atom of CO2 molecule are compared to find out that the CO2 has specific interaction with a carbon atom present in the imidazolium ring. The CO2 is also found to be very well organized around the terminal carbon atom of the butyl chain. The partial RDFs for the oxygen atoms around oxygen and carbon atoms of the CO2 suggests that there is very good organization of CO2 molecules around themselves even in the [bmim][PF6] – CO2 mixture. The instantaneous quadrupole moment tensor has been calculated for the anion and the cation. The ensemble average of diagonal components of quadrupole moment tensor of the cation have finite values, whereas the off-diagonal components of the cation and both the diagonal and off-diagonal components of the anion have the value of zero with a large standard deviation. The CPMD studies performed on CO2 clusters reveals the greater tendency of the clusters with more CO2 units, to deviate from the linear geometry.

  4. Ultra-fast and sensitive photo-induced phase switching in (EDO-TTF)2PF6

    International Nuclear Information System (INIS)

    Organic conductor (EDO-TTF)2PF6 crystal having 14 filled band shows a metal (M)-insulator (I) transition accompanied with Peierls transition, charge ordering, and anion ordering at transition temperature, TC=280K. This crystal is an important and fascinating candidate for photo-induced M-I transition because the multi-instability will afford sensitivity to the tiny stimulation. We make the report of the reflectivity change in (EDO-TTF)2PF6 crystal induced by the irradiation of femto-second (fs) pulsed laser (pulse width: 120fs, main wavelength: 800nm, repetition rate: 1kHz). The obtained results indicate that the highly efficient I-to-M transition occurs within 3ps in this material. Based on these results, the strong electron-lattice cooperative interaction is proved to play an essential role in the driving process of this M-I transition. Also, 14 filled materials, which show M-I transition, accompanied with the charge ordering, can be classified as fascinating candidates not only for superconductivity but also for photo-induced cooperative phenomena and application in phase switching devices

  5. Electrochemical fabrication of TiO2 nanoparticles/[BMIM]BF4 ionic liquid hybrid film electrode and its application in determination of p-acetaminophen

    International Nuclear Information System (INIS)

    A water soluble ionic liquid, 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIM]BF4), was incorporated into TiO2 nanoparticles to fabricate a hybrid film modified glassy carbon electrode (nano‐TiO2/[BMIM]BF4/GCE) through electrochemical deposition in a tetrabutyltitanate sol solution containing [BMIM]BF4. The obtained nano‐TiO2/[BMIM]BF4/GCEs were characterized scanning electronic microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). Electrochemical behaviors of p‐acetaminophen at the nano‐TiO2/[BMIM]BF4/GCEs were thoroughly investigated. Compared to the redox reaction of p‐acetaminophen using an unmodified electrode under the same conditions, a new reduction peak was observed clearly at 0.26 V with the modified electrode. In addition, the peak potential for the oxidation of p‐acetaminophen was found to shift negatively about 90 mV and the current response increased significantly. These changes indicate that the nano‐TiO2/[BMIM]BF4 hybrid film can improve the redox reactions of p‐acetaminophen in aqueous medium. Under optimum conditions, a linear relationship was obtained for the p‐acetaminophen solutions with concentration in the range from 5.0 × 10−8 to 5.0 × 10−5 M. The estimated detection limit was 1.0 × 10−8 M (S/N = 3). The newly developed method was applied for the determination of p-acetaminophen in urine samples. - Highlights: ► Nano-TiO2/[BMIM]BF4 hybrid film electrode was fabricated with electrodeposition. ► Voltammetric behavior of p-acetaminophen at the obtained electrode was investigated. ► The hybrid film electrode shows good electrocatalytic response to p-acetaminophen. ► p-acetaminophen in urine samples was successfully determined.

  6. Isothermal and non-isothermal crystallization kinetics of PVA + ionic liquid [BDMIM][BF4]-based polymeric films

    Science.gov (United States)

    Saroj, A. L.; Chaurasia, S. K.; Kataria, Shalu; Singh, R. K.

    2016-06-01

    The effect of ionic liquid (IL), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [BDMIM][BF4], on crystallization behavior of poly(vinyl alcohol) (PVA) has been studied by isothermal and non-isothermal differential scanning calorimetry techniques. The PVA + IL based polymer electrolyte films have been prepared using solution casting technique. To describe the isothermal and non-isothermal crystallization kinetics, several kinetic equations have been employed on PVA + IL based films. There is strong dependence of the peak crystallization temperature (Tc), relative degree of crystallity (Xt), half-time of crystallization (t1/2), crystallization rate constants (Avrami Kt and Tobin AT), and Avrami (n) and Tobin (nT) exponents on the cooling rate and IL loading.

  7. Synthesis, characterization and cytotoxic activities of the [RuCl2(NO)(dppp)(L)]PF6 complexes.

    Science.gov (United States)

    Golfeto, Camilla C; Von Poelhsitz, Gustavo; Selistre-de-Araújo, Heloísa S; de Araujo, Márcio P; Ellena, Javier; Castellano, Eduardo E; Lopes, Luiz G L; Moreira, Icaro S; Batista, Alzir A

    2010-05-01

    The synthesis and characterization of ruthenium compounds of the type [RuCl(2)(NO)(dppp)(L)]PF(6) [dppp=1,3-bis(diphenylphosphino)propane; L=pyridine, 4-methylpyridine, 4-phenylpyridine and dimethyl sulfoxide] are described. The complexes were characterized by elemental analysis, UV/Vis and infrared spectroscopy, cyclic voltammetry, and X-ray crystallography for the complexes with the pyridine and 4-methylpyridine ligands. In vitro evaluation of these nitrosyl complexes revealed cytotoxic activity from 7.1 to 19.0 microM against the MDA-MB-231 breast tumor cells and showed that, in this case, they are more active than the reference metallodrug cisplatin. The 1,3-bis(diphenylphosphino)propane and the N-heterocyclic ligands alone failed to show cytotoxic activities at the concentrations tested (maximum concentration utilized=200 microM). PMID:20117840

  8. Electrochemical behavior of Ru(H2bpp)2(PF6)2 and its interaction with bovine serum albumin (BSA)

    Institute of Scientific and Technical Information of China (English)

    Qiao Hua Wei; Li Jing Han; Jing Hua Chen; Fang Nan Xiao; Shen Liang Zeng; Guo Nan Chen

    2011-01-01

    In this paper, it was found that Ru(H2bpp)2(PF6)2 (H2bpp = 2,6-bis(pyrazol-3-yl)pyridine) complex had excellent electrochemical activity at the carbon paste electrode in the buffer solution of Tris-HCl (pH 7.0) with a couple reversible redox peaks at 0.296 V and 0.348 V, respectively. Voltammetry was used to investigate the electrochemical behavior of Ru(H2bpp)2(PF6)2 and the interaction between Ru(H2bpp)2(PF6)2 and bovine serum albumin (BSA). In the present of BSA, the oxidation peak current of Ru(H2bpp)2(PF6)2 complex was decreased linearly and the decrease of oxidation peak current of Ru(H2bpp)2(PF6)2 is proportional to BSA concentration from 0.1 to 2.5 mg/L with a detection limit 0.02 mg/L.

  9. [BMIM] [BF4] ionic liquid assistance effect on the crystallinity and morphology of Sb2S3 nanostructures synthesized by ultrasound

    International Nuclear Information System (INIS)

    Unidimensional crystalline Sb2S3 nanostructures were successfully synthesized by ultrasound irradiation assisted with the ionic liquid 1-n-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4]. The starting reagents were SbCl3, thioacetamide, absolute ethanol (AET), and the used ionic liquid was [BMIM][BF4]. The resultant materials were thermally annealed at 155 and 200 oC under controlled vacuum conditions. The experiments showed that IL assistance played a key role in the crystallinity and morphology of the obtained products. The resultant materials were characterized by powder X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray analysis (EDX). (author).

  10. NMR determination of the ordering of CH3NO2 co-intercalated with PF6-, AsF6-, or SbF6- in graphite

    International Nuclear Information System (INIS)

    Comparison of the intensities of the 19F and 1H NMR spectra of the graphite intercalation compound prepared by reaction of highly-oriented pyrolytic graphite with NO2PF6 dissolved in CH3NO2 showed that the number of CH3NO2 molecules present per PF6- ion varied from 1.64 to 1.14 depending upon sample preparation. The 1H NMR spectra of CH3NO2 in single pieces of HOPG intercalated with PF6-, AsF6-, or SbF6- show 1:2:1 triplets due to dipolar splittings resulting from partial ordering of the CH3NO2 molecules with the molecular symmetry axis parallel to the graphite planes. (Auth.)

  11. Synthesis and Structural Characterization of the Tetrakis(methimazolyl)borates Li[Bmt4] and [Ru(p-cymene)(Bmt4)][PF6

    OpenAIRE

    Kunz, Kerstin; Bolte, Michael; Wagner, Matthias; Lerner, Hans-Wolfram

    2009-01-01

    Abstract The lithium tetrakis(methimazolyl)borate Li[Bmt4] is accessible from the reaction of Li[BH4] with four equivalents of methimazole. The crystal structure of Li[Bmt4] supported by four water molecules is described. Reaction of Li[Bmt4] with [Ru(p-cymene)Cl2]2 and subsequent treatment with NH4PF6 in CH3CN results in the formation of the complex [Ru(p-cymene)(Bmt4)][PF6]. In addition, we report the result of the X-ray structure analysis of the chiral Ru complex [Ru(p-cymene)(B...

  12. [PAMIM][PF6]离子液体作为气相色谱固定相的研究%Research of [PAMIM][PF6] ionic liquid as stationary phase for gas chromatography

    Institute of Scientific and Technical Information of China (English)

    郑建华; 申书昌; 陈光

    2013-01-01

    以1-甲基咪唑、氯丙烯、六氟磷酸钾为原料合成了一种聚合离子液体聚-1-丙烯基-3-甲基咪唑六氟磷酸盐([PAMIM][PF6]).通过红外光谱法和核磁共振波谱法表征了产物的结构,通过热重分析,考察了其分解温度,并确定了此离子液体作为气相色谱固定液的最高使用温度.以离子液体作为气相色谱固定相,制备了色谱填充柱,通过对烃系物、醇系物的分离,考察了色谱柱的分离效果、极性.%A kind of polymer ionic liquid which is called poly (l-allyl-3- methylimidazolium hexafluo-rophosphate) was synthesized using 1-methylimidazole, allyl chloride and hexafluorophosphate as raw meterials. The structure of the ionic liquid was characterized by IR and NMR. The maximum.operating of this ionic liquid temperature as gas chromatography stationary phase was confirmed by TGA The chromatography column was made of the ionic liquids and supporter .The separating character and polarity of the chromatography column were studied by the hydrocarbons and alcohols mixtures respectively.

  13. First-Principles United Atom Force Field for the Ionic Liquid BMIM(+)BF4(-): An Alternative to Charge Scaling.

    Science.gov (United States)

    Son, Chang Yun; McDaniel, Jesse G; Schmidt, J R; Cui, Qiang; Yethiraj, Arun

    2016-04-14

    Molecular dynamics study of ionic liquids (ILs) is a challenging task. While accurate fully polarizable atomistic models exist, they are computationally too demanding for routine use. Most nonpolarizable atomistic models predict diffusion constants that are much lower than experiment. Scaled charge atomistic models are cost-effective and give good results for single component ILs but are in qualitative error for the phase behavior of mixtures, due to inaccurate prediction of the IL cohesive energy. In this work, we present an alternative approach for developing computationally efficient models that importantly preserves both the correct dynamics and cohesive energy of the IL. Employing a "top-down" approach, a hierarchy of coarse-grained models for BMIM(+)BF4(-) are developed by systematically varying the polarization/atomic resolution of the distinct functional groups. Parametrization is based on symmetry-adapted perturbation theory (SAPT) calculations involving the homomolecular species; all cross interactions are obtained from mixing rules, and there are no adjustable parameters. We find that enhanced dynamics from a united-atom description counteracts the effect of reduced polarization, enabling computationally efficient models that exhibit quantitative agreement with experiment for both static and dynamic properties. We give explicit suggestions for reduced-description models that are computationally more efficient, more accurate, and more fundamentally sound than existing nonpolarizable atomistic models. PMID:26900644

  14. Initiation and growth of a single pit on 316L stainless steel: Influence of SO42- and ClO4- anions

    International Nuclear Information System (INIS)

    In this paper, an ion micro dispenser (IMD) was used to initiate a single pit by generating chloride anions above a 316L stainless steel electrode in either H2SO4 or HClO4 electrolyte. The current variations with respect to time provided an unambiguous characterization of the single pit evolution. Different pit shapes were observed depending on both the nature of the electrolyte and potential applied to the electrode. Substituting SO42- for ClO4- gave smaller (in diameter) but deeper pits at the early stage of pitting. However, when using a different setup that allows the sustaining of the pit propagation with a continuous supply of Cl-, the deeper pits were observed in HClO4 rather than H2SO4. The formation of an iron sulphate salt film at the bottom of the pit by precipitation of dissolution products in H2SO4 slowed down the corrosion rate. At high potentials, the repassivation mechanism outweighed the metal dissolution in the ClO4- containing solution. (authors)

  15. Crystal structure and characterization of the novel NH+⋯N hydrogen bonded polar crystal [NH2(CH2)4NH][BF4

    Science.gov (United States)

    Wojtaś, M.; Gaģor, A.; Czupiński, O.; Medycki, W.; Jakubas, R.

    2012-03-01

    Dielectric properties and phase transitions of the piperazinium tetrafluoroborate ([NH2(CH2)4NH][BF4], abbreviated as PFB) crystal are related to the one-dimensional arrangement of the cations linked by the bistable NH+⋯N hydrogen bonds and molecular motions of the [BF4]- units. The crystal structure of [NH2(CH2)4NH][BF4] is monoclinic at room temperature with the polar space group Pn. The polar/acentric properties of the room temperature phase IV have been confirmed by the piezoelectric and pyroelectric measurements. DSC measurements show that the compound undergoes three first-order structural phase transitions: at 421/411 K (heating/cooling), at 386/372 K and at 364/349 K. 1H and 19F NMR measurements indicate the reorientational motions of [BF4]- anions and piperazinium(+) cations as well as the proton motion in the hydrogen-bonded chains of piperazine along the [001] direction. Over the phase I the isotropic reorientational motions or even self-diffusion of the cations and anions are expected. The conductivity measurements in the vicinity of the II-I PT indicate a superionic phase over the phase I.

  16. Mixing thermodynamic properties of 1-butyl-4-methylpyridinium tetrafluoroborate [b4mpy][BF4] with water and with an alkan-1ol (methanol to pentanol)

    International Nuclear Information System (INIS)

    This article presents a study of the behaviour in solution of 1-butyl-4-methylpyridinium tetrafluoroborate [b4mpy][BF4] in water and in the first five alkanols of the series methanol to pentan-1-ol. The excess enthalpies, HmE and volumes, VmE were determined at the temperatures (298.15 and 318.15) K. At these temperatures, the [b4mpy][BF4] was completely miscible in water, methanol, and ethanol, but only partially miscible in the other alkanols. A solubility study was carried out and the (liquid + liquid) equilibria of the ([b4mpy][BF4] + alkanol) systems were experimentally determined, evaluating zones of complete miscibility and determining the UCST in each case. The mixtures with water gave positive values of HmE and VmE, being also positive the changes of these quantities with temperature. The mixtures with alkanols gave values of HmE>0 and VmEmE/dT)p>0 and (dVmE/dT)p4]. Excess properties were correlated with a suitable equation and the area and volume parameters were calculated for [b4mpy][BF4

  17. Crystal structure and characterization of the novel NH+⋯N hydrogen bonded polar crystal [NH2(CH2)4NH][BF4

    International Nuclear Information System (INIS)

    Dielectric properties and phase transitions of the piperazinium tetrafluoroborate ([NH2(CH2)4NH][BF4], abbreviated as PFB) crystal are related to the one-dimensional arrangement of the cations linked by the bistable NH+⋯N hydrogen bonds and molecular motions of the [BF4]− units. The crystal structure of [NH2(CH2)4NH][BF4] is monoclinic at room temperature with the polar space group Pn. The polar/acentric properties of the room temperature phase IV have been confirmed by the piezoelectric and pyroelectric measurements. DSC measurements show that the compound undergoes three first-order structural phase transitions: at 421/411 K (heating/cooling), at 386/372 K and at 364/349 K. 1H and 19F NMR measurements indicate the reorientational motions of [BF4]− anions and piperazinium(+) cations as well as the proton motion in the hydrogen-bonded chains of piperazine along the [001] direction. Over the phase I the isotropic reorientational motions or even self-diffusion of the cations and anions are expected. The conductivity measurements in the vicinity of the II–I PT indicate a superionic phase over the phase I. - Graphical abstract: It must be emphasized that the titled compound represents the first organic–inorganic simple salt containing the single-protonated piperazinium cation which was studied by means of the wide variety of experimental techniques. A survey of Cambridge Structural Database (CSD version 5.32 (November 2010) and updates (May 2011)) for structure containing the piperazinium cations yields 248 compounds with the doubly protonated piperazinium(2+) cations and only eight compounds with the singly protonated piperazinium(+) cations. Among these structures only one is the hybrid organic–inorganic material. This is piperazinium nitrate characterized structurally. The crystal packing of [NH2(CH2)4NH][BF4], phase IV. The dashed lines stand for the hydrogen bonds. The hydrogen bonds to BF4 groups are not included for the picture quality Highlights:

  18. Activated carbon and single-walled carbon nanotube based electrochemical capacitor in 1 M LiPF6 electrolyte

    International Nuclear Information System (INIS)

    Highlights: • Activated carbon and single-walled CNT based electrochemical capacitor. • Electrochemical analysis by means of CV, charge/discharge and impedance. • 1 M LiPF6 non-aqueous solution as an electrolyte. • AC/SWCNT electrode exhibits a maximum capacitance of 60.97 F g−1. - Abstract: Carbon nanotubes have been extensively studied because of their wide range of potential application such as in nanoscale electric circuits, textiles, transportation, health, and the environment. Carbon nanotubes feature extraordinary properties, such as electrical conductivities higher than those of copper, hardness and thermal conductivity higher than those of diamond, and strength surpassing that of steel, among others. This research focuses on the fabrication of an energy storage device, namely, an electrochemical capacitor, by using carbon materials, i.e., activated carbon and single-walled carbon nanotubes, of a specific weight ratio as electrode materials. The electrolyte functioning as an ion carrier is 1 M lithium hexafluorophosphate. Variations in the electrochemical performance of the device, including its capacitance, charge/discharge characteristics, and impedance, are reported in this paper. The electrode proposed in this work exhibits a maximum capacitance of 60.97 F g−1 at a scan rate of 1 mV s−1

  19. Proton NMR study of spin density wave thermal fluctuations in (TMTSF)2PF6, where TMTSF is tetramethyltetraselenafulvalene

    International Nuclear Information System (INIS)

    Measurements of the proton spin-lattice relaxation rate (1/T1) at a pressure of 1 bar in a single crystal of (TMTSF)2PF6 (TMTSF is tetramethyltetraselenafulvalene) are reported for the magnetic field in the range 0.25-1.48 T aligned along the b'- and c*-axes over the temperature range 2-30 K. The methyl group rotation contribution to 1/T1 is subtracted to obtain the spin density wave (SDW) contribution. Through measurements of 1/T1 below and above the spin flop transition it is determined that phason fluctuations of the SDW are responsible for most of the relaxation. Depinning the SDW's by an electric field leaves 1/T1 nearly unchanged, which indicates that the SDW and its fluctuation rate near 108 rad/s persist when the SDW is sliding. Analysis of the peak in 1/T1 near 3 K on the applied magnetic field suggests that it represents a slowing of thermally activated fluctuations with an activation energy Δ/kB = 18.3 ± 4.0 K, which is close to the single particle gap for this material. The contribution of critical fluctuations to 1/T1 is consistent with the transition being weakly first order. Unlike the relaxation in the ordered phase, the contribution of the critical fluctuations is isotropic and has little, if any dependence on magnetic field. (orig.)

  20. Enzymatic synthesis of phytosterol esters catalyzed by Candida rugosa lipase in water-in-[Bmim]PF6 microemulsion.

    Science.gov (United States)

    Zeng, Chaoxi; Qi, Suijian; Li, Zhigang; Luo, Riming; Yang, Bo; Wang, Yonghua

    2015-05-01

    A water-in-ionic liquid microemulsion ([Bmim]PF6/Tween20/H2O) was applied as reusable reaction medium to esterify phytosterols with fatty acid by Candida rugosa lipase (CRL) successfully. Two kinds of commercial CRLs, AY30 and AYS which cannot effectively catalyze esterification in conventional reaction system were found effective in the microemulsion system. Effects of reaction parameters on esterification were investigated; results showed that the conversion rate of 87.9 and 95.1 % was obtained in 24 and 48 h of reaction, respectively, under the optimized condition: the molar ratio of water to Tween 20 (w 0 value) at 5.4, Tween 20 at a concentration of 305 mM, 50 °C,pH 7.4, 10 % of enzyme loading (w/w, with respect to total reactants), and phytosterols/lauric acid molar ratio of 1:2. Moreover, by using n-hexane as the extraction agent, the lipase-encapsulated microemulsion could be reused at least seven times (>168 h) without significant changes in the conversion rate, while achieving a purpose of simple separation and purification. PMID:25575761

  1. Reaction of the Anticancer Organometallic Ruthenium Compound, [(η6-p-CymeneRu(ATSCCl]PF6 with Human Serum Albumin

    Directory of Open Access Journals (Sweden)

    Floyd A. Beckford

    2010-01-01

    Full Text Available The reaction of [(η6-p-cymeneRu(ATSCCl]PF6 (ATSC =9-anthraldehyde thiosemicarbazone with human serum albumin was investigated at different temperatures using fluorescence and infrared spectrophotometry. The binding constant, K, for the reaction was determined using a number of different methods. Using a modified Stern-Volmer equation, K was determined to be 9.09×104,12.1×104, and 13.1×104 M−1 at 293 K, 298 K, and 308 K, respectively. A thermodynamic analysis showed that the reaction is spontaneous with ΔG being negative. The enthalpy of reaction ΔH=16.5 kJ mol−1 and the entropy of reaction ΔS=152 Jmol−1K−1. The values of ΔH and ΔS suggest that hydrophobic forces are dominant in the mode of interaction and that the process is mostly entropy driven.

  2. Novel electrolyte mixtures based on dimethyl sulfone, ethylene carbonate and LiPF6 for lithium-ion batteries

    Science.gov (United States)

    Hofmann, Andreas; Hanemann, Thomas

    2015-12-01

    In this study, novel electrolyte mixtures for Li-ion cells are presented which are composed of ethylene carbonate/dimethyl sulfone (80:20 wt./wt.) as a solvent mixture and LiPF6, lithium bis(oxalato)borate and lithium difluoro(oxalato)borate as conducting salts. The main advantages of the solvent mixture are high flash points of >140 °C which enhance the intrinsic safety of Li-ion cells while maintaining good cell performance above 0-5 °C. The movability of the lithium ions in the electrolyte is investigated via programmed current derivative chronopotentiometry. It is found that pure electrolyte properties cannot necessarily predict the electrolyte behavior in real Li-ion cells but the complex interplay between electrolytes, electrode materials and separators has to be taken into account. Using the newly developed electrolytes, it is possible to achieve C-rates up to 1.5C with >80% of the initial specific discharge capacity (25 °C). Within 200 cycles during one month in cell tests (C||NMC) it is proven that the retention of the specific capacity is >98% of the third discharge cycle in dependence of the conducting salt.

  3. Hydrolysis mechanisms for the organopalladium complex [Pd(CNN)P(OMe)3]BF4 in sulfuric acid.

    Science.gov (United States)

    García, Begoña; Hoyuelos, Francisco J; Ibeas, Saturnino; Muñoz, María S; Peñacoba, Indalecio; Leal, José M

    2009-08-13

    The acid-catalyzed hydrolysis of the organopalladium complex [Pd(CNN)P(OMe)3]BF4 species was monitored spectrophotometrically at different sulfuric acid concentrations (3.9 and 11.0 M) in 10% v:v ethanol-water over the 25-45 degrees C temperature range and in 30% and 50% (v/v) ethanol-water at 25 degrees C. Two acidity regions (I and II) could be differentiated. In each of the two regions the kinetic data pairs yielded two different rate constants, k(1obs) and k(2obs), the former being faster. These constants were fitted by an Excess Acidity analysis to different hydrolyses mechanisms: A-1, A-2, and A-SE2. In region I ([H2SO4] 7.0 M), a switchover was observed from an A-1 mechanism (k(0,A1) = 1.3 x 10(-4) s(-1)) to an A-2 mechanism (k(0,A2) = 3.6 x 10(-3) M(-1) s(-1)). The temperature effect on the rate constants in 10% (v/v) ethanol-water yielded positive DeltaH and negative DeltaS values, except for the A-1 mechanism, where DeltaS adopted positive values throughout. The solvent permittivity effect, epsilonr, revealed that k(1obs)(av) and k(0,A2) dropped with a fall in epsilonr, whereas the k(0,ASE2) value remained unaffected. The set of results deduced is in line with the schemes put forward. PMID:19621916

  4. Electrochemical characterisation and modelling of the mass transport phenomena in LiPF6-EC-EMC electrolyte

    International Nuclear Information System (INIS)

    The conductivity, the salt diffusion coefficient, the lithium-ion transport number and the thermodynamic factor of the salt and the solvent were reported for LiPF6 in EC:EMC (3:7) at 25 deg. C and for concentrations between 0.2 and 2.0 mol/dm3. The mass transport in the electrolyte was fully characterised by combining three types of electrochemical experiments; concentration cells, galvanostatic polarisation experiments and electrochemical impedance measurements with a mathematical description of the mass transport in the electrolyte. The apparent salt diffusion coefficient had a local maximum in the concentration range, while the viscosity-dependent salt diffusion coefficient decreased from 4.1 x 10-10 m2/s at 0.2 mol/dm3 to 4.4 x 10-11 m2/s at 2.0 mol/dm3. Both the thermodynamic factor and the conductivity varied strongly with the concentration. The conductivity had a maximum of 9.5 mS/cm at 1.0 mol/dm3. The lithium-ion transport number with respect to the room decreased with increasing salt concentration, with a maximum of 0.37 at 0.2 mol/dm3 in the concentration range. The Maxwell-Stefan diffusivities and the electrolyte potential drop in a lithium-ion battery at steady state were lastly calculated from the obtained transport properties. An analysis of the characterisation method was also done on the basis of the characterisation results

  5. Design and Fabrication of a 200N Thrust Rocket Motor Based on NH4ClO4+Al+HTPB as Solid Propellant

    Science.gov (United States)

    Wahid, Mastura Ab; Ali, Wan Khairuddin Wan

    2010-06-01

    The development of rocket motor using potassium nitrate, carbon and sulphur mixture has successfully been developed by researchers and students from UTM and recently a new combination for solid propellant is being created. The new solid propellant will combine a composition of Ammonium perchlorate, NH4ClO4 with aluminium, Al and Hydroxyl Terminated Polybutadiene, HTPB as the binder. It is the aim of this research to design and fabricate a new rocket motor that will produce a thrust of 200N by using this new solid propellant. A static test is done to obtain the thrust produced by the rocket motor and analyses by observation and also calculation will be done. The experiment for the rocket motor is successful but the thrust did not achieve its required thrust.

  6. Spectroscopic and quantum-chemical investigation of association of ions in acetonitrile - LiX (X=I, ClO4, NCS) systems

    International Nuclear Information System (INIS)

    Data on association constants of ions in acetonitrile-salt binary systems, obtained from the data on intensity of IR absorption bands of acetonitrile (Acn) molecules contained in solvate shells of Li+ cations, have been analyzed. Using the CCP MO LCAO semiempirical method in the PPDP approximation, electronic structure of acetonitrile molecule and AcnkLi+ and AcnmLi+X- complexes has been studied. It is ascertained that relative stability of ionic pairs Acn3Li+X-, estimated by the squares of their dipole momenta (characterizing solvation energy) increases in the series X=I, ClO4, NCS in agreement with data of spectroscopic experiment, according to which the constant of ion association for LiNCS solution in acetonitrile is much higher than for the systems CH3CN-LiI and CH3CN-LiClO4. 13 refs.,2 figs., 2 tabs.64

  7. Extraction of penicillin G by aqueous two-phase system of [Bmim]BF4/NaH2PO4

    Institute of Scientific and Technical Information of China (English)

    LIU Qingfen; HU Xuesheng; WANG Yuhong; YANG Ping; XIA Hansong; YU Jiang; LIU Huizhou

    2005-01-01

    A novel approach for the extraction of penicillin G by aqueous two-phase system comprised of hydrophilic ionic liquid [Bmim]BF4 (1-butyl-3- methylimidazolium tetrafluoroborate) and NaH2PO4 is reported. The effects of some important parameters involving the concentration of NaH2PO4, the concentration of penicillin G, the amount of [Bmim]BF4 on the formation of aqueous two-phase system and the extraction yield of penicillin were investigated. The primary result shows that the ATPS can take advantage of penicillin concentrated in upper phase at higher pH value for penicillin extraction from its aqueous solution without emulsification.

  8. Physicochemical properties and electrochemical performance of [ Pmim ] [ ClO4 ] ionic liquid electrolyte in supercapacitor%[ Pmim ][ ClO4]电解质的物化性质及其在超级电容器中的性能研究

    Institute of Scientific and Technical Information of China (English)

    武宣宇; 李美超; 张鑫源; 张庆国

    2015-01-01

    A novel ionic liquid 1 -Pentyl -3 -methylimidazolium perchlorate salts ([ Pmim] ClO4 ) was synthesized by two -steps method .The density , surface tension , and electrical conductivity of the ionic liquid were investigated in different temperatures .A supercapacitor composed of the activated carbon electrode and the [ Pmim] ClO4 electrolyte was prepared .The electrochemical performance of the supercapacitor was studied by cy-clic voltammograms, alternating current resistance , and constant current charge -discharge tests, respectively. The results showed that the density and the surface tension of [ Pmim] ClO4 decreased with the increase of tem-perature.The working voltage window of the supercapacitor reached to 5.0 V.Moreover, the capacitor possessed typical capacitance characteristic , good reversibility , and better cycleability , which showed a great potential of this ionic liquid electrolyte in supercapacitor applications .%采用两步法设计合成了一种新型离子液体电解质(液)1-戊基-3-甲基咪唑高氯酸盐([ Pmim][ ClO4]),对这种电解质的密度、表面张力、电导率等物化性质进行了测定.并将其与活性炭电极组装成超级电容器,通过交流阻抗、循环伏安及恒流充放电等测试手段对其电化学性能进行了研究.测试结果表明,该离子液体的密度和表面张力都随温度升高而减小,超级电容器的电化学窗口可以达到5.0 V,并且具有良好的电容特性、可逆性及循环特性,是一种具有应用潜力的超级电容器电解液.

  9. Organic-inorganic compounds with strong nonlinear optical properties based on 2,4,6-trimethylpyridinium and tetrahedral BF4- networks

    Science.gov (United States)

    Wojtaś, Maciej; Bil, Andrzej; Jakubas, Ryszard; Gągor, Anna; Pietraszko, Adam; Czupiński, Olaf; Tylczyński, Zbigniew; Isakov, Dmitry

    2011-04-01

    A different organic-inorganic crystal—[2,4,6-trimethylpyridinium][BF4]—of nonlinear optical properties at room temperature was synthesized and characterized. The compound is built up of the organic [2,4,6-trimethylpyridinium] cations incorporated into inorganic, tetrahedral BF4 anions. It crystallizes at room temperature in the polar space group Pmn21, and undergoes three first-order phase transitions at [cooling (heating)] 241 (245) K, 297 (328) K, and 389 (406) K. The lowest temperature ferroic phase transition (ferroelastic; mm2→m type) is related to the significant pyroelectric effect. The compound was studied by single-crystal x-ray diffraction at several temperatures, using thermal (differential scanning calorimetry and thermogravimetric analysis) methods and dielectric spectroscopy. The piezoelectric, pyroelectric, and second-harmonic generation (SHG) properties were determined. Density-functional theory calculations in two stable phases are given. The [2,4,6-trimethylpyridinium][BF4] crystal exhibits a SHG efficiency of 1.7 times that of KDP. The mechanism of structural phase transitions in the title compound is discussed.

  10. Studies on the micropolarities of bmimBF4/TX-100/toluene ionic liquid microemulsions and their behaviors characterized by UV-visible spectroscopy.

    Science.gov (United States)

    Li, Na; Gao, Yan'an; Zheng, Liqiang; Zhang, Jin; Yu, Li; Li, Xinwei

    2007-01-30

    Ionic liquids (ILs), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), were substituted for polar water and formed nonaqueous microemulsions with toluene by the aid of nonionic surfactant TX-100. The phase behavior of the ternary system was investigated, and microregions of bmimBF4-in-toluene (IL/O), bicontinuous, and toluene-in-bmimBF4 (O/IL) were identified by traditional electrical conductivity measurements. Dynamic light scattering (DLS) revealed the formation of the IL microemulsions. The micropolarities of the IL/O microemulsions were investigated by the UV-vis spectroscopy using the methyl orange (MO) and methylene blue (MB) as absorption probes. The results indicated that the polarity of the IL/O microemulsion increased only before the IL pools were formed, whereas a relatively fixed polar microenvironment was obtained in the IL pools of the microemulsions. Moreover, UV-vis spectroscopy has also shown that ionic salt compounds such as Ni(NO3)2, CoCl2, CuCl2, and biochemical reagent riboflavin could be solubilized into the IL/O microemulsion droplets, indicating that the IL/O microemulsions have potential application in the production of metallic or semiconductor nanomaterials, and in biological extractions or as solvents for enzymatic reactions. The IL/O microemulsions may have some expected effects due to the unique features of ILs and microemulsions. PMID:17241018

  11. Lithium difluoro(oxalate)borate and LiBF4 blend salts electrolyte for LiNi0.5Mn1.5O4 cathode material

    Science.gov (United States)

    Zhou, Hongming; Xiao, Kaiwen; Li, Jian

    2016-01-01

    The electrochemical behaviors of lithium difluoro(oxalate)borate (LiODFB) and LiBF4 blend salts in ethylene carbonate + dimethyl carbonate + ethyl(methyl) carbonate (EC + DMC + EMC, 1:1:1, by wt.) have been investigated for LiNi0.5Mn1.5O4 cathode in lithium-ion batteries. The electric conductivity tests are utilized to examine the relationship among solution conductivity, the electrolyte composition and temperature. Through cyclic voltammetry, charge-discharge test and AC impedance measurements, we compare the capacity and cycling efficiency of LNMO cathode in different electrolyte systems at different temperatures and discharge current rates. Scanning electron microscopy (SEM) analysis and X-ray photoelectron spectroscopy (XPS) are served to analyze the surface nature of LNMO cathode after cycles at elevated temperature. These results demonstrate that LNMO cathode can exert excellent electrochemical performance with the increase of LiODFB concentration at room temperature and elevated temperature and it is found that just slight LiBF4, mixed with LiODFB as blend salts, can strikingly improve the cyclability at -20 °C, especially in high-rate cycling. Grouped together, the optimum LiODFB/LiBF4 molar ratio is around 4:1, which can present an excellent affinity to LNMO cathode in a wide electrochemical window.

  12. Densities and Viscosities of 1-butyl-3-methylimidazolium Hexafluorophosphate [bmim][PF6]+CO2 Binary System:Determination and Correlation

    Institute of Scientific and Technical Information of China (English)

    乔燕; 闫方友; 夏淑倩; 马沛生

    2013-01-01

    A gas-dissolving device was designed and connected to the falling-body viscometer, which was used to determine the viscosities of liquids in our lab before. The equipment can be used to determine the gas composition, the densities and viscosities of the solution at the same time. The densities and viscosities of [bmim][PF6]+CO2 binary system were determined in the temperature range of 313.2 to 413.2 K and pressure range of 5.0 to 25.0 MPa by the equipment. Then the viscosities of [bmim][PF6]+CO2 binary system at constant temperature, constant pres-sure, and different temperature and pressure were correlated, respectively. For the correlation at different tempera-ture and different pressure for different concentration mixtures the average relative deviation ARD is 0.037.

  13. Pd nanoparticles immobilized in [bmim][PF6] supported on laponite clay as highly recyclable catalysts for the Mizoroki-Heck reaction

    OpenAIRE

    Martínez, Alejandro V.; Mayoral, José A.; García, José I.

    2014-01-01

    Mizoroki-Heck cross-couplings of aryl halides catalyzed by highly active palladium nanoparticles, immobilized on [bmim][PF6] films supported on laponite clay, have been investigated. The reactions are performed at 100 °C in solventless conditions to afford the corresponding coupling products in good to excellent yields under non-anhydrous and non-degassed conditions. Highly recoverable catalytic systems have been prepared, allowing up to 17 catalytic cycles with good yields and excellent sele...

  14. Solvent extraction of Pu(IV) by CMPO in 1-octyl 3-methyl imidazolium hexa fluorophosphate (C8mim PF6)

    International Nuclear Information System (INIS)

    The solvent extraction of Pu(IV) from nitric acid by octyl phenyl diisobutyl carbamoyl methyl phosphine oxide (CMPO) dissolved in a room temperature ionic liquid (RTIL) viz. 1-octyl 3- methyl imidazolium hexa fluorophosphate (C8mimPF6) was carried out and the stoichiometry of extracted complex was determined. Slope analysis does not indicate the extraction of neutral Pu(NO3)4. CMPO complex in to the RTIL phase. (author)

  15. Low-temperature thermodynamic investigation of the sulphur organic salts (TMTTF)2PF6 and (TMTTF)2Br (TMTTF ≡ tetramethyltetrathiafulvalene): I. General aspects

    International Nuclear Information System (INIS)

    A detailed thermodynamical investigation of the quasi-one-dimensional sulphur-based organic salts (TMTTF)2PF6 and (TMTTF)2Br is presented in the temperature range from 30 mK to 7 K. In this part (part I), we consider the general aspects of the low-temperature specific heat of these materials in relationship with their ground states and we compare them with those previously measured for selenium members of the same family. All these compounds exhibit very similar thermodynamical behaviour, despite a variety of electronic ground states: spin-Peierls for (TMTTF)2PF6, commensurate antiferromagnetic spin modulation for (TMTTF)2Br, incommensurate spin-density wave for (TMTSF)2PF6 (TMTSF≡tetramethyltetraselenafulvalene). We show that the low-energy excitations which are predominant below 1 K have a similar character to that observed in glassy systems, at least on short timescales of measurements. The dynamical aspects of the non-equilibrium thermodynamics will be presented separately in the following part (part II). (author)

  16. Effects of irradiation disorder on the insulating phases of (TMTSF) (DMTCNQ) and (TMTSF)2PF6: the stabililization of the metallic state by a weak disorder

    International Nuclear Information System (INIS)

    The ordering of charge density waves (CDW) drives the organic conductor (TMTSF) (DMTCNQ) to an insulating state below 49 K while the magnetic ordering of spin density waves (SDW) produces the same effect around 20 K in (TMTSF)2PF6. X-ray irradiation has been used to introduce defects in low concentration of the order of 10-3 mole fraction. The mosaicity induced by these defects in the CDW or SDW phases has important consequences on the transport and magnetic properties of the two compounds. Measurements of conductivity, Hall effect, magnetoresistance, thermopower, electron spin resonance (EPR) linewidth, g-factor and susceptibility are presented and discussed. A X-ray diffuse scattering study of the disordered CDW in (TMTSF) (DMTCNQ) provides an accurate determination of the longitudinal and transverse coherence lengths of the CDW's. It shows that each defect fixes the phase rigidly in a volume containing 3 chain segments of 10 molecules. In (TMTSF)2PF6, the EPR linewidth is used to follow the magnetic ordering under irradiation. In both compounds, the coherence loss of the low temperature condensed phases produces a large increase of the number of free carriers in irradiated samples. Even at low doses, the mobility of these carriers decreases quickly under irradiation in (TMTSF)2PF6, while it changes much more slowly in (TMTSF) (DMTCNQ)

  17. Toward new organometallic architectures: synthesis of carbene-centered rhodium and palladium bisphosphine complexes. stability and reactivity of [PC(BIm)PRh(L)][PF6] pincers.

    Science.gov (United States)

    Plikhta, Andriy; Pöthig, Alexander; Herdtweck, Eberhardt; Rieger, Bernhard

    2015-10-01

    In this article, we report the synthesis of a tridentate carbene-centered bisphosphine ligand precursor and its complexes. The developed four-step synthetic strategy of a new PC(BIm)P pincer ligand represents the derivatization of benzimidazole in the first and third positions by (diphenylphosphoryl)methylene synthone, followed by phosphine deprotection and subsequent insertion of a noncoordinating anion. The obtained ligand precursor undergoes complexation, with PdCl2 and [μ-OCH3Rh(COD)]2 smoothly forming the target organometallics [PC(BIm)PPdCl][PF6] and [PC(BIm)PRh(L)][PF6] under mild hydrogenation conditions. A more detailed study of the rhodium complexes [PC(BIm)PRh(L)][PF6] reveals significant thermal stability of the PC(BIm)PRh moiety in the solid state as well as in solution. The chemical behavior of 1,3-bis(diphenylphosphinomethylene)benzimidazol-2-ylrhodium acetonitrile hexafluorophosphate has been screened under decarbonylation, hydrogenation, and hydroboration reaction conditions. Thus, the PC(BIm)PRh(I) complex is a sufficiently stable compound, with the potential to be applied in catalysis. PMID:26390389

  18. Crystal structures and magnetic properties of the honeycomb-lattice antiferromagnet M2(pymca)3(ClO4), (M = Fe, Co, Ni)

    Science.gov (United States)

    Honda, Zentaro; Kodama, Takafumi; Hagiwara, Masayuki; Kida, Takanori; Okutani, Akira; Sakai, Masamichi; Fukuda, Takeshi; Kamata, Norihiko

    2016-09-01

    We report on the syntheses, crystal structures, and magnetic properties of a series of transition metal coordination polymers M2(pymca)3(ClO4), (pymca = pyrimidine-2-carboxylic acid, M = Fe (1), Co (2), and Ni (3)). These compounds are found to crystallize in a trigonal crystal system, space group P31m, with the lattice constants a = 9.727 Å and c = 5.996 Å for 1, a = 9.608 Å and c = 5.996 Å for 2, and a = 9.477 Å and c = 5.958 Å for 3 at room temperature. In these compounds, each pymca ligand connects to two M2+ ions, forming a honeycomb network in the ab plane. The temperature dependences of magnetic susceptibilities in these compounds show broad maxima, indicating antiferromagnetic interactions within two-dimensional honeycomb layers. We also observed an antiferromagnetic phase transition at low temperatures by magnetic susceptibility and heat capacity measurements. From the crystal structures and magnetic properties, we conclude that the compounds 1, 2, and 3 are good realizations of honeycomb-lattice antiferromagnets.

  19. Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI] and [EMIM][BF4

    Science.gov (United States)

    Haskins, Justin B.; Bennett, William R.; Hernandez-Lugo, Dione M.; Wu, James; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

    2014-01-01

    Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-Nbutylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-Npropylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of x(sub Li) we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing x(sub Li), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of x(sub Li) is approximately 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 - 0.3 mS/cm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

  20. Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI], [EMIM][BF4

    Science.gov (United States)

    Haskins, Justin B.; Bennett, William R.; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W., Jr.; Lawson, John W.

    2014-01-01

    Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

  1. On structural phase transitions in 4-aminopyridinium fluoroborate, [4-NH 2C 5H 5N][BF 4]: differential scanning calorimetry, dielectric and infrared studies

    Science.gov (United States)

    Czupiński, O.; Jakubas, R.; Pietraszko, A.

    2004-10-01

    Crystal structure of the 4-aminopyridinium tetrafluoroborate, [4-NH 2C 5H 5N][BF 4], has been determined at 293 K by means of X-ray diffraction as monoclinic space group, C2. The crystal shows a reach sequence of phase transition, four solid-solid transitions: at 250, 281, 388 and 485 K on heating. Most of the phase transitions, except that at 388 K, are clearly of first order and classified as an 'order-disorder' type. The rotational disorder both of cations and anions was studied by differential scanning calorimetry, dielectric and infrared spectroscopy. The low temperature phase transitions are associated with plastic crystal behavior.

  2. LiPF6/LiBOB混合锂盐改善LiFePO4/石墨动力电池高温循环性能研究%Use of LiPF6/LiBOB blend salt for improving cycling performances of LiFePO4/graphite battery at elevated temperature

    Institute of Scientific and Technical Information of China (English)

    宋海申; 赖延清; 李劼; 刘业翔; 张治安

    2013-01-01

    分别以 LiPF6、LiBOB 和 LiPF6/LiBOB 混合盐为电解质,研究了不同电解液对 LiFePO4/石墨动力电池高温循环性能的影响。结果表明,LiBOB 盐抑制了正极溶铁行为,并提高了正极高温循环充放电效率;由于 LiBOB基电解液对正极的保护及在负极表面良好的成膜作用,使得LiFePO4/石墨电池高温循环性能得到明显改善,但是增大了电池阻抗。LiPF6/Li-BOB混合盐可以发挥 LiBOB盐的优点增加正极稳定性,在石墨表面形成致密的 SEI 膜并能够有效改善电池高温循环性能,同时避免了单纯使用 LiBOB盐时阻抗较高的缺点。使用 LiPF6/LiBOB 混合盐,利用LiPF6盐低阻抗特性及 LiBOB盐对正、负电极的保护作用,可以有效提高电池电化学性能。%LiPF6 ,LiBOB and LiPF6/LiBOB blend salt-based electrolytes were investigated for improving cycling performances of LiFePO4/graphite lithium-ion batteries at elevated temperature.It was demonstrated that dis-solution of Fe from LiFePO4 was depressed in LiBOB based electrolyte,and columbic efficiency of LiFePO4/Li cell at elevated temperature was increased;LiBOB was reduced earlier on anode surface,forming compact SEI layer;and the capacity retention of LiFePO4/graphite cells at 55℃ increases with LiBOB concentration due to protective depositions of LiBOB on cathode surface and the SEI layer on anode surface,while the impedance of the cell is increased.LiPF6/LiBOB blend salt-based electrolyte combines the advantages of the different salts and maximizes the performance of cells.When electrolytes with LiPF6/LiBOB blend salt was used,the LiFe-PO4/graphite cells have excellent capacity retention at 55℃,while the impedance was dramatically decreased.

  3. Visible Light Driven Photocascade Catalysis: Ru(bpy)3(PF6)2/TBHP-Mediated Synthesis of Fused β-Carbolines in Batch and Flow Microreactors.

    Science.gov (United States)

    Chandrasekhar, D; Borra, Satheesh; Nanubolu, Jagadeesh Babu; Maurya, Ram Awatar

    2016-06-17

    1,2,3,4-Tetrahydro-β-carbolines were coupled with α-keto vinyl azides through an unprecedented visible light-Ru(bpy)3(PF6)2/TBHP mediated photocascade strategy that involves photosensitization, photoredox catalysis and [3 + 2] cycloaddition reaction. The scope and scale-up feasibility of the photocascade strategy was demonstrated by synthesizing 18 different fused β-carbolines in moderate to good yields using batch and continuous flow microreactor. This operationally simple synthetic protocol allows the formation of one C-C and two C-N new bonds in the overall transformation. PMID:27226119

  4. Solvent extraction studies of Pu(IV) with CMPO in 1-octyl 3-methyl imidazolium hexa fluorophosphate (C8mimPF6) room temperature ionic liquid (RTIL)

    International Nuclear Information System (INIS)

    Solvent extraction studies of Pu(IV) from aqueous nitric acid by carbamoyl methyl phosphine oxide (CMPO) in 1-octyl 3-methyl imidazolium hexa fluorophosphate (C8mimPF6) room temperature ionic liquid (RTIL) were carried out. It was inferred that the stoichiometry of the Pu(IV) species extracted into RTIL phase, through cation exchange mechanism, is [Pu(NO3)(CMPO)x]-3 where x varies from 1 to 2 under the experimental conditions used. Thermodynamic parameters showed the extraction to be favoured by negative enthalpy change, but counteracted by negative entropy change. (orig.)

  5. Interaction of ionic liquid with water with variation of water content in 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF6])/TX-100/water ternary microemulsions monitored by solvent and rotational relaxation of coumarin 153 and coumarin 490

    Science.gov (United States)

    Seth, Debabrata; Chakraborty, Anjan; Setua, Palash; Sarkar, Nilmoni

    2007-06-01

    The interaction of water with room temperature ionic liquid (RTIL) [bmim][PF6] has been studied in [bmim][PF6]/TX-100/water ternary microemulsions by solvent and rotational relaxation of coumarin 153 (C-153) and coumarin 490 (C-490). The rotational relaxation and average solvation time of C-153 and C-490 gradually decrease with increase in water content of the microemulsions. The gradual increase in the size of the microemulsion with increase in w0 (w0=[water]/[surfactant]) is evident from dynamic light scattering measurements. Consequently the mobility of the water molecules also increases. In comparison to pure water the retardation of solvation time in the RTIL containing ternary microemulsions is very less. The authors have also reported the solvation time of C-490 in neat [bmim][PF6]. The solvation time of C-490 in neat [bmim][PF6] is bimodal with time constants of 400ps and 1.10ns.

  6. Unique role of ionic liquid [bmin][BF 4] during curcumin-surfactant association and micellization of cationic, anionic and non-ionic surfactant solutions

    Science.gov (United States)

    Patra, Digambara; Barakat, Christelle

    2011-09-01

    Hydrophilic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroburate, modified the properties of aqueous surfactant solutions associated with curcumin. Because of potential pharmaceutical applications as an antioxidant, anti-inflammatory and anti-carcinogenic agent, curcumin has received ample attention as potential drug. The interaction of curcumin with various charged aqueous surfactant solutions showed it exists in deprotonated enol form in surfactant solutions. The nitro and hydroxyl groups of o-nitrophenol interact with the carbonyl and hydroxyl groups of the enol form of curcumin by forming ground state complex through hydrogen bonds and offered interesting information about the nature of the interactions between the aqueous surfactant solutions and curcumin depending on charge of head group of the surfactant. IL[bmin][BF 4] encouraged early formation of micelle in case of cationic and anionic aqueous surfactant solutions, but slightly prolonged micelle formation in the case of neutral aqueous surfactant solution. However, for curcumin IL [bmin][BF 4] favored strong association (7-fold increase) with neutral surfactant solution, marginally supported association with anionic surfactant solution and discouraged (˜2-fold decrease) association with cationic surfactant solution.

  7. High-pressure densities and derived volumetric properties (excess, apparent, and partial molar volumes) of binary mixtures of {methanol (1) + [BMIM][BF4] (2)}

    International Nuclear Information System (INIS)

    The density of seven {(0.0087, 0.0433, 0.1302, 0.2626, 0.4988, 0.7501, and 0.9102) mole fraction of [BMIM][BF4]} binary {methanol (1) + [BMIM][BF4] (2)} (1-butyl-3-methylimidazolium tetrafluoroborate) mixtures has been measured with a vibrating-tube densimeter. Measurements were performed at temperatures from (298 to 398) K and at pressures up to 40 MPa. The total uncertainties of density, temperature, pressure, and concentration measurements was estimated to be less than 0.15 kg . m-3, 15 mK, 5 kPa, and 10-4, respectively. The uncertainties reported in this paper are expanded uncertainties at the 95% confidence level with a coverage factor of k = 2. The effect of temperature, pressure, and concentration on the density and derived volumetric properties such as excess, apparent, and partial molar volumes was studied. The measured densities were used to develop a Tait-type equation of state for the mixture. The structural properties such as direct and total correlation function integrals and cluster size were calculated using the Krichevskii function concept and the equation of state for the mixture at infinite dilution

  8. Self-aggregation of ionic liquid 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [C4mmim][BF4] in aqueous media: A conductometric, volumetric and spectroscopic study

    International Nuclear Information System (INIS)

    Highlights: • Self-aggregation behaviour of [C4mmim][BF4] has been studied using various techniques. • Thermodynamic parameters showing aggregation is an entropy-driven process. • Volumetric analysis indicates aggregation is influenced by solute–solvent interactions. • 1H NMR revealed formation of loosely bound aggregates in the system. - Abstract: Aggregation behaviour of ionic liquid (IL), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, [C4mmim][BF4] in aqueous media has been studied by electrical conductivity, density and speed of sound measurements across temperature range (288.15–308.15) K. The critical aggregation concentration (cac), the standard Gibb’s free energy of aggregation, ΔG°agg, adiabatic compressibility, βS and changes in the adiabatic compressibility upon aggregation, ΔβS,agg for the IL in aqueous solution have been derived from the experimental data. Further to get the deeper insights into the aggregation process spectroscopic study using 1H NMR measurements have been carried out. The aggregation behaviour observed from conductance and volumetric approaches has been found to be in good agreement with each other. NMR study revealed the formation of loosely bound ion associates as aggregates in the system upon aggregation

  9. Effects of Propylene Carbonate Content in CsPF6-Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries.

    Science.gov (United States)

    Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo; Xiang, Hongfa; Engelhard, Mark H; Polzin, Bryant J; Wang, Chongmin; Zhang, Ji-Guang; Xu, Wu

    2016-03-01

    The effects of propylene carbonate (PC) content in CsPF6-containing electrolytes on the performances of graphite electrode in lithium half cells and in graphite∥LiNi0.80Co0.15Al0.05O2 (NCA) full cells are investigated. It is found that the performance of graphite electrode is significantly affected by PC content in the CsPF6-containing electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode can be attributed to the synergistic effects of the PC solvent and the Cs(+) additive. The synergistic effects of Cs(+) additive and appropriate amount of PC enable the formation of a robust, ultrathin, and compact solid electrolyte interphase (SEI) layer on the surface of graphite electrode, which is only permeable for desolvated Li(+) ions and allows fast Li(+) ion transport through it. Therefore, this SEI layer effectively suppresses the PC cointercalation and largely alleviates the Li dendrite formation on graphite electrode during lithiation even at relatively high current densities. The presence of low-melting-point PC solvent improves the sustainable operation of graphite∥NCA full cells under a wide temperature range. The fundamental findings also shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in various energy-storage devices. PMID:26862677

  10. Simultaneous determination of α-, β- and γ-asarone in Acorus tatarinowii by microemulsion electrokinetic chromatography with [BMIM]PF6 as oil phase.

    Science.gov (United States)

    Wang, Ying; Li, Feng; Yang, Feng-Qing; Zuo, Hua-Li; Xia, Zhi-Ning

    2012-11-15

    In the present study, a rapid and repeatable microemulsion electrokinetic chromatography (MEEKC) method was developed for the simultaneous determination of three isomers (α-, β- and γ-asarone) in Acorus tatarinowii by using ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF(6)) as oil phase. Experimental parameters including the microemulsion compositions (concentrations of surfactant, co-surfactant and oil phase), pH, concentration of borate buffer, capillary temperature and voltage were intensively investigated. Finally, the main compounds in the methanol extract of A. tatarinowii were well separated within 11 min using a running buffer composed of 40 mmol/L sodium dodecyl sulfonate (SDS), 2.0 mol/L n-propanol, 8 mmol/L [BMIM]PF(6) in 10 mmol/L borate buffer of pH 9.5. The developed method was applied to determine the contents of α-, β- and γ-asarone in A. tatarinowii from five different producing areas in China (Anhui, Hebei, Sichuan, Zhejiang and Chongqing). The results indicated that the contents of three asarones are quite different in the investigated A. tatarinowii samples. On the other hand, the MEEKC with ionic liquid as oil phase should be a promising method for the analysis of volatile components especially isomers in medicinal herbs. PMID:23158356

  11. Low-temperature thermodynamic investigation of the sulphur organic salts (TMTTF)2PF6 and (TMTTF)2Br (TMTTF = tetramethyltetrathiafulvalene): II. Dynamical aspects

    Science.gov (United States)

    Lasjaunias, J. C.; Monceau, P.; Staresinic, D.; Biljakovic, K.; Carcel, C.; Fabre, J. M.

    2002-09-01

    This contribution is in continuation of our preceding publication (Lasjaunias J C, Brison J P, Monceau P, Staresinic D, Biljakovic K, Carcel C and Fabre J M 2002 J. Phys.: Condens. Matter 14 837) in which we have considered general aspects of the low-temperature thermodynamical properties of the quasi-one-dimensional organic salts based on sulphur donors with different ground states: (TMTTF)2PF6 in the spin-Peierls state and (TMTTF)2Br (TMTTF = tetramethyltetrathiafulvalene) with commensurate spin modulation. In this part, part II, we present our results on the dynamical aspects related to the non-equilibrium phenomena measured below 1 K. The metastable states excited to slightly higher temperature (by only a few per cent of the starting T0) relax very slowly to the heat bath environment, depending on the duration of the heat pumping. We compare the features observed in the relaxation rates in these two sulphur compounds with those measured for the incommensurate spin-density-wave compound (TMTSF)2PF6. We discuss the possible nature of the long-living low-energy excitations lying at the origin of this complex dynamical behaviour, in relation to their ground states.

  12. Dinuclear Cu(II) complexes of compartmental Schiff base ligands formed from unsymmetrical tripodal amines of varying arm lengths: Crystal structure of [Cu2L1](ClO4)2 and theoretical studies

    Science.gov (United States)

    Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Sayin, Koray

    2016-05-01

    Three new dinuclear copper complexes were synthesized via condensation reaction of three new unsymmetrical N-capped tripodal amines and 2,6-diformyl-4-methylphenol, in the presence of copper(II) perchlorate. The solid-state structure of the dinuclear complex, [Cu2L1](ClO4)2, has been determined by X-ray crystallography, showing that the CuII centers have distorted square-pyramidal geometry with N3O2 coordination. The copper (II) ions are bridged by phenolic and hydroxyalkyl groups when in both cases, deprotonation of the hydrogen atoms of the OH groups occurs. The distance between the copper atoms is 3.062 Å. This compound consists of the dication [Cu2L1]2+ and two ClO4- anions in which one of ClO4- groups has a week interaction with one of the Cu atoms. All complexes were characterized by a variety of physico-chemical techniques such as elemental analyses, IR, mass spectra, conductivity measurements and electronic spectral studies. Computational investigation of mentioned binuclear Cu(II) complexes was done by using M062X method with LANL2DZ basis set in vacuo.

  13. Synthesis, crystal structure and spectral properties of Np5+ complex with triphenylphosphine oxide, [NpO2(PO(C6H5)3)4]ClO4

    International Nuclear Information System (INIS)

    Monocrystals [NpO2(TPO)4]ClO4 (1) were prepared by interaction of NpO2ClO4 with triphenylphosphine oxide (TPO). The crystals of (1) are triclinic, unit cell parameters at 20 deg C are as follows: a 9.140 (2), b 13.528 (3), c = 13.918 (3) A, α = 97.14 (3), β 108.17 (3), γ = 91.75 (3), sp. gr. P1-bar, Z = 1, dcalcld. = 1.521 g/cm3. Compound (1) consists of complex cations [NpO2(TPO)4]+ and disordered anions ClO4-. Neptunium atom has tetragonal-bipyramid oxygen surrounding (coordination number 6). The length of Np-O axial bond is 1.797 (2) A, average value of Np-O equatorial bonds equals 2.438 A. Data of IR and absorption spectroscopy suggest the absence of cation-cation interaction of NpO2+ dioxocations centrally symmetric in the equatorial plane

  14. A facile route for the preparation of nanoparticles of the spin-crossover complex [Fe(Htrz)2(trz)](BF4) in xerogel transparent composite films.

    Science.gov (United States)

    Faulmann, Christophe; Chahine, Joe; Malfant, Isabelle; de Caro, Dominique; Cormary, Benoît; Valade, Lydie

    2011-03-21

    Films and monoliths containing the spin crossover complex [Fe(Htrz)(2)(trz)](BF(4)) (trz = 1,2,4-triazole) as nanoparticles have been obtained. The dispersion and consecutive inclusion of the Fe complex in a silica matrix prepared from tetramethoxysilane or tetraethoxysilane afford monoliths or films with a violet colour at room temperature, which turns white above 380 K. This change of colour is reversible. This thermochromic behaviour has been characterized by measuring the magnetic properties together with thermogravimetric studies and Raman spectroscopy, the result of which all demonstrate that both films and monoliths undergo a spin crossover. Microscopy studies confirm the occurrence of the Fe complex as nanoparticles, in both the monoliths and the films. The facile synthesis of these materials as nanoparticles in transparent films should open the possibility of the synthesis of high quality films. PMID:21290082

  15. Preparation and characterization of electropolymerized poly(3,4-ethylenedioxythiophene) thin films with different dopant anions

    Science.gov (United States)

    Deguchi, Toshiaki; Tomeoku, Hiroya; Takashiri, Masayuki

    2016-06-01

    We investigated the structural and thermoelectric properties poly(3,4-ethylenedioxythiophene) (PEDOT) films with several dopants (counter ions, ClO4, PF6, and BF4), synthesised by electropolymerization. We first performed cyclic voltammetry analysis to determine the optimum synthesis conditions of the PEDOT thin films. We found that the surface morphology of the PEDOT thin films was dependent on the type of the dopant. The PF6-doped PEDOT (PEDOT:PF6) thin films showed a dense structure, and the PEDOT:ClO4 thin films showed a highly porous microstructure. Fourier transform infrared (FT-IR) spectroscopy showed that all the PEDOT thin films showed similar chemical structures and the p-type state. Regarding their thermoelectric properties, the electrical conductivity of the all the doped PEDOT thin films increased as the dopant concentration increased, with the PEDOT:PF6 thin films showing the highest value. On the other hand, the Seebeck coefficient of the PEDOT thin films with all the dopants decreased as the dopant concentration increased, with the PEDOT:BF4 thin films achieving the highest value. As a result, the PEDOT:BF4 thin films exhibited the highest power factor of 0.75 µW/(m·K2) at a dopant concentration of 1.0 M. We think that the PEDOT microstructure produced using the different types of dopant may affect the thermoelectric properties.

  16. Study on thermo physical and excess molar properties of binary systems of ionic liquids. I: [Cnmim][PF6] (n = 6, 8) and alkyl acetates

    International Nuclear Information System (INIS)

    Highlights: • Densities, speeds of sound and refractive indices were reported for [Cnmim][PF6] (n = 6, 8) + alkyl acetates. • The measurements were performed at T = 5 K interval between (293.15 and 323) K over full range of concentrations. • Excess molar properties were derived from measured values of density, speed of sound and refractive index. • The effects of temperature and chain length of IL and acetate on excess molar properties were discussed. • Excess molar volumes VmE were predicted by PFP theory. - Abstract: The measurements of densities, ρ, speeds of sound, u and refractive indices, nD for binary mixtures containing 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6mim][PF6]) and 1-octyl-3-methylimidazolium hexafluorophosphate ([C8mim][PF6]) + ethyl acetate (EA) and butyl acetate (BA) were reported over full range of concentrations. The measurements were performed at atmospheric pressure and seven different temperatures of five degree intervals between (293.15 and 323.15) K. The excess properties on mixing were derived from measured values of these properties. The values of density were utilized to obtain excess molar volumes, VmE, speeds of sound to obtain excess molar isentropic compressibilities, κS,mE and refractive index to get refractive index deviations, ΔφnD. The binary co-efficients of excess properties were obtained by Redlich–Kister polynomial equation. The influences of temperature and addition of –CH2 group in imidazolium cation of ionic liquids as well as acetate on excess properties have been discussed. The VmE and κS,mE are negative and decease with increase in temperature while ΔφnD are positive and increase with increase in temperature. For common acetate, The VmE increases with each increment of –CH2 group in imidazolium cation of IL and similar is true when –CH2 group increases in alkyl acetate for common IL. The deviation in VmEwas investigated by employing Prigogine–Flory–Patterson theory

  17. Combination of acid-resistor and -scavenger improves the SEI stability and cycling ability of tin–nickel battery anodes in LiPF6-containing electrolyte

    International Nuclear Information System (INIS)

    Control of electrode–electrolyte interfacial reactivity and the formation of the solid electrolyte interphase (SEI) layer is a key technology for high performance rechargeable lithium batteries. Here we present the first report on a promising interfacial approach for Sn–Ni electrode that the use of acid-resisting and -scavenging fluorine-dopant on Sn combined with acid-scavenging trimethyl phosphite electrolyte additive to LiPF6-contiaing carbonate-based organic electrolyte improves the interfacial stability of Sn to acidic electrolyte species. As a result, a stable SEI layer consisting of a plenty of carbonate decomposition products forms and cycling ability significantly improves, in contrast to less efficient SEI formation and rapid performance fade for the electrodes without fluorine-dopant or trimethyl phosphite additive

  18. Cycling profile of MgAl2O4-incorporated composite electrolytes composed of PEO and LiPF6 for lithium polymer batteries

    International Nuclear Information System (INIS)

    Magnesium aluminate (MgAl2O4)-incorporated poly(ethylene oxide) (PEO)–lithium hexafluorophosphate (LiPF6) based composite polymer electrolyte (CPE) membranes were prepared by a hot press for the first time. The membranes were subjected to X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric (TG), differential scanning calorimetry (DSC), tensile, impedance spectroscopy, compatibility and transport number studies. The incorporation of MgAl2O4 greatly enhanced the ionic conductivity, compatibility and mechanical integrity of the polymeric membrane. Finally, an all solid state lithium cell composed of Li/CPE/LiFePO4 was assembled and its cycling profile was analyzed at 70 °C. The cells delivered a discharge capacity of 127 mAh g−1 at 1 C-rate with very good capacity retention up to 100 cycles which is found to be better than those reported earlier

  19. Solvation of uranyl-CMPO complexes in dry vs. humid forms of the [BMI][PF6] ionic liquid. A molecular dynamics study.

    Science.gov (United States)

    Chaumont, Alain; Wipff, Georges

    2006-01-28

    The solvation of the [UO(2)(NO(3))(CMPO)](+) and [UO(2)(NO(3))(2)(CMPO)(2)] complexes (CMPO = octyl(phenyl)-N,N-diisobutylmethylcarbamoyl phosphine oxide) is investigated by molecular dynamics in the "dry" and "humid" forms of a room temperature ionic liquid (IL) based on the 1-butyl-3-methylimidazolium (BMI(+)) cation and the hexafluorophosphate (PF(6)(-)) anion. The simulations reveal the importance of the solvent anions in "dry" conditions and of water molecules in the "humid" solvent. For the [UO(2)(NO(3))(CMPO)](+) complex, the monodentate vs. bidentate coordination modes of CMPO are compared, and the first solvation shell of uranyl is completed by 1-3 PF(6)(-) anions in the dry IL and by 2-3 water molecules in the humid IL, leading to a total coordination number close to 5. The energy analysis shows that interactions with the IL stabilize the [UO(2)(NO(3))(bi)(CMPO)(mono)](+) form (with bidentate nitrate and monodentate CMPO) in the dry IL and the [UO(2)(NO(3))(mono)(CMPO)(mono)](+) form (with monodentate nitrate and CMPO) in the humid IL. The extracted compound characterized by EXAFS is thus proposed to be the [UO(2)(NO(3))(mono)(CMPO)(mono)(H(2)O)(3)](+) species. Furthermore we compare the [UO(2)(NO(3))(2)(CMPO)(2)] complex in its associated and dissociated forms ([UO(2)(NO(3))(mono)(CMPO)(mono)](+) + CMPO + NO(3)(-)) and discuss the results in the context of uranyl extraction by CMPO to ionic liquids. PMID:16482292

  20. Effects of ionic liquid [bmim][PF6] on absorption spectra and reaction kinetics of the duroquinone triplet state in acetonitrile.

    Science.gov (United States)

    Zhu, Guanglai; Wu, Guozhong; Sha, Maolin; Long, Dewu; Yao, Side

    2008-04-10

    The transient absorption spectra and photoinduced electron-transfer process of duroquinone (DQ) in mixed binary solutions of ionic liquid (IL) [bmim][PF6] and acetonitrile (MeCN) have been investigated by laser photolysis at an excitation wavelength of 355 nm. A spectral blue shift of 3DQ* was observed in the IL/MeCN mixtures compared to MeCN. At lower VIL(volume fraction of IL), the interaction between DQ and the solvent is dominant, and the decay rate constant (kobs) of 3DQ* increases steadily with the increasing of VIL; to the contrary, at higher VIL, the network structures due to the hydrogen bond and viscosity are dominant, and the decay rate constant decreases obviously with increasing VIL. A critical point (turnover) was observed at VIL = approximately 0.30. The dependence of the observed growth rate (kgr) of the photoinduced electron-transfer (PET) products on VIL is complex and shows a special change; kgr first decreases with increasing VIL, then increases, and finally decreases slowly with further increasing of VIL. It is speculated that the PET process in the mixture can be affected by factors including the local structure and the reorganization energy of the solvent and salt and cage effects. The change of local structure of [bmim][PF6]/MeCN is supported by following the steady-state fluorescence behavior of the mixture, in combination with the molecular dynamics simulation of the thermodynamic property. The results revealed that the degree of self-aggregation of monomeric cations (bmim+) to associated forms increases with increasing VIL. This is in good agreement with the laser photolysis results for the same solutions. PMID:18331005

  1. Effects of Propylene Carbonate Content in CsPF6-Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo; Xiang, Hongfa; Engelhard, Mark H.; Polzin, Bryant; Wang, Chong M.; Zhang, Jiguang; Xu, Wu

    2016-02-10

    Cesium salt has been demonstrated as an efficient electrolyte additive in suppressing the lithium (Li) dendrite formation and directing the formation of an ultrathin and stable solid electrolyte interphase (SEI) even in propylene carbonate (PC)-ethylene carbonate (EC)-based electrolytes. Here, we further investigate the effect of PC content in the presence of CsPF6 additive (0.05 M) on the performances of graphite electrode in Li||graphite half cells and in graphite||LiNi0.80Co0.15Al0.05O2 (NCA) full cells. It is found that the performance of graphite electrode is also affected by PC content even though CsPF6 additive is present in the electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode is attributed to the synergistic effects of the Cs+ additive and the PC solvent. The formation of a robust, ultrathin and compact SEI layer containing lithium-enriched species on the graphite electrode, directed by Cs+, effectively suppresses the PC co-intercalation and thus prevents the graphite exfoliation. This SEI layer is only permeable for de-solvated Li+ ions and allows fast Li+ ion transport through it, which therefore largely alleviates the Li dendrite formation on graphite electrode during lithiation even at high current densities. The presence of low-melting-point PC solvent also enables the sustainable operation of the graphite||NCA full cells under a wide spectrum of temperatures. The fundamental findings of this work shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in a variety of energy storage devices.

  2. The EPR zero-field splitting D and its pressure and temperature dependence for trigonal Mn2+ centers in [Zn(H2O)6](BF4)2:Mn2+ crystal

    International Nuclear Information System (INIS)

    The EPR zero-field splitting D (= b20) and its pressure and temperature dependence for trigonal Mn2+ centers in low and room temperature phases in [Zn(H2O)6](BF4)2:Mn2+ crystal are studied by a high-order perturbation formula based on the dominant spin-orbit coupling mechanism. From the studies, the local trigonal distortion angles, the local angular compressibilities and the local angular thermal expansion coefficients for Mn2+ centers in both phases of the [Zn(H2O)6](BF4)2 crystal are estimated. The results are discussed. (orig.)

  3. Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni(II)2(L)(μ1,1-N3)][ClO4] (L = Macrocyclic N6S2 Ligand).

    Science.gov (United States)

    Jeremies, Alexander; Gruschinski, Sina; Meyer, Michel; Matulis, Vitaly; Ivashkevich, Oleg A; Kobalz, Karolin; Kersting, Berthold

    2016-02-15

    The dinuclear Ni(II) complex [Ni2(L(2))][ClO4]2 (3) supported by the 28-membered hexaaza-dithiophenolate macrocycle (L(2))(2-) binds the N3(-) ion specifically end-on yielding [Ni2(L(2))(μ1,1-N3)][ClO4] (7) or [Ni2(L(2))(μ1,1-N3)][BPh4] (8), while the previously reported complex [Ni2L(1)(μ1,3-N3)][ClO4] (2) of the 24-membered macrocycle (L(1))(2-) coordinates it in the end-to-end fashion. A comparison of the X-ray structures of 2, 3, and 7 reveals the form-selective binding of complex 3 to be a consequence of its preorganized, channel-like binding pocket, which accommodates the azide anion via repulsive CH···π interactions in the end-on mode. In contrast to [Ni2L(1)(μ1,3-N3)][ClO4] (2), which features a S = 0 ground state, [Ni2(L(2))(μ1,1-N3)][BPh4] (8) has a S = 2 ground state that is attained by competing antiferromagnetic and ferromagnetic exchange interactions via the thiolato and azido bridges with a value for the magnetic exchange coupling constant J of 13 cm(-1) (H = -2JS1S2). These results are further substantiated by density functional theory calculations. The stability of the azido-bridged complex determined by isothermal titration calorimetry in MeCN/MeOH 1/1 v/v (log K11 = 4.88(4) at I = 0.1 M) lies in between those of the fluorido- (log K11 = 6.84(7)) and chlorido-bridged complexes (log K11 = 3.52(5)). These values were found to compare favorably well with the equilibrium constants derived at lower ionic strength (I = 0.01 M) by absorption spectrophotometry (log K11 = 5.20(1), 7.77(9), and 4.13(3) for N3(-), F(-), and Cl(-) respectively). PMID:26836637

  4. Low-temperature heat capacity and thermal decomposition of crystalline [Er2(His·H+)(H2O)8](ClO4)6·4H2O

    International Nuclear Information System (INIS)

    The heat capacities of rare earth complex with amino acid histidine, [Er2(His·H+)(H2O)8](ClO4)6·4H2O, were measured with an automatic adiabatic calorimeter from 79 to 320 K. It was found that there was a sudden increment in heat capacity within the temperature range 182-190 K. Thermal decomposition behavior of the complex in nitrogen atmosphere was studied by thermogravimetric (TG) analysis, and a possible decomposition mechanism was suggested according to TG-DTG results

  5. Development of the PF-6 Device ffor the Goal Of the Mainstream Fusion Research and Spin-Off Applications; Medocine, Biology, Material Sciences etc

    International Nuclear Information System (INIS)

    In the framework of the Project we have elaborated a new design of the electrical circuit (in co-operation with ICTP) to increase the repetition rate f of the operational regime of PF-6 device till the level: U = 23 kV, E = 7.4 kJ, f = 5 Hz. With this power supply we have elaborated and tested our new DPF chambers able to work with the deuterium-tritium mixture as a working gas. We have developed, implemented and tested new diagnostics of X ray and neutron pulses with temporal resolution 0.3 ns and 16-frame 1-ns laser interferometry. In cooperation with our partners on this IAEA CRP we provided radiation tests of materials candidate for the main-stream fusion reactors (tungsten, CFC, ceramics Al2O3 and NB, low- activation steels, etc.) using besides the PF-6 facility the Dense Plasma Focus devices PF-5M, ING-103 and PF-1000. In addition with the same partners we undertake initial experiments with an aim to improve characteristics of the surface layer of materials (mechanical and tribological behavior, radiation resistance, etc.) using the above devices. The idea is to use hot plasma streams and beams of fast ions generated in DPF in treatment of internal hard-to-reach compartments of the machine components. In cooperation with Pirelli we have provided first experiments in the field of X ray dynamic quality control with DPF aimed to disclosure imperfections in car tyres. Also we spread our previous X ray based experiments on pulsed radio- enzymology to the pulsed neutron irradiation of enzymes and other bio-test objects. We have provided experiments intended to detect large-volume objects containing illegal substances (explosives, drugs, etc.) and first experiments on irradiation by neutron pulses a fuel element containing fissile materials by means of time-of flight neutron technique. These experiments give an opportunity to use DPF in a single-shot technique of unveiling illegal materials hidden in a luggage or in containers. (author)

  6. Synthesis, structural characterization, and gas-phase unimolecular reactivity of the silver hydride nanocluster [Ag3((PPh2)2CH2)3(μ3-H)](BF4)2.

    Science.gov (United States)

    Zavras, Athanasios; Khairallah, George N; Connell, Timothy U; White, Jonathan M; Edwards, Alison J; Mulder, Roger J; Donnelly, Paul S; O'Hair, Richard A J

    2014-07-21

    A bis(diphenylphosphino)methane-ligated trinuclear silver hydride nanocluster, [Ag3((Ph2P)2CH2)3(μ3-H)](BF4)2, featuring three silver(I) ions coordinated to a μ3-hydride, and its deuteride analogue, [Ag3((Ph2P)2CH2)3(μ3-D)](BF4)2, have been isolated and structurally characterized using electrospray ionization mass spectrometry (ESI-MS), X-ray crystallography, NMR and IR spectroscopy. The position of the deuteride in [Ag3((Ph2P)2CH2)3(μ3-D)](BF4)2 was determined by neutron diffraction. ESI-MS of [Ag3L3(μ3-H/D)](BF4)2 [L = ((Ph2P)2CH2)2] produces [Ag3L3(μ3-H/D)](2+) and [Ag3L3(μ3-H/D)(BF4)](+). A rich gas-phase ion chemistry of [Ag3L3(μ3-H/D)](2+) is observed under conditions of collision-induced dissociation (CID) and electron-capture dissociation (ECD). CID gives rise to the following complementary ion pairs: [Ag3L2](+) and [L+(H/D)](+); [Ag2(H/D)L2](+) and [AgL](+); [Ag2(H/D)L](+) and [AgL2](+). ECD gives rise to a number of dissociation channels including loss of the bis(phosphine) ligand, fragmentation of a coordinated bis(phosphine) ligand via C-P bond activation, and loss of a hydrogen (deuterium) atom with concomitant formation of [Ag3L3](+). Under CID conditions, [Ag3L3(μ3-H/D)(BF4)](+) fragments via ligand loss, the combined loss of a ligand and [H,B,F4], and cluster fragmentation to give [Ag2(BF4)L2](+) and [Ag2(L-H)L](+) [where (L-H) = (Ph2P)2CH(-)]. PMID:24991699

  7. Inelastic and elastic neutron scattering studies of the vibrational and reorientational dynamics, crystal structure and solid-solid phase transition in [Mn(OS(CH3)2)6](ClO4)2 supported by theoretical (DFT) calculations

    Science.gov (United States)

    Szostak, Elżbieta; Hetmańczyk, Joanna; Migdał-Mikuli, Anna

    2015-06-01

    The vibrational and reorientational dynamics of CH3 groups from (CH3)2SO ligands in the high- and low-temperature phases of [Mn(OS(CH3)2)6](ClO4)2 were investigated by quasielastic and inelastic incoherent neutron scattering (QENS and IINS) methods. The results show that above the phase transition temperature (detected earlier by differential scanning calorimetry (DSC) at TC5c = 222.9 K on cooling and at TC5h = 225.4 K on heating) the CH3 groups perform fast (τR ≈ 10-12-10-13 s) reorientational motions. These motions start to slow down below TC5c Neutron powder diffraction (NPD) measurements, performed simultaneously with QENS and IINS, indicated that this phase transition is associated with a change of the crystal structure, too. Theoretical infrared absorption, Raman and inelastic incoherent neutron scattering spectra were calculated using DFT method (B3LYP functional, LANL2DZ ECP basis set (on Mn atom) and 6-311+G(d,p) basis set (on C, H, S, O atoms) for the isolated equilibrium model (isolated [Mn(DMSO)6]2+ cation and ClO4- anion). Calculated spectra show a good agreement with the experimental spectra (FT-IR, RS and IINS). The comparison of the results obtained by these complementary methods was made.

  8. Synthesis, characterization of a new photosensitive compound [Ru(bpy)2 (TPAD)](PF6)2 and its application for photocatalytic hydrogen production

    Science.gov (United States)

    Zheng, Hui-Qin; Guo, Yi-Ping; Yin, Ming-Cai; Fan, Yao-Ting

    2016-06-01

    A new photosensitive compound based on triphenylamine donor and ruthenium(II), namely [Ru(bpy)2(TPAD)](PF6)2 (PS1, bpy = 2,2‧-bipyridine, TPAD = N-(4-(1H-imidazo[4,5-f][1,10] phenanthroline-2-yl)phenyl)-N-phenylbenzenamine), had been synthesized and characterized by elemental analysis, 1H NMR, MS spectra, UV, PL and CV measurements. The target photocatalyst, PS1/0.5 wt% Pt/TiO2, was prepared by sensitizing PS1 to 0.5 wt% Pt/TiO2 and characterized by SEM and XRD. The highest hydrogen evolution reached to 9500 μmol·(g·catalyst)-1 (475 μmol, 31.7 TON and TOF 5.8 vs. PS1) under the optimal conditions with 0.05 g·L-1 of PS1, and 5% of TEOA at pH 11 with the irradiation of 5.5 h. The mechanism of hydrogen evolution was also briefly discussed in the present work.

  9. Synthesis and Crystal Structure of{[Mn(H2O)4(3, 3′-azpy)](3, 3′-azpy)3(PF6)2}n

    Institute of Scientific and Technical Information of China (English)

    李宝龙; 曹正白; 王寿武; 徐正; 郁开北

    2002-01-01

    The complex {[Mn(H2O)4(3, 3?-azpy)](3, 3?-azpy)3(PF6)2}n (3, 3?-azpy = 3, 3?- azobispyridine) has been synthesized and characterized. The crystal (C40H40F12MnN16O4P2, Mr = 1153.76) belongs to the triclinic system, space group P ī with the following crystallographic parameters: a = 10.761(2), b = 11.040(2), c = 23.365(4) ?, ( = 85.52(1), ( = 82.69(1), ( = 70.44(1)°, V = 2592.5(8) ?3, Dc = 1.478 g/cm3, ((MoK() = 4.16 cm-1, F(000) = 1174, Z = 2, final R = 0.0493 and wR = 0.1158 for the observed reflections (I > 2.00((I)). The X-ray analysis revealed that manganese(Ⅱ) cation coordination environment is a distorted octahedral geometry, and the Mn2+ cation is coordinated by four oxygen atoms of water in the equatorial plane, while the two nitrogen atoms of 3, 3?-azpy occupy the axial positions. The complex forms a one-dimensional chain structure via 3, 3?-azpy bridging ligand.

  10. Effect of water on structure and dynamics of [BMIM][PF6] ionic liquid: An all-atom molecular dynamics simulation investigation

    Science.gov (United States)

    Sharma, Anirban; Ghorai, Pradip Kr.

    2016-03-01

    Composition dependent structural and dynamical properties of aqueous hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) ionic liquid (IL) have been investigated by using all-atom molecular dynamics simulation. We observe that addition of water does not increase significant number of dissociated ions in the solution over the pure state. As a consequence, self-diffusion coefficient of the cation and anion is comparable to each other at all water concentration similar to that is observed for the pure state. Voronoi polyhedra analysis exhibits strong dependence on the local environment of IL concentration. Void and neck distributions in Voronoi tessellation are approximately Gaussian for pure IL but upon subsequent addition of water, we observe deviation from the Gaussian behaviour with an asymmetric broadening with long tail of exponential decay at large void radius, particularly at higher water concentrations. The increase in void space and neck size at higher water concentration facilitates ionic motion, thus, decreasing dynamical heterogeneity and IL reorientation time and increases self-diffusion coefficient significantly.

  11. Reactions of [Cu(X)(BPEP-Ph)] (X = PF6, SbF6) with silyl compounds. Cooperative bond activation involving non-coordinating anions.

    Science.gov (United States)

    Nakajima, Yumiko; Tsuchimoto, Takahiro; Chang, Yung-Hung; Takeuchi, Katsuhiko; Ozawa, Fumiyuki

    2016-02-01

    Bond activation of silyl compounds, assisted by the cooperative action of non-coordinating anions, is achieved using Cu(I) complexes coordinated with a PNP-pincer type phosphaalkene ligand, [Cu(X)(BPEP-Ph)] (X = PF6 (1a), SbF6 (1b); BPEP-Ph = 2,6-bis[1-phenyl-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyl]pyridine). Complexes 1a and 1b react with Me3SiCN to form Me3SiF and Cu(i) cyanide complexes of the formula [Cu(CN-EF5)(BPEP-Ph)] (E = P (2a), Sb (2b)), in which the CN ligand is associated with the EF5 group arising from EF6(-). Formation of the intermediary isonitrile complex [Cu(CNSiMe3)(BPEP-Ph)](+)SbF6(-) (3b) is confirmed by its isolation. Thus, a two-step reaction process involving coordination of Me3SiCN, followed by nucleophilic attack of SbF6(-) on the silicon atom of 3b is established for the conversion of 1b to 2b. Complex 1b cleaves the H-Si bond of PhMe2SiH as well. The isolation and structural identification of [Cu(BPEP-Ph)](+)BAr(F)4(-) (1c) (BAr(F)4 = B{3,5-(CF3)2C6H3}4) as a rare example of a T-shaped, three-coordinated Cu(i) complex is reported. PMID:26455594

  12. Deposition, accumulation, and alteration of Cl-, NO3-, ClO4- and ClO3- salts in a hyper-arid polar environment: Mass balance and isotopic constraints

    Science.gov (United States)

    Jackson, Andrew; Davila, Alfonso F.; Böhlke, John Karl; Sturchio, Neil C.; Sevanthi, Ritesh; Estrada, Nubia; Brundrett, Maeghan; Lacelle, Denis; McKay, Christopher P.; Poghosyan, Armen; Pollard, Wayne; Zacny, Kris

    2016-06-01

    The salt fraction in permafrost soils/sediments of the McMurdo Dry Valleys (MDV) of Antarctica can be used as a proxy for cold desert geochemical processes and paleoclimate reconstruction. Previous analyses of the salt fraction in MDV permafrost soils have largely been conducted in coastal regions where permafrost soils are variably affected by aqueous processes and mixed inputs from marine and stratospheric sources. We expand upon this work by evaluating permafrost soil/sediments in University Valley, located in the ultraxerous zone where both liquid water transport and marine influences are minimal. We determined the abundances of Cl-, NO3-, ClO4- and ClO3- in dry and ice-cemented soil/sediments, snow and glacier ice, and also characterized Cl- and NO3- isotopically. The data are not consistent with salt deposition in a sublimation till, nor with nuclear weapon testing fall-out, and instead point to a dominantly stratospheric source and to varying degrees of post depositional transformation depending on the substrate, from minimal alteration in bare soils to significant alteration (photodegradation and/or volatilization) in snow and glacier ice. Ionic abundances in the dry permafrost layer indicate limited vertical transport under the current climate conditions, likely due to percolation of snowmelt. Subtle changes in ClO4-/NO3- ratios and NO3- isotopic composition with depth and location may reflect both transport related fractionation and depositional history. Low molar ratios of ClO3-/ClO4- in surface soils compared to deposition and other arid systems suggest significant post depositional loss of ClO3-, possibly due to reduction by iron minerals, which may have important implications for oxy-chlorine species on Mars. Salt accumulation varies with distance along the valley and apparent accumulation times based on multiple methods range from ∼10 to 30 kyr near the glacier to 70-200 kyr near the valley mouth. The relatively young age of the salts and relatively low and homogeneous anion concentrations in the ice-cemented sediments point to either a mechanism of recent salt removal, or to relatively modern permafrost soils (end-member of stratospheric sources not subject to biological processes or extensive remobilization.

  13. Deposition, Accumulation, and Alteration of Cl(-), NO3(-), ClO4(-) and ClO3(-) Salts in a Hyper-Arid Polar Environment: Mass Balance and Isotopic Constraints

    Science.gov (United States)

    Jackson, Andrew; Davila, Alfonso F.; Boehlke, J. K.; Sturchio, Neil C.; Sevanthi, Ritesh; Estrada, Nubia; Brundrette, Megan; Lacell, Denis; McKay, Christopher P.; Poghosyan, Armen; Pollard, Wayne; Zacny, Kris

    2016-01-01

    The salt fraction in permafrost soils/sediments of the McMurdo Dry Valleys (MDV) of Antarctica can be used as a proxy for cold desert geochemical processes and paleoclimate reconstruction. Previous analyses of the salt fraction in MDV permafrost soils have largely been conducted in coastal regions where permafrost soils are variably affected by aqueous processes and mixed inputs from marine and stratospheric sources. We expand upon this work by evaluating permafrost soil/sediments in University Valley, located in the ultraxerous zone where both liquid water transport and marine influences are minimal. We determined the abundances of Cl(-), NO3(-, ClO4(-)and ClO3(-)in dry and ice-cemented soil/sediments, snow and glacier ice, and also characterized Cl(-) and NO3(-) isotopically. The data are not consistent with salt deposition in a sublimation till, nor with nuclear weapon testing fall-out, and instead point to a dominantly stratospheric source and to varying degrees of post depositional transformation depending on the substrate, from minimal alteration in bare soils to significant alteration (photodegradation and/or volatilization) in snow and glacier ice. Ionic abundances in the dry permafrost layer indicate limited vertical transport under the current climate conditions, likely due to percolation of snowmelt. Subtle changes in ClO4(-)/NO3(-) ratios and NO3(-) isotopic composition with depth and location may reflect both transport related fractionation and depositional history. Low molar ratios of ClO3(-)/ClO4(-) in surface soils compared to deposition and other arid systems suggest significant post depositional loss of ClO3(-), possibly due to reduction by iron minerals, which may have important implications for oxy-chlorine species on Mars. Salt accumulation varies with distance along the valley and apparent accumulation times based on multiple methods range from approximately 10 to 30 kyr near the glacier to 70-200 kyr near the valley mouth. The relatively young age of the salts and relatively low and homogeneous anion concentrations in the ice-cemented sediments point to either a mechanism of recent salt removal, or to relatively modern permafrost soils (less than 1 million years). Together, our results show that near surface salts in University Valley serve as an end-member of stratospheric sources not subject to biological processes or extensive remobilization.

  14. Multiple light-induced NO linkage isomers in the dinitrosyl complex [RuCl(NO)2(PPh3)2]BF4 unravelled by photocrystallographic and IR analysis.

    Science.gov (United States)

    Casaretto, Nicolas; Pillet, Sebastien; Bendeif, El Eulmi; Schaniel, Dominik; Gallien, Anna K E; Klüfers, Peter; Woike, Theo

    2015-01-01

    Multiple light-induced reversible metastable NO linkage isomers (PLIs) have been detected in the dinitrosyl compound [RuCl(NO)2(PPh3)2]BF4 by a combination of photocrystallographic and IR analysis. The IR signature of three PLI states has been clearly identified, with estimated populations of 59% (PLI-1), 8% (PLI-2) and 5% (PLI-3) for a total population of the metastable state of 72%. The structural configuration of the major component (PLI-1) has been derived by X-ray photocrystallography. In the ground state, the structure is characterized by a bent and a linear nitrosyl, the bent one being oriented towards the linear equatorial nitrosyl with an Ru-N-O angle of 133.88 (9)°. X-ray Fourier difference maps indicate a selectivity of the photo-isomerization process in PLI-1: only the bent NO ligand changes its position, while the linear NO is unaffected. After irradiation at 405 nm, the orientation is changed by rotation towards the Cl ligand opposite the linear NO, with an Ru-N-O angle in this new position of 109 (1)°. The photocrystallographic analysis provides evidence that, in the photo-induced metastable state, the bent NO group is attached to the Ru atom through the N atom (Ru-N-O), rather than in an isonitrosyl Ru-O-N binding mode. In the IR spectra, the asymmetric NO vibrational band shifts by -33 cm(-1) to a lower value, whereas the symmetric band splits and shifts by 5 cm(-1) to a higher value and by -8 cm(-1) to a lower value. The down shift is a clear indication of the structural change, and the small upward shift in response to the new electronic configuration of the metastable structure. Variable-temperature IR kinetic measurements in the range 80-114 K show that the decay of the PLI-1 state follows an Arrhenius behaviour with an activation energy of 0.22 eV. PMID:25610626

  15. Multiple light-induced NO linkage isomers in the dinitrosyl complex [RuCl(NO2(PPh32]BF4 unravelled by photocrystallographic and IR analysis

    Directory of Open Access Journals (Sweden)

    Nicolas Casaretto

    2015-01-01

    Full Text Available Multiple light-induced reversible metastable NO linkage isomers (PLIs have been detected in the dinitrosyl compound [RuCl(NO2(PPh32]BF4 by a combination of photocrystallographic and IR analysis. The IR signature of three PLI states has been clearly identified, with estimated populations of 59% (PLI-1, 8% (PLI-2 and 5% (PLI-3 for a total population of the metastable state of 72%. The structural configuration of the major component (PLI-1 has been derived by X-ray photocrystallography. In the ground state, the structure is characterized by a bent and a linear nitrosyl, the bent one being oriented towards the linear equatorial nitrosyl with an Ru—N—O angle of 133.88 (9°. X-ray Fourier difference maps indicate a selectivity of the photo-isomerization process in PLI-1: only the bent NO ligand changes its position, while the linear NO is unaffected. After irradiation at 405 nm, the orientation is changed by rotation towards the Cl ligand opposite the linear NO, with an Ru—N—O angle in this new position of 109 (1°. The photocrystallographic analysis provides evidence that, in the photo-induced metastable state, the bent NO group is attached to the Ru atom through the N atom (Ru—N—O, rather than in an isonitrosyl Ru—O—N binding mode. In the IR spectra, the asymmetric NO vibrational band shifts by −33 cm−1 to a lower value, whereas the symmetric band splits and shifts by 5 cm−1 to a higher value and by −8 cm−1 to a lower value. The down shift is a clear indication of the structural change, and the small upward shift in response to the new electronic configuration of the metastable structure. Variable-temperature IR kinetic measurements in the range 80–114 K show that the decay of the PLI-1 state follows an Arrhenius behaviour with an activation energy of 0.22 eV.

  16. Perchlorate cerium(3) complexes with 1,10-phenanthroline. Crystal structure of [Ce(C12H8N2)4(CH3CN)2](ClO4)3 · 3CH3CN

    International Nuclear Information System (INIS)

    The Ce(ClO4)3 · 2Phen · 2H2O (1) and Ce(ClO4)3 · 3Phen (2) complexes are obtained through interaction of anhydrous Ce(ClO4)3 · H2O with 1,10-phenanthroline. The Ce(ClO4)3 · 4Phen · 5CH3CN (3) complex is separated from the solution 2. The IR-spectra of compounds 1-3, their thermal behavior are studied, X-ray diffraction data on compounds 1 and 2 are presented. The RSA is carried out for compound 3: rhombic crystals, a = 12.059(3), b 20.657(5), c = 24.170(6) A, sp. gr. Pccn, Z = 4. The structure 3 consists of complex cations [Ce(Phen)4 · (CH3CN)2]3+, outerspheric anions ClO4- and solvate molecules of acetonitrile

  17. Does [TcF(CO)5] exist? The crystal and molecular structure of [Tc(CO)3(OH)0.49F0.51]4·[Tc(CO)5(BF4)].

    Science.gov (United States)

    Stepanova, E S; Gurzhiy, V V; Tyupina, M Yu; Miroslavov, A E; Sidorenko, G V; Lumpov, A A

    2016-05-17

    Technetium pentacarbonyl fluoride [TcF(CO)5] was prepared for the first time by reaction of [TcI(CO)5] with solid AgF in a dichloromethane solution at -23 °C. Low temperature crystallization of the resulting compound in a glass vial yielded an unusual complex [Tc(CO)3(OH)0.49F0.51]4·[Tc(CO)5(BF4)] characterized by single crystal XRD. PMID:27108652

  18. Synthesis of the compound tetrakis (2- methoxy isobutyl isonitrile) copper (I) tetrafluoroborate -(Cu[MIBI]4BF4): substance used in the production of the radiopharmaceutical sestamibi 99m Tc

    International Nuclear Information System (INIS)

    The radiopharmaceutical SESTAMIBI-99mTc presents interest and application in the clinical routine in Nuclear Medicine, especially for evaluation of the myocardium function and in the diagnosis of some tumors types, and the Center of Radiopharmacy of the IPEN has interest in the development of this radiopharmaceutical for attendance of the nuclear medicine class necessities. In this work it was demonstrated the synthesis and characterization of the active compound tetrakis (2- methoxy isobutyl isonitrile) copper (I) tetrafluoroborate - Cu[MIBI]4BF4- to be used in the preparation of lyophilized reagents for labeling with technetium-99m as well as labeling studies and biological distribution. The synthesis of the reagent Cu[MIBI]4BF4 was carried out in accordance with previously described procedures, in 5 steps and the compounds were characterized for infra-red, magnetic nuclear resonance, melting point and thin layer chromatography. The characterization of the chelate of MIBI -Cu[MIBI]4BF4 - was carried out using high performance liquid chromatography, compared with a standard sample of the product and presented similar results, as described in literature. The lyophilized reagent was prepared and labeled with technetium-99m, showing high radiochemical purity, higher than 97%, with high stability. Biological distribution in different animals showed good uptake in the heart, in time compatible with the acquisition of scintigraphy images, demonstrating the applicability of the reagent synthesized in the attainment of cardiac scintigraphy images. (author)

  19. Effect of LiPF6 concentration in Li[Ni0.4Mn0.4Co0.2]O2/graphite pouch cells operated at 4.5 V

    Science.gov (United States)

    Petibon, R.; Madec, L.; Abarbanel, D. W.; Dahn, J. R.

    2015-12-01

    The effect of LiPF6 concentration in the 1 M-2.5 M range was studied in Li[Ni0.4Mn0.4Co0.2O]2 (NMC(442))/graphite and LaPO4 coated-NMC(442)/graphite pouch cells cycled to high voltage. Electrochemical impedance spectroscopy on symmetric cells revealed that the dramatic impedance growth observed in NMC(442)/graphite cells cycled to high voltage comes from the interface impedance of the positive electrode. The use of high LiPF6 concentrations in the 2-2.5 M range dramatically slowed down the impedance growth of both coated and uncoated NMC(442)/graphite cells containing certain electrolyte additive blends and cycled to high voltage. However no beneficial effect was observed in control cells containing no electrolyte additive. X-ray photoelectron spectra of cycled electrodes of coated-NMC(442)/graphite cells showed that LiPF6 concentration greatly affected the composition of the solid electrolyte interphase of both the positive and negative electrodes of cells containing additives.

  20. 离子液体[C4mim ][PF6]萃取-石墨炉原子吸收法检测食品中的痕量铅%The Determination of Lead by Graphit Furnace Atomic Absorption Spectrometry Couple with Ionic Liquid [C4 min][PF6 ] Extraction in Food

    Institute of Scientific and Technical Information of China (English)

    王乃丽; 王金梅

    2013-01-01

    离子液体因其具有不挥发,粘度大等特性,已被广泛代替有机溶剂用于液液萃取。建立了以二乙基二硫代氨基甲酸钠(DDTC)为螯合剂、离子液体1-丁基-3-甲基咪唑六氟磷酸盐([C4 mim][PF6])为萃取剂、稀硝酸为反萃取溶剂的萃取体系,并对所建立的萃取体系的相关影响因素进行了优化,包括:体系pH、螯合剂DDTC的用量、反萃取溶剂的选择等。同时对该离子液体是否可循环利用以及该体系的抗干扰能力进行了评价。此外,将所建立的离子液体萃取-稀硝酸反萃取体系结合石墨炉原子吸收分光光度法应用于大米,茶,鱼,小麦,蛤以及油菜中的痕量铅的检测。%The ionic liquid has replaced the organic solvent as the extraction solvent for it's including non-volatile and high viscosity .DDTC was selected as chelating agent ,[C4 mim][PF6 ] as the extraction agent and HNO3 as back-extraction agent .The optimized experimental condition was :pH of the extraction , the concentration of DDTC ,the back-extraction solvent .Meanwhile ,recyclable of the ionic liquid and an-ti-interference were also discussed .Finally ,this method was successfully applied in the determination of the trace Pb existed in the rice ,tea ,fish ,wheat ,clam and rape .

  1. Microcalorimetric study about biological effect of a synthetic complex: La(Glu)(Im)6(ClO4)3.4HClO4.4H2O

    International Nuclear Information System (INIS)

    A complex of lanthanum perchloric acid coordinated with glutamic acid, La(Glu)(Im)6(ClO4)3.4HClO4.4H2O was synthesized and characterized. The biological effect of the complex was evaluated by microcalorimetry on the growth of E. coli DH5α. Power-time curves of the growth metabolism of E. coli DH5α were studied using a TAM Air Isothermal Microcalorimeter at 37 oC. From the power-time curves, the parameters such as growth rate constants (k), inhibitory ratio (I), the maximum heat power (Pm) and the time of the maximum heat power (tm) were obtained. The results show that the concentrations of the complex affect obviously the growth metabolism of E. coli DH5α. The stimulatory effect on growth of E. coli DH5α was observed when the concentration of the complex was kept in the range of (0-0.5 μg mL-1). In contrast to the lower concentration, in the case of higher concentration of the complex (0.5-5.0 μg mL-1), an inhibitory effect occurred.

  2. Low-temperature heat capacity and thermodynamic properties of [Re2(Ile)4(H2O)8](ClO4)6 (Re=Nd, Er, Ile=isoleucine)

    International Nuclear Information System (INIS)

    The heat capacities of two kinds of rare-earth element solid complexes with isoleucine [Re2(Ile)4(H2O)8](ClO4)6 (where Re=Nd, Er, and Ile=isoleucine) have been measured by an automatic adiabatic calorimeter in the temperature range from 80 to 370 K. Two solid-solid phase transitions were found from the Cp curve of Nd formed complex in the range of 165-175 K with a peak temperature of 167.88 K and in the range of 195-210 K with a peak temperature of 202.13 K. The corresponding molar enthalpies of these phase transitions were determined to be 404.61 J mol-1 and 2.955 kJ mol-1, respectively. One solid-solid phase transition was found for the Er formed complex in the range of 190-205 K with a peak temperature of 193.42 K. The corresponding molar enthalpy of this transition was 14.11 kJ mol-1. Smooth heat capacities and thermodynamic functions relative to the standard state (298.15 K), HT-H298.15, ST-S298.15 and -[GT-G298.15], of the two compounds, were calculated on basis of experimental heat capacity data. Possible mechanisms of thermal decompositions for the pair of compounds were suggested according to the thermogravimetric (TG) analysis

  3. Heat capacity and thermodynamical properties of the crystal of [RE2(Glu)2(H2O)8](ClO4)4·H2O (RE=Nd,Eu,Dy)

    Institute of Scientific and Technical Information of China (English)

    WU XinMin; LI Wei; TAN ZhiCheng; QU SongSheng

    2009-01-01

    Thermodynamical data of rare earth complexes with amino acid are important for engineering chemistry and fundamental chemistry.However,they have rarely been reported.In this work,a series of crystalline complexes of rare earth perchlorate coordinated with glutamic acid have been synthesized in water medium,and their thermodynamical data,including the heat capacity in low temperature range and the standard enthalpy of formation,were determined.These complexes were identified to be [RE2(Glu)2(H2O)8](ClO4)4.H2O (RE=Nd,Eu,Dy) by using thermogravimetric analysis (TG),differential thermal analysis (DTA),and chemical and elementary analyses.Their purity has been determined.No melting points were observed for all the three complexes.The heat capacity of the complexes was measured by an adiabatic calorimeter from 79 to 370 K.Abnormal heat capacity values were detected for two of the complexes and the decomposition range of one complex was found.The temperature,enthalpy change and entropy change of the decomposition processes of the three complexes were calculated.The polynomial equations of heat capacity in the experimental temperature range have been obtained by least squares fitting.The standard enthalpy of formation was determined by an isoperibol reaction calorimeter at 298.15 K.

  4. Influence of the intermolecular interaction on photo-induced spin-transition of [Fe(R-pap)2]X

    International Nuclear Information System (INIS)

    Iron(III) spin-crossover complexes [Fe(pap)2]ClO4 x H2O, [Fe(pap)2]BF4 x H2O, [Fe(pap)2]PF6 x CH3OH), [Fe(CH3-pap)2]ClO4 x H2O, [Fe0.5Al0.5(pap)2]ClO4 x CH3OH and [Fe0.25Al0.75(pap)2] ClO4 x CH3OH were prepared and the spin transition behaviors of the complexes have been studied from magnetic susceptibility and Moessbauer spectroscopy measurements. The magnetic properties of light-induced metastable state are measured using Hg-Xe light source. T1/2 is temperature at which the populations of the high-spin and low-spin species are fifty-fifty. Metastable HS is produced by light irradiation at 5 K. T(LIESST) is the temperature at which the populations of the metastable high-spin species decrease to one half and cooperativity factor Cis defined as the parameter which presents the strength of cooperativity. The value of T(LIESST) decreases as T1/2 increases and the plots of T(LIESST) vs. C show linear correlation. The effect of cooperativity of the complexes on the relaxations in solid was confirmed for the iron(III) complexes. (author)

  5. Magnetism and Pressure-Induced Superconductivity of Checkerboard-Type Charge-Ordered Molecular Conductor β-(meso-DMBEDT-TTF2X (X = PF6 and AsF6

    Directory of Open Access Journals (Sweden)

    Yutaka Nishio

    2012-11-01

    Full Text Available The metallic state of the molecular conductor β-(meso-DMBEDT-TTF2X (DMBEDT-TTF = 2-(5,6-dihydro-1,3-dithiolo[4,5-b][1,4]dithiin-2-ylidene-5,6-dihydro-5,6-dimethyl-1,3-dithiolo[4,5-b][1,4]dithiin, X = PF6, AsF6 is transformed into the checkerboard-type charge-ordered state at around 75–80 K with accompanying metal-insulator (MI transition on the anisotropic triangular lattice. With lowering temperatures, the magnetic susceptibility decreases gradually and reveals a sudden drop at the MI transition. By applying pressure, the charge-ordered state is suppressed and superconductivity appears in β-(meso-DMBEDT-TTF2AsF6 as well as in the reported β-(meso-DMBEDT-TTF2PF6. The charge-ordered spin-gapped state and the pressure-induced superconducting state are discussed through the paired-electron crystal (PEC model, where the spin-bonded electron pairs stay and become mobile in the crystal, namely the valence-bond solid (VBS and the resonant valence bonded (RVB state in the quarter-filled band structure.

  6. Study on Stability and Electrochemical Properties of Nano-LiMn1.9Ni0.1O3.99S0.01-Based Li-Ion Batteries with Liquid Electrolyte Containing LiPF6

    Directory of Open Access Journals (Sweden)

    Monika Bakierska

    2016-01-01

    Full Text Available Herein, we report on the stability and electrochemical properties of nanosized Ni and S doped lithium manganese oxide spinel (LiMn1.9Ni0.1O3.99S0.01, LMN1OS in relation to the most commonly used electrolyte solution containing LiPF6 salt. The influence of electrochemical reaction in the presence of selected electrolyte on the LMN1OS electrode chemistry was examined. The changes in the structure, surface morphology, and composition of the LMN1OS cathode after 30 cycles of galvanostatic charging/discharging were determined. In addition, thermal stability and reactivity of the LMN1OS material towards the electrolyte system were verified. Performed studies revealed that no degradative effects, resulting from the interaction between the spinel electrode and liquid electrolyte, occur during electrochemical cycling. The LMN1OS electrode versus LiPF6-based electrolyte has been indicated as an efficient and electrochemically stable system, exhibiting high capacity, good rate capability, and excellent coulombic efficiency. The improved stability and electrochemical performance of the LMN1OS cathode material originate from the synergetic substitution of LiMn2O4 spinel with Ni and S.

  7. Effective asymmetric bioreduction of ethyl 4-chloro-3-oxobutanoate to ethyl (R)-4-chloro-3-hydroxybutanoate by recombinant E. coli CCZU-A13 in [Bmim]PF6-hydrolyzate media.

    Science.gov (United States)

    He, Yu-Cai; Tao, Zhi-Cheng; Di, Jun-Hua; Chen, Liang; Zhang, Lin-Bing; Zhang, Dan-Ping; Chong, Gang-Gang; Liu, Feng; Ding, Yun; Jiang, Chun-Xia; Ma, Cui-Luan

    2016-08-01

    It was the first report that the concentrated hydrolyzates from the enzymatic hydrolysis of dilute NaOH (3wt%)-soaking rice straw at 30°C was used to form [Bmim]PF6-hydrolyzate (50:50, v/v) media for bioconverting ethyl 4-chloro-3-oxobutanoate (COBE) into ethyl (R)-4-chloro-3-hydroxybutanoate [(R)-CHBE] (>99% e.e.) with recombinant E. coli CCZU-A13. Compared with pure glucose, the hydrolyzates could promote both initial reaction rate and the intracellular NADH content. Furthermore, emulsifier OP-10 (20mM) was employed to improve the reductase activity. Moreover, Hp-β-cyclodextrin (0.01mol Hp-β-cyclodextrin/mol COBE) was also added into this bioreaction system for enhancing the biosynthesis of (R)-CHBE from COBE by E. coli CCZU-A13 whole-cells. The yield of (R)-CHBE (>99% e.e.) from 800mM COBE was obtained at 100% in the [Bmim]PF6-hydrolyzate (50:50, v/v) media by supplementation of OP-10 (20mM) and Hp-β-CD (8mM). In conclusion, an effective strategy for the biosynthesis of (R)-CHBE was successfully demonstrated. PMID:27155796

  8. Influence of gamma irradiation on the physical properties of hydrophobic room temperature ionic liquids [BuMeIm]PF6 and [BuMeIm][(CF3SO2)2N

    International Nuclear Information System (INIS)

    It was shown that density, surface tension, and refraction index of room temperature ionic liquids (RTIL) [BuMeIm]X, where BuMeIm+ is 1-butyl-3-methyl-imidazolium and X- is PF6-, and (CF3SO2)2N-, are not changed being subjected to approximately 600 kGy of absorbed dose of gamma irradiation (137Cs). At the same time gamma radiolysis causes significant increase in viscosities of RTILs. Studied RTILs exhibit darkening under the gamma irradiation. The light absorbance of ionic liquids increases linearly with irradiation dose. Water has no influence on the radiolytic darkening. Formation of colored products is related to radiolysis of BuMeIm+ cation. The kinetics of radiolytic darkening of RTILs is influenced by the anions as follows: Cl-3SO2)2N-6-. The revealed effect is attributed to the interaction of the primary products of anion radiolysis with BuMeIm+ cation. (authors)

  9. trans-[Ru(NO)Cl(cyclam)](PF6)2 and [Ru(NO)(Hedta)] incorporated in PLGA nanoparticles for the delivery of nitric oxide to B16-F10 cells: cytotoxicity and phototoxicity.

    Science.gov (United States)

    Gomes, Anderson J; Espreafico, Enilza M; Tfouni, Elia

    2013-10-01

    The immobilization and characterization of trans-[Ru(NO)Cl(cyclam)](PF6)2 (cyclam=1,4,8,11-tetraazacyclotetradecane), and [Ru(NO)(Hedta)] (Hedta=ethylenediaminetetraacetic acid) entrapped in poly(d,l-lactic-co-glycolic) acid (PLGA) nanoparticles (NP) using the double emulsification process is described. Scanning electron microscopy and dynamic light scattering revealed that the particles are spherical in shape, have a size distribution between 220 and 840 nm of diameter, and have a tendency to aggregate confirmed by a zeta potential between -3.2 and +3.5 mV. Using this method the loading efficiency was 26% for trans-[Ru(NO)Cl(cyclam)](PF6)2 and 32% for [Ru(NO)(Hedta)]. The release of the complexes from the NPs shows that cyclam-NP and Hedta-NP exhibited a two-phase exponential association release pattern, which was characterized by an initial complex burst during the first 24 h, followed by a slower release phase complex profile, due to a few pores observed in surface of nanoparticles using atomic force microscopy. The in vitro cytotoxic activity of the nitrosyl complexes in solution and incorporated in PLGA nanoparticles on melanoma cancer cells (cell line B16-F10) was investigated. The lower cytotoxicity of trans-[RuCl(cyclam)(NO)]2+ (12.4±2.6%) and [Ru(NO)(Hedta)] (4.0±2.7%) in solution compared to that of trans-[Ru(NO)(NH3)4py]3+ (46.1±6.4%) is consistent with the rate constant release of NO of these complexes (k-NO=6.2×10(-4) s(-1), 2.0×10(-3) s(-1), and 6.0×10(-2) s(-1), respectively); the cytotoxicities are also inhibited in the presence of the NO scavenger carboxy-PTIO. The phototoxicity of these complexes is due to NO release, which lead to 53.8±6.2% of cell death in the presence of trans-[Ru(NO)Cl(cyclam)](PF6)2 and 22.3±5.1% in the presence of [Ru(NO)(Hedta)]. The PLGA nanoparticles loaded with trans-[Ru(NO)Cl(cyclam)](PF6)2 and [Ru(NO)(Hedta)] exerted in vitro a reduced activity against melanoma cells when compared to the activity of complex in

  10. Epoxidação do óleo de soja com o sistema catalítico [MoO2(acac2]/TBHP EM [bmim][PF6

    Directory of Open Access Journals (Sweden)

    Maritana Farias

    2012-01-01

    Full Text Available Epoxidation of soybean oil was investigated using 1-n-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] ionic liquid as biphasic medium with molybdenum(VI acetylacetonate complex and tert-butyl hydroperoxide TBHP as oxidizing agent. Reaction conditions were molar ratio TBHP:number of double bonds of oil:catalyst of 100:100:1, reaction temperature of 60 ºC and reaction time between 2 and 24 h. The proposed system showed catalytic activity for epoxidation reactions under tested conditions. Reuse of ionic liquid/catalyst system for epoxidation reactions was also investigated. Evaluation of epoxidation observed in this catalytic system was done by quantitative ¹H NMR data.

  11. Exceptionally long-lived light-emitting electrochemical cells: multiple intra-cation π-stacking interactions in [Ir(C^N)2(N^N)][PF6] emitters

    OpenAIRE

    Buenzli, Andreas M.; Constable, Edwin C.; Housecroft, Catherine E.; Prescimone, Alessandro; Zampese, Jennifer A.; Longo, Giulia; Gil-Escrig, Lidon; Pertegas, Antonio; Orti, Enrique; Bolink, Henk J.

    2015-01-01

    A series of cyclometalated iridium(III) complexes [Ir(C^N)2(N^N)][PF6] (N^N = 2,2′-bipyridine (1), 6-phenyl-2,2′-bipyridine (2), 4,4′-di-tert-butyl-2,2′-bipyridine (3), 4,4′-di-tert-butyl-6-phenyl-2,2′-bipyridine (4); HC^N = 2-(3-phenyl)phenylpyridine (HPhppy) or 2-(3,5-diphenyl)phenylpyridine (HPh2ppy)) are reported. They have been synthesized using solvento precursors so as to avoid the use of chlorido-dimer intermediates, chloride ion contaminant being detrimental to the performance of [Ir...

  12. On the changes of the structure of perchlorate (ClO4-)-degrading bacterial communities under heterotrophic conditions%异养条件下高氯酸盐降解细菌群落变化研究

    Institute of Scientific and Technical Information of China (English)

    谢宇轩; 关翔宇; 王阳; 王鹤立

    2014-01-01

    了解特定环境中高氯酸盐(ClO4-)降解菌的群落组成,对ClO4-的降解具有重要的指导意义.通过添加醋酸盐作为电子供体降解ClO4-,利用高通量测序(HiSeq 2000)的方法获得了复杂环境中生物群落的组成,对比了降解前后菌种结构的变化.结果表明,补充醋酸盐的降解体系(Acetate Degradation,AD)将10 mg/L ClO4-降至检出限以下需100 h.降解完毕后代表性的ClO4-降解菌Dechloromonas的相对丰度为0.2%,与原始活性污泥相比无明显差别;另一典型ClO2降解菌脱氯菌属Azospira相对丰度为3.2%;一些同时参与ClO4-降解和脱氮作用的细菌如假单胞菌属Pseudomonas也有检出,相对丰度为8%.异养条件下ClO4-降解是假单胞菌属Pseudomonas和脱氨菌属Azospira起主导作用.AD体系内菌种多样性小于原始活性污泥.电子供体的加入使活性污泥类的混合体系内生物群落结构单一化,使降解基质具备了在特定环境下针对某种污染物降解的能力.

  13. Synthesis, crystal structure and magnetic properties of a thiocyanate bridged dinuclear copper(Ⅱ) complex:[μ-SCN Cu dien]2 (ClO4)2%硫氰酸根桥连双核铜配合物[μ-(SCN)Cu(dien)]2(ClO4)2的合成、晶体结构和磁性研究

    Institute of Scientific and Technical Information of China (English)

    米春喜; 胡怀明

    2004-01-01

    合成了硫氰酸根桥连双核铜配合物[μ-(SCN)Cu(dien)]2(ClO4)2,测定了它的晶体结构.晶体为三斜晶系,P-1空间群,a=0.746 5(2),b=0.748 4(2),c=1.182 2(2)nm,α=90.51(3),β=105.39(3),γ=109.06(3)°,V=0.598 5(2)nm3,Dc=1.799 Mg/m3,μ=2.227 mm-1,F(000)=330,Z=1.最小二乘修正得R1=0.0325,wR2=0.0906.结构由高氯酸根离子和双核铜配正离子组成,两个铜离子由两个硫氰酸根离子桥连,两个铜离子之间的距离为0.5512(2)nm.每个铜离子与二乙烯三胺的三个氮原子和硫氰酸根的一个氮原子在赤道平面上配位,另一个硫氰酸根的一个硫原子和高氯酸根的一个氧原子在轴向配位,形成了畸变的八面体配位几何构型.Cu-N键长在0.195 0(1)~0.20l 8(1)nm范围内,Cu-S键长0.276 6(1),Cu-O键长0.288 4(2)nm.研究了75~300K温度范围内固体样品的磁性,表明在铜离子间存在着反铁磁相互作用.

  14. Two-Step Photon Absorption Driving the Chemical Reaction in the Model Ruthenium Nitrosyl System [Ru(py)4Cl(NO)](PF6)2·(1)/2H2O.

    Science.gov (United States)

    Khadeeva, Liya; Kaszub, Wawrzyniec; Lorenc, Maciej; Malfant, Isabelle; Buron-Le Cointe, Marylise

    2016-05-01

    Various systems containing the [ML5NO] molecule, where M = Fe, Ru, ... and L = F, Cl, ..., exhibit switching under continuous light (CW) irradiation between the ground-state nitrosyl (GS), isonitrosyl (MSI), and side-on (MSII) configurations. The metastable populations, however, are often limited to a few percent. The [Ru(py)4Cl(NO)](PF6)2·(1)/2H2O system is thus a remarkable model compound as the GS to MSI transformation is nearly complete in a single crystal. A predominant two-step photon absorption process during GS to MSI switching under blue light is revealed by visible absorption spectroscopy, although a low concentration of the transient species hinders the determination of this process by the structural signature. During the depopulation of MSI, both two-step and direct processes are evidenced under red CW irradiation. Different intermediate visible spectra revealing transient species during GS to MSI and the reverse photochemical processes are discussed in relation to MSII properties. PMID:27054377

  15. Fire behavior of carbonates-based electrolytes used in Li-ion rechargeable batteries with a focus on the role of the LiPF6 and LiFSI salts

    Science.gov (United States)

    Eshetu, Gebrekidan Gebresilassie; Bertrand, Jean-Pierre; Lecocq, Amandine; Grugeon, Sylvie; Laruelle, Stephane; Armand, Michel; Marlair, Guy

    2014-12-01

    A detailed investigation of the combustion behavior of LiPF6 or LiFSI-based carbonate electrolytes was conducted with the objective of getting better knowledge of lithium-ion battery system fire induced thermal and chemical threats. The well-controlled experimental conditions provided by the Tewarson calorimeter have enabled the accurate evaluation of fire hazard rating parameters such as heat release rate and effective heat of combustion and the quantification of toxic effluents (HF, SO2, NOx…). Results have shown that all the electrolytes tested burn in phases depending on the flammability nature of their mixture constituents. The first stage of combustion is solely governed by the more volatile solvent (linear carbonate) and the influence of adding salt comes into effect predominantly in the second stage. It has been also shown that combustion enthalpy of electrolytes lies in the solvent mixture, irrespective of the salt added. The fire induced toxicity in well-ventilated conditions is found to be mainly dictated by the salt and its chemical structure, showing very limited concerns that emanate from the organic solvents.

  16. A perspective on coatings to stabilize high-voltage cathodes: LiMn1.5Ni0.5O4 with subnanometer Lipon cycled with LiPF6 electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yoongu [ORNL; Dudney, Nancy J [ORNL; Chi, Miaofang [ORNL; Martha, Surendra K [ORNL; Nanda, Jagjit [ORNL; Veith, Gabriel M [ORNL; Liang, Chengdu [ORNL

    2013-01-01

    High voltage Li-ion cathodes push the limits of stability for both cathode and electrolyte. Here subnanometer coatings of an amorphous thin film electrolyte (Lipon) improved the room temperature and 60 C cycling stability of a LiMn1.5Ni0.5O4 spinel cathode when charged to 4.9V with a standard LiPF6 carbonate electrolyte. The cathodes delivered superior C-rate performances up to a 5C discharge, when compared to the uncoated cathodes. Enhanced performance extended for at least 100 cycles. Electrochemical impedance spectroscopy indicates that Lipon slows the increase of interface resistance. Thicker 1-3nm Lipon coatings are sufficiently insulating as to block electronic transport to the cathode particles. Thick coatings also slow Mn dissolution. Results suggest that Lipon may act to scavenge impurities or block active sites that promote electrolyte decomposition. While greatly improved by the Lipon coating, this cathode is not sufficiently stable for long cycle life applications. Further work is needed to assess if and what surface coatings will ultimately stabilize the high voltage cathodes. Comments include insight from other studies of Lipon coated cathodes and directions for future research.

  17. 离子液体[C4mim][PF6]与N,N-二甲基甲酰胺二元混合物在298.15 K~318.15 K的密度和粘度%Densities and Viscosities of the Ionic Liquid [C4mim][PF6]+N,N-dimethylformamide Binary Mixtures at 293.15 K to 318.15 K

    Institute of Scientific and Technical Information of China (English)

    耿彦芳; 王腾芳; 虞大红; 彭昌军; 刘洪来; 胡英

    2008-01-01

    Viscosities and densities for 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) and N,N-dimethylformamide (DMF) binary mixtures have been measured at the temperature range from 293.15 K to 318.15 K. It is shown that the viscosities and densities decrease monotonously with temperature and the content of DME Various correlation methods including Arrhenius-like equation, Seddon et al.'s equation, Redlich-Kister equation with four parameters, and other empirical equations were applied to evaluate these experimental data. A model based on an equation of state for estimating the viscosity of mixtures containing ionic liquids were proposed by coupling with the excess Gibbs free energy model of viscosity, which can synchronously calculate the viscosity and the molar volume. The results show that the model gives a deviation of 8.29% for the viscosity, and a deviation of 1.05% for the molar volume when only one temperature-independent adjustable parameter is adopted. The cor-relation accuracy is further improved when two parameters or one temperature-dependent parameter is used.

  18. Host-guest supramolecular interactions in the coordination compounds of 4,4'-azobis(pyridine) with MnX2 (X = NCS–, NCNCN–, and PF6(–)): structural analyses and theoretical study.

    Science.gov (United States)

    Kar, Paramita; Biswas, Rituparna; Drew, Michael G B; Frontera, Antonio; Ghosh, Ashutosh

    2012-02-01

    Three new Mn(II) coordination compounds {[Mn(NCNCN)(2)(azpy)]·0.5azpy}(n) (1), {[Mn(NCS)(2)(azpy)(CH(3)OH)(2)]·azpy}(n) (2), and [Mn(azpy)(2)(H(2)O)(4)][Mn(azpy)(H(2)O)(5)]·4PF(6)·H(2)O·5.5azpy (3) (where azpy = 4,4'-azobis(pyridine)) have been synthesized by self-assembly of the primary ligands, dicyanamide, thiocyanate, and hexafluorophosphate, respectively, together with azpy as the secondary spacer. All three complexes were characterized by elemental analyses, IR spectroscopy, thermal analyses, and single crystal X-ray crystallography. The structural analyses reveal that complex 1 forms a two-dimensional (2D) grid sheet motif. These sheets assemble to form a microporous framework that incorporates coordination-free azpy by host-guest π···π and C-H···N hydrogen bonding interactions. Complex 2 features azpy bridged one-dimensional (1D) chains of centrosymmetric [Mn(NCS)(2)(CH (3)OH)(2)] units which form a 2D porous sheet via a CH(3)···π supramolecular interaction. A guest azpy molecule is incorporated within the pores by strong H-bonding interactions. Complex 3 affords a 0-D motif with two monomeric Mn(II) units in the asymmetric unit. There exist π···π, anion···π, and strong hydrogen bonding interactions between the azpy, water, and the anions. Density functional theory (DFT) calculations, at the M06/6-31+G* level of theory, are used to characterize a great variety of interactions that explicitly show the importance of host-guest supramolecular interactions for the stabilization of coordination compounds and creation of the fascinating three-dimensional (3D) architecture of the title compounds. PMID:22272694

  19. Effects of Rut-bpy (Cis-[Ru(bpy2(SO3(NO]PF 6, a novel nitric oxide donor, in L-NAME-induced hypertension in rats Efeitos do Rut-bpy (Cis-[Ru(bpy2(SO3(NO]PF 6, um novo doador de óxido nítrico, na hipertensão induzida com L-NAME em ratos

    Directory of Open Access Journals (Sweden)

    Marcio Wilker Soares Campelo

    2011-01-01

    Full Text Available PURPOSE: To evaluate the effect of Rut-bpy (Cis-[Ru(bpy2(SO3(NO]PF 6, a novel nitric oxide donor in Nω-nitro-L-arginine methyl ester (L-NAME-induced hypertensive rats. METHODS: Twenty-four male Wistar rats were randomly assigned to four groups (n=6, named according to the treatment applied (G1-Saline, G2-Rut-bpy, G3-L-NAME and G4-L-NAME+Rut-bpy. L-NAME (30 mg/Kg was injected intraperitoneally 30 minutes before the administration of Rut-bpy (100 mg/Kg. Mean abdominal aorta arterial blood pressure (MAP was continuously monitored. RESULTS: Mean arterial blood pressure (MAP in G3 rats rose progressively, reaching 147±16 mmHg compared with 100±19 mm Hg in G1 rats (pOBJETIVO: Avaliar o efeitos do Rut-bpy (Cis-[Ru (bpy2(SO3(NO] PF6, um novo doador de óxido nítrico, em ratos hipertensos induzidos pelo éster metílico de N-nitro-L-arginina (L-NAME. MÉTODOS: Vinte e quatro ratos Wistar machos foram distribuídos aleatoriamente em quatro grupos (n = 6, nomeados de acordo com o tratamento aplicado (G1-Salina, G2-Rut-bpy, G3-L-NAME e G4-L-NAME+Rut -bpy. L-NAME (30 mg / Kg foi injetado por via intraperitoneal 30 minutos antes da administração de Rut-bpy (100 mg / kg. A pressão arterial média (PAM da aorta abdominal foi monitorada continuamente. RESULTADOS: A pressão arterial média (PAM em ratos do grupo G3 subiu progressivamente, chegando a 147 ±16 mm Hg, em comparação com 100 ±19 mm Hg em ratos do G1 (p <0,05. Em ratos G4, tratados com L-NAME + Rut-bpy, a PAM atingiu 149±11 milímetros de Hg, enquanto no G2 (ratos tratados com Rut bpy os valores da PAM foram 106 ±11 mm Hg. No G1 esses valores decresceram progressivamente, atingindo 87±14 mm Hg após 30 minutos. Um achado importante foi a manutenção da PAM durante todo o experimento em ratos do grupo G2. CONCLUSÃO: O uso de Rut bpy não diminui a PAM em ratos hipertensos por L-NAME. No entanto, quando ele é usado em ratos anestesiados, hipotensos, uma pressão arterial estável

  20. Anodic behavior of stainless-steel substrate in organic electrolyte solutions containing different lithium salts

    International Nuclear Information System (INIS)

    Highlights: • We investigated anodic behavior of stainless-steel in organic electrolytes for advanced capacitor. • Anion of the electrolyte affected the anodic stability of the alloy. • Anodic passivation occurs in LiPF6 solution but pitting or active dissolution proceeds in other electrolyte solutions. • Fluoride source in the solution contributes to forming a stable surface layer on the stainless steel. - Abstract: The anodic behavior of austenitic stainless-steel, SUS304, as a current collector of positive electrode in lithium-ion battery/capacitor has been investigated in organic electrolyte solutions based on a mixed alkyl carbonate solvent with different lithium salts. Stable passivation characteristics were observed for the stainless-steel in the LiPF6 solution, but pitting corrosion or active dissolution proceeded in the solutions containing other anions, BF4-, (CF3SO2)2N- (TFSA-) and ClO4-. The mass ratios of the dissolved metal species in the solutions of LiTFSA and LiClO4 were equivalent to that of the alloy composition, which suggests that no preferential dissolution occurs during the anodic polarization in these electrolyte solutions. An HF component formed by decomposition of PF6- with the contaminate water will act as an F- source for the formation of a surface fluoride layer, that will contribute to the anodic stability of SUS304 in the LiPF6 solution. The anodic corrosion in the LiTFSA solution was suppressed in part by mixing the PF6 salt or adding HF in the electrolyte

  1. FIRST X-RAY CRYSTAL STRUCTURE OF A BIMETALLIC COMPLEX CONTAINING A p -COORDINATED HYDRAZONE: [(h 5-CpFe(h 6-p-MeOC6H4-NHN=CH-(h 5-C5H4Fe(h 5-Cp]+PF6

    Directory of Open Access Journals (Sweden)

    Carolina Manzur

    2001-12-01

    Full Text Available The dinuclear organometallic hydrazone [(h 5-CpFe(h 6-p-MeO-C6H4-NHN=CH-(h 5-C5H4Fe(h 5-Cp]+PF6- (Cp=C5H5 is stereoselectively prepared as its trans isomer by reacting the organometallic hydrazine precursor [(h 5-CpFe(h 6-p-MeO-C6H4-NHNH2]+PF6- with the ferrocenecarboxaldehyde. Its crystalline and molecular structure has been determined and consists of two iron(II sandwiches of the type [(h 5-CpFe(h 6-arene]+ and [(h 5-C5H4Fe(h 5-Cp], in anti position one with respect to the other, and linked by a zigzag hydrazonic spacerLa hidrazona organometálica dinuclear [(h 5-CpFe(h 6-p-MeO-C6H4-NHN=CH-(h 5-C5H4Fe(h 5-Cp]+PF6- es preparada estereoquímicamente como su isómero trans por reacción de la hidracina organometálica precursora [(h 5-CpFe(h 6-p-MeO-C6H4-NHNH2]+PF6- con ferrocencarboxaldehido. Se ha determinado su estructura cristalina y molecular que consiste en dos sanwiches de hierro(II del tipo [(h 5-CpFe(h 6-areno]+ y [(h 5-C5H4Fe(h 5-Cp] en posición anti uno respecto del otro, los que se encuentran enlazados por un espaciador hidrazónico en forma de zig-zag

  2. Excess Molar Volume, Refractive Index and Viscosity of N-Butylpyridinium Tetrafluoroborate Ionic Liquid + Methanol Binary System%离子液体[BPy]BF4和甲醇二元混合体系的超额摩尔体积、折射率和黏度

    Institute of Scientific and Technical Information of China (English)

    许映杰; 黄钗英; 李浩然

    2011-01-01

    合成了室温离子液体N-丁基吡啶四氟硼酸盐([BPy]BF4),通过核磁共振1H-NMR和红外光谱IR对其结构进行了表征.在298.15 K和常压下,采用U形振荡管密度计测定[BPy]BF4-甲醇体系的密度;用阿贝尔折射仪测定了该二元混合体系在相同温度和压力下的折射率;用乌氏黏度计测定了该二元混合体系在相同温度和压力下的黏度,并由密度数据计算出超额摩尔体积(VE)、由折射率数据计算出了折射率改变值(△nD)、由黏度数据计算出了体系的黏度B系数.结果表明:[BPy]BF4-甲醇体系的VE在全浓度范围内为负值,而△nD在全浓度范围内为正值,两者均在摩尔分数x1≈0.4处出现极值;采用Redlich-Kister方程对VE、△nD与组成的关系进行了关联,最大标准偏差小于3%,说明此方程可适用于回归该二元体系上述的物性数据.由Jones-Dole方程计算出体系的黏度B系数为0.35608,这表明甲醇有效地降低了离子液体的黏度.%Room temperature ionic liquid N-butylpyridinium tetrafluoroborate ([BPy]BF4) was synthesized, and its structure was characterized and confirmed by 1H-NMR and IR. The densities and refractive indices of binary mixtures ([BPy]BF4+methanol) with different compositions were determined at T= 298.15 K and under atmospheric pressure by using a vibrating U-shaped sample tube densimeter and semi-automatic refractometer,respectively. The viscosities of the mixtures were also determined at T= 298.15 K and under atmospheric pressure by using Ubbelohde Suspended-level viscometer. Density values were used in the calculation of the excess molar volumes (V E), and the refractive indices were used to calculate the changes of refractive index (△nD). The achieved viscosities were used to calculate the viscosity B coefficient of the mixtures. The results show that the values of VE are negative over the entire composition range, while the △nD are positive. When the mole fraction of [BPy]BF4

  3. Primary retention following nuclear recoil in β-decay: Proposed synthesis of a metastable rare gas oxide (38ArO4) from (38ClO4−) and the evolution of chemical bonding over the nuclear transmutation reaction path

    International Nuclear Information System (INIS)

    Argon tetroxide (ArO4) is the last member of the N=50 e– isoelectronic and isosteric series of ions: SiO44−, PO43−, SO42−, and ClO4−. A high level computational study demonstrated that while ArO4 is kinetically stable it has a considerable positive enthalpy of formation (of ∼298 kcal/mol) (Lindh et al., 1999. J. Phys. Chem. A 103, pp. 8295–8302) confirming earlier predictions by Pyykkö (1990. Phys. Scr. 33, pp. 52–53). ArO4 can be expected to be difficult to synthesize by traditional chemistry due to its metastability and has not yet been synthesized at the time of writing. A computational investigation of the changes in the chemical bonding of chlorate (ClO4−) when the central chlorine atom undergoes a nuclear transmutation from the unstable artificial chlorine isotope 38Cl to the stable rare argon isotope 38Ar through β-decay, hence potentially leading to the formation of ArO4, is reported. A mathematical model is presented that allows for the prediction of yields following the recoil of a nucleus upon ejecting a β-electron. It is demonstrated that below a critical angle between the ejected β-electron and that of the accompanying antineutrino their respective linear momentums can cancel to such an extent as imparting a recoil to the daughter atom insufficient for breaking the Ar–O bond. As a result, a primary retention yield of ∼1% of ArO4 is predicted following the nuclear disintegration. The study is conducted at the quadratic configuration interaction with single and double excitations [QCISD/6−311+G(3df)] level of theory followed by an analysis of the electron density by the quantum theory of atoms in molecules (QTAIM). Crossed potential energy surfaces (PES) were used to construct a PES from the metastable ArO4 ground singlet state to the Ar–O bond dissociation product ArO3+O(3P) from which the predicted barrier to dissociation is ca. 22 kcal/mol and the exothermic reaction energy is ca. 28 kcal/mol [(U)MP2/6–311+G(d)]. - Highlights: • Mathematical model for the yield of primary retention after β-decay. • The nature of metastable chemical bonding in thermodynamically unstable compounds. • The changes in the nature of chemical bond upon nuclear transmutation. • Synthetic protocol of metastable rare gas oxides (ArO4) from a hot chemistry route

  4. Crystal and molecular structure of four copper(II) ethylenediaminedisuccinates, [Cu2(RR,SS-Edds)] . 6H2O, Ba2[Cu(RR,SS-Edds)](ClO4)2 . 8H2O, Ba[Cu(SS-HEdds)]ClO4 . 2H2O, and Ba3[Cu2(RR,SS-Edds)2](ClO4)2 . 6H2O

    International Nuclear Information System (INIS)

    Four Cu(II) complexes with the RR,SS-Edds4- and SS-HEdds3- anions are synthesized, and their crystal structures are studied. In the compounds [Cu2(RR,SS-Edds)] . 6H2O (I) and Ba2[Cu(RR,SS-Edds)](ClO4)2 . 8H2O (II), the ligand forms hexacoordinate chelate [Cu(Edds)]2- complexes with the N atoms and O atoms of the propionate groups in the equatorial positions and the O atoms of the acetate groups in the axial vertices. In the compounds Ba[Cu(SS-HEdds)]ClO4 . 2H2O (III) and Ba3[Cu2(RR,SS-Edds)2](ClO4)2 . 6H2O (IV), one of the propionate arms, the protonated arm in III and the deprotonated arm in IV, does not enter into the coordination sphere of the Cu atom. An acetate arm moves to its position in the equatorial plane, and the free axial vertex is occupied by an O atom of the perchlorate ion. In I-IV, the lengths of the equatorial Cu-N and Cu-O bonds fall in the ranges 1.970-2.014 and 1.921-1.970 A, respectively. The axial Cu-O bonds with the acetate groups and ClO4- anions are elongated to 2.293-2.500 and 2.727-2.992 A, respectively. In structure I, the second Cu atom acts as a counterion forming bonds with the O atoms of two water molecules and three O atoms of the Edds ligands. In II-IV, the Ba2+ cations are hydrated and bound to the O atoms of the anionic complexes and (except for one of the cations in IV) ClO4- anions. The coordination number of the Ba cations is nine. The structural units in I-IV are connected into layers. In I, an extended system of hydrogen bonds links the layers into a framework. In II and III, the layers are linked only by weak hydrogen bonds, one bond per structural unit. In IV, ClO4- anions are bound to the Ba and Cu atoms of neighboring layers, thus serving as bridges between the layers.

  5. Synthesis, crystal structure and thermochemical behaviour of complex of host-guest type [(LH2)(BF4)2·H2O] (L=racemate-5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)

    International Nuclear Information System (INIS)

    Interaction of BF3·(C2H5)2O with racemate 5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane in the presence of moisture of air results in [(LH2)(BF4)2·H2O] complex formation structure of which is determined by the method of x-ray diffraction analysis and is confirmed by thermogravimetry data. Crystal of the complex are monoclinic, space group - P21/n, a=25.570(7), b=11.231(5), c=8,715(4) A. Structure is built from two-charged organic cations of tetraazamacrocycle, tetrafluoroborate anions and water molecules in correlation 1:2:1 combined by hydrogen bond system in which all four nitrogen atoms of macrocycle performs the function of proton donors. Macrocycle in the complex takes a symmetry close by C2

  6. Spectral reflectance of the one-dimensional organic metals (perylene)2(PF6)1.1 × 0.8CH2Cl2 and (perylene)2(AsF6)1.1 × 0.7CH2Cl2

    OpenAIRE

    Wilckens, Rudolf; Geserich, Hans Peter; Ruppel, Wolfgang; Koch, P.; Schweitzer, Dieter; Keller, Heimo J.

    1982-01-01

    We report on the optical reflectance of (perylene)2(PF6)1.1 × 0.8CH2Cl2 and (perylene)2(AsF6)1.1 × 0.7CH2Cl2 single crystals in the energy range from 0.25 to 4 eV. For light polarized perpendicular to the molecular stacks the crystals exhibit the optical behaviour of an insulating molecular crystals, whereas for light polarized parallel to the stacks a pronounced plasma edge at hω=0,9eV image is observed. The experimental data were analyzed by a Lorentz-Drude model in order to determine ...

  7. Sulfur-containing trinuclear arene ruthenium clusters

    OpenAIRE

    Tschan, Mathieu; Therrien, Bruno; Chérioux, Frédéric; Süss-Fink, Georg

    2006-01-01

    The single-crystal X-ray structure analyses of [HRu3(C6H6)(C6Me6)2(μ3-SC6H4Me)(μ2-O)][BF4]2 ([1][BF4]2), [HRu3(C6H6)(C6Me6)2(μ3-SC6H4Me)(μ2-S)][PF6]2 ([2][PF6]2) and [H2Ru3(1,2,4,5-Me4C6H2)3(μ2-S)(Cl)]PF6([3][PF6]) are presented. The structures show the sulfur ligands to act as bridges between ruthenium atoms. In [1][BF4]2 and [2][PF6]2 the metallic core adopts a nido framework. However, in [3][PF6] the absence of a μ3-SR ligand combined with the presence of one terminal chloro unit gives ris...

  8. Synthesis, Crystal Structure and Polyphenol Oxidase Activities Study of [Cu(NTB)Cl] ClO4·2.5CH3 OH%[Cu(NTB)Cl]ClO4·2.5CH3OH的合成、晶体结构和多酚氧化酶活性研究

    Institute of Scientific and Technical Information of China (English)

    邱江华; 王光辉; 廖展如; 孟祥高

    2008-01-01

    合成了配合物[Cu(NTB)Cl]ClO4·2.5CH3OH(NTB为N,N,N-三(2(-苯并咪唑甲基)胺),并进行了紫外可见光谱、元素分析、循环伏安和单晶X射线衍射分析等表征.用UV-Vis.研究了以邻苯二酚、邻苯三酚为底物时配合物的多酚氧化酶活性,结果表明:配合物的多酚氧化酶活性符合米氏方程曲线;在pH为8.0和30℃的条件下,配合物催化邻苯三酚和邻苯二酚反应的转化数分别为88.2 h-1和0.54 h-1.通过动力学数据比较发现,邻苯三酚比邻苯二酚更容易氧化,而且它们的催化氧化速率都随着pH的升高而增大.%The title complex [ Cu (NTB) Cl ] ClO4 2.5 CH3 OH (NTB=Tris (benzimidazolyl-2-methyl) amine) has been synthesized and characterized by UV-Vis.,elemental analysis,cyclic voltammetry and single crystal X-ray diffraction anal-ysis.Polyphenol oxidase activities toward pyrogallol and catechol have been studied spectroscopically. Their kinetics obey the Michaelis-Menten equation. The turnover numbers of the complex toward pyrogallol are 88.2 h-1 and 0.54 h-1 for cate-chol at pH 8.0 and 30 ℃. Compared with the kinetic data,it is apparent that pyrogallol oxidation is easier than catechol,and catalytic activities increase with increasing of pH values.

  9. 水/离子液体[BMIM]PF6两相体系中全细胞催化生成单葡萄糖醛酸基甘草次酸%Biosynthesis of glycyrrhetic acid 3-O-mono-β-D-glucuronide by whole cell in ionic liquid/water biphasic system

    Institute of Scientific and Technical Information of China (English)

    陈金燕; 邹树平; 何冬梅; 杨晓刚; 李春

    2011-01-01

    研究了水/离子液体两相体系中重组毕赤酵母Pichia pastoris GS115(r-PGUS-P)全细胞转化甘草酸(GL)生成单葡萄糖醛酸基甘草次酸(GAMG)的反应.确定最适反应体系为离子液体[BMIM] PF6/水(2∶8,体积比),最适缓冲液pH、反应温度、底物浓度和细胞加入量分别为5.4、45℃、6.O mmol·L-1和8.0g·L-1.在此条件下反应58 h,产物GAMG得率和化学键选择性分别为69.6%和67.2%,与纯水相反应体系相比,分别提高了12.4%和12.61%.离子液体循环使用7次后,回收利用率为93.47%.产物GAMG和副产物甘草次酸(GA)在此两相体系中得到有效分离,为后续产物分离带来便利.%Glycyrrhizin (GL), the biologically active compounds of liquorice, can be hydrolysed to glycyrrhetic acid 3-O-mono-β-D-glucuronide (GAMG) by whole cells containing β-D-glucuronidase. GAMG is widely used in the pharmaceutical and food industries due to its stronger physiological functions, higher biological activity, more favorable sweetness, and lower caloric value as compared with GL. The recombinant Pichia pastoris (r-PGUS-P) designated in this work expressing β-D-glucuronidase, was used as a whole-cell biocatalyst catalyzing GL to GAMG in non-aqueous solvents systems. The results showed that r-PGUS-P gave the highest yield of GAMG in l-butyl-3-methylimidazolium hexafluorophosphate ( [BMIM] PF6 )/water (2 ∶ 8, vol) biphasic system. The optimal conditions of this reaction were determined as follows; optimum pH, substrate concentration, temperature and cell content were 5. 4, 6. 0 mmol · L-1, 45°C, and 8. 0 g · L-1, respectively. Under these optimized conditions, 69.6% yield of GAMG and 67. 2% of the chemical bond selectivity was achieved after 58 h reaction time, increase by 12. 4% and 12. 61%, respectively against aqueous phase. Simultaneously, the ionic liquid [BMIM]PF6 also remained at higher recovery percentage of about 93.47% during repeated use for 7 reaction cycles. Especially

  10. 离子液体[Bmim]PF6萃取-火焰原子吸收法测定水中痕量镉%Determination of Trace Cadmium in Water by Flame Atomic Absorption Spectrometry/with Ionic Liquid Extraction

    Institute of Scientific and Technical Information of China (English)

    王良; 李清; 闫永胜; 崔运成

    2011-01-01

    A novel method for the separation and determination of trace cadmium in environmental water sample by flame atomic absorption spectrometry (FAAS) with ionic liquid extraction was proposed. When the acidity of the solvent was pH 8, ionic liquid 1-butyl-3-methylimi dazolium hexafluorophosphate ([Bmim]PF6) was used as extractant, dithizone as the chelant, the sample was extracted for 3 min and determined by FAAS. The research result indicated that under optimum conditions, there was favorable linearity relation between 0. 15 and 58. 2 μg/L, detection limit (3δ) was 0. 095 ng/L (n=11). The recovery of this method was in the range of 90. 0% -108. 0% . The relative standard deviation is less than 5. 8% for the analysis of practical sample.%1 引言化学工业排放的废水含有大量金属镉,对环境产生严重危害,因而环境水样中痕量镉的准确测定具有重要意义.目前,常用原子吸收光谱法[1]测定痕量的镉,但由于环境水样中镉的含量低且样品复杂,为了提高分析方法的灵敏度和选择性,样品的预分离与富集至关重要.液-液萃取是一种常用的预分离与富集方法,但常用有机溶剂作萃取剂,易带来二次污染.离子液体是一种无毒、无污染、不挥发的"绿色溶剂"[2],具有安全、高效、环保等优点[3],已萃取分离了多种金属离子[4-5].本实验以双硫腙(H2Dz)为螯合剂,以离子液体1-丁基-3-甲基咪唑六氟磷酸盐( [Bmim]PF6)为萃取剂.用火焰原子吸收光谱法(FAAS)测定了离子液体相中的Cd,建立了痕量Cd的分离与分析方法,并应用于环境水样的分析.

  11. 水/[ NH2 ebim][ PF6]/Triton X-100/正丁醇/环己烷微乳液体系的制备%Preparation of microemulsion system based on[ NH2 ebim] [ BF6 ]/H2 O/TritonX-100/n-butonal/cyclohexane

    Institute of Scientific and Technical Information of China (English)

    刘红晶; 焦阳; 潘阳; 李冬

    2016-01-01

    Microemulsion with self-made task-specific ionic liquid[ NH2 ebim] [ BF6 ] ,[ NH2 ebim] [ BF6 ]/H2 O/TritonX-100/n-bu-tonal/cyclohexane microemulsion has been prepared. Microemulsion types have been determined by the analysis of electrical con-ductivity and the dynamic light scattering technique,and microemulsion region is divided into O/( S+W) and O/W microemulsion. The ternary phase diagrams has been drawn according to the experimental results. The aggregation behavior of water in the microe-mulsion system was studied by dissipative particle dynamics(DPD). The results of simulation are agree with those of experiment. The effects of the microemulsion region on the proportion of Triton X-100 and n-butonal were investigated. Experimental results show that the region of microemulsion increases with the increase of the proportion of Triton X-100 and n-butonal.%采用自制的功能离子液体1-(胺乙基)-3-丁基咪唑六氟磷酸盐([NH2ebim][PF6]),制备了水/[ NH2 ebim][ PF6]/Triton X-100/正丁醇/环己烷微乳液体系,通过动态光散射技术测定微乳液的粒径分布和分散相浓度,通过电导率仪测定体系电导率的变化,由这两种分析方法确定微乳液类型,微乳液类型被分为表面活性剂与水的互溶相包油型(O/S+W)和水包油型(O/W),并绘制出拟三元相图;通过耗散动力学(DPD)模拟不同水含量时微乳液体系中的聚集行为,模拟结果呈现出的微乳液类型与实验测定分析结果一致,证明了相图绘制的正确性;文中还考察了Triton X-100与正丁醇的比例对微乳液区域的影响,实验结果表明,随着Triton X-100与正丁醇的比例增加微乳液区域增大。

  12. Two Related Copper(I) π-Complexes Based on 2-Allyl-5-(2-pyridyl)-2H-tetrazole Ligand: Synthesis and Structure of [Cu(2-apyt)NO3] and [Cu(2-apyt)(H2O)](BF4) Compounds.

    Science.gov (United States)

    Slyvka, Yurii; Goreshnik, Evgeny; Pokhodylo, Nazariy; Pavlyuk, Oleksiy; Mys'kiv, Marian

    2016-01-01

    By means of the alternating current electrochemical technique two new π-compounds [Cu(2-apyt)NO3] (1) and [Cu (2-apyt)(H2O)](BF4) (2) have been obtained starting from the mixture of 1-allyl-5-(2-pyridyl)-2H-tetrazole (1-apyt), 2-allyl-5-(2-pyridyl)-2H-tetrazole (2-apyt) and corresponding copper(II) salts, and have been structurally studied. Selective complexation towards 2-allyl- isomer results in a formation of 2-apyt complexes. Copper(I) ion in both 1 and 2 complexes coordinates the allylic C=C bond, one pyridyl and one tetrazole N atoms. In both structures Cu+ center adopts distorted tetrahedral surrounding which additionally includes oxygen of NO3 - in 1 and H2O moiety in 2. Structure 1 is built from [Cu(2-apyt)NO3]2 dimeric fragments. Contrary, participation of H2O in the metal coordination in 2 leads to the infinite [Cu(2-apyt)(H2O)]+n chain construction. To analyze interactions between the particles in 1 and 2 Hirshfeld surface analysis was performed. PMID:27333565

  13. Study of reactivity of p-cymene ruthenium(II) dimer towards diphenyl-2-pyridylphosphine: Synthesis, characterization and molecular structures of [(6--cymene)RuCl2(PPh2Py)] and [(6--cymene)RuCl(PPh2Py)]BF4

    Indian Academy of Sciences (India)

    R Lalrempuia; Patrick J Carroll; Mohan Rao Kollipara

    2004-01-01

    The reaction of [{(6--cymene)Ru(-Cl)}2Cl2] with functionalized phosphine viz, diphenyl-2-pyridylphosphine yielded complexes of the type: (a) P-bonded complex [(6--cymene)RuCl2(PPh2Py)] (1), (b) P-, N-chelated complex [(6--cymene)RuCl-(PPh2Py)]BF4 (2) and [RuCl2(PPh2Py)2] (3) resulting from the displacement of the -cymene ligand. These complexes were characterized by 1H NMR, 31P NMR and analytical data. The structures of complexes 1 and 2 have been confirmed by single crystal X-ray diffraction study. Complex 1 crystallised in triclinic space group $\\bar{1}$ with = 10.9403 (3) Å, = 13.3108 (3) Å, = 10.5394 (10) Å, = 88.943 (2)°, = 117.193 (2)°, = 113.1680 (10)°, = 2 and = 1230.39 (5) Å3. The complex 2 crystallises in monoclinic space group 21 with = 9.1738 (4) Å, =14.0650 (6) s, = 10.7453 (5) Å, = 106.809 (1)°, = 2 and = 1327.22 (10) Å3.

  14. Theoretical Study on Ionic Liquid Based on 1-Ethyl-3-Methyl- Imidazolium Cation and Hexafluorophosphate or Tetrafluoroborate

    Institute of Scientific and Technical Information of China (English)

    Renqing Lü; Zuogang Cao; Guoping Shen

    2007-01-01

    The Hartree-Fock and DFT/B3LYP methods have been employed to investigate the electronic structures of l-ethyl-3-methyl-imidazolium cation (EMIM+), BF-4 , PF-6, EMIM+-BF-4, and EMIM+-PF6-using the Gaussian-94 soft-package at 6-31+G(d,p) basis set level for hydrogen, carbon, nitrogen, boron, phosphorus, and fluorine atoms. Comparison of the electronic structures of the lowest energy of EMIM+-BF4- and EMIM+-PF6- pairs, and single EMIM+, BF-4 and PF-6 showed that the optimized EMIM+-BF-4 and EMIM+-PF-6 pair conformers were BF-4 and PF-6 outside the 5-ring plane between the ethyl group and the methyl group. The cohesion of C-H…F hydrogen bond between cation and anion is reinforced by charge assistance. The interaction energy between EMIM+ and PF-6 is 328.8 kJ/mol at the B3LYP level and 326.6 kj/mol at the Hartree-Fock level, whereas that between EMIM+ and BFJ is 353.5 kj/mol at the B3LYP level and 350.5 kj/mol at the Hartree-Fock level. The low energy interactions caused by bulky asymmetric EMIM+, and charge dispersion of cation and anion give rise to the low melting point of ionic liquid EMIM+-BF-4 and EMIM+-PF-6. The two hydrogen bonding models of single hydrogen bond formation, and the hydrogen transfer between C2 in EMIM+ and F in BF-4 or PF-6 were principally depicted.

  15. INK-JET PRINTING OF PF6 FOR OLED APPLICATIONS

    International Nuclear Information System (INIS)

    In the last years there has been much interest in applying ink-jet printing (IJP) technology to the deposition of several materials for organic electronics applications, including metals, polymers and nanoparticles dispersions on flexible substrates. The aim of this work is to study the effect of ink-jet deposition of polymer films in the manufacturing of OLED devices comparing their performances to standard technologies. The ink-jet printed polymer is introduced in an hybrid structure in which other layers are deposited by vacuum thermal evaporation. The electrical and optical properties of the obtained devices are investigated.OLEDs with the same structure were fabricated by spin-coating a polymer film by the same solution used as ink. Results have been compared to the above ones to determine how the deposition method affects the device optoelectronic properties

  16. Oxidative degradation of the organometallic iron(II) complex [Fe{bis[3-(pyridin-2-yl)-1H-imidazol-1-yl]methane}(MeCN)(PMe3)](PF6)2: structure of the ligand decomposition product trapped via coordination to iron(II).

    Science.gov (United States)

    Haslinger, Stefan; Pöthig, Alexander; Cokoja, Mirza; Kühn, Fritz E

    2015-12-01

    Iron is of interest as a catalyst because of its established use in the Haber-Bosch process and because of its high abundance and low toxicity. Nitrogen-heterocyclic carbenes (NHC) are important ligands in homogeneous catalysis and iron-NHC complexes have attracted increasing attention in recent years but still face problems in terms of stability under oxidative conditions. The structure of the iron(II) complex [1,1'-bis(pyridin-2-yl)-2,2-bi(1H-imidazole)-κN(3)][3,3'-bis(pyridin-2-yl-κN)-1,1'-methanediylbi(1H-imidazol-2-yl-κC(2))](trimethylphosphane-κP)iron(II) bis(hexafluoridophosphate), [Fe(C17H14N6)(C16H12N6)(C3H9P)](PF6)2, features coordination by an organic decomposition product of a tetradentate NHC ligand in an axial position. The decomposition product, a C-C-coupled biimidazole, is trapped by coordination to still-intact iron(II) complexes. Insights into the structural features of the organic decomposition products might help to improve the stability of oxidation catalysts under harsh conditions. PMID:26632838

  17. 二苯并噻吩及其氧化物与离子液体相互作用的理论研究%Theoretical study on the interactions between dibenzothiophene/dibenzothiophene sulfone and ionic liquids

    Institute of Scientific and Technical Information of China (English)

    吕仁庆; 林进; 曲占庆

    2012-01-01

    采用密度泛函理论方法比较了DBT/DBTO2和[BMIM]+[PF6]-/[BMIM]+[BF4]-的相互作用.对最稳定的[BMIM]+[PF6]-、[BMIM]+[PF6--DBT、[BMIM]+[PF6]-DBTO2、[BMIM]+[BF4]-、[BMIM]+ [BF4]--DBT、[BMIM]+[BF4]--DBTO2进行了NBO和AIM分析.结果表明,DBT和[BMIM]+[PF6]/[BMIM]+[BF4]-中的咪唑环彼此相互平行,NBO和AIM分析表明它们之间发生了π-π相互作用.H1’和H9’形成的F…H氢键有利于π-π堆积作用的形成.DBTO2倾向于趋近C2-H2和甲基基团形成O…H相互作用;DBTO2优先吸附在[BMIM]+[PF6]-/[BMIM]+[BF4]-.在模拟油中,[BMIM]+[PF6]-和[BMIM]+[BF4]-离子液体对DBTO2的萃取能力大于DBT,其原因是可能是DBTO2具有较大的极性和O…H与F…H的氢键作用.%The interactions between sulfur-containing compounds of dibenzothiophene (DBT) and dibenzothiophene sulfone (DBTO2) and ionic liquids of 1-butyl-3-methylimidazolium hexafiuoropnospnate ([BMIM] + [PF6]-) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM] + [BF4]-) were comparatively studied by using density functional theory.The most stable structures of [BMIM]+ [PF6]-,[BMIM]+ [PF6]--DBT,[BMIM]+ [PF6]--DBTO2,[BMIM]+ [BF4]-,[BMIM] + [BF4]--DBT,and [BMIM] + [BF4]--DBTO2 systems were obtained by natural bond orbitals (NBO) and atoms in molecules (AIM) anaiyses.The results indicated that DBT and [BMIM] rings of [BMIM] + [PF6]-/[BMIM] + [BF4]-are parallel to each other.There is a strong π-π interaction between them in terms of NBO and AIM analyses.The H1' and H9' involved F…H hydrogen bonding interactions may favor the formation of π-π stacking interactions.The DBTO2 preferentially locates near the C2-H2 and methyl group of [BMIM] + to form O…H interactions.The predicted geometries and interaction energies imply the preferential adsorption of DBTO2 on [BMIM] + [PF6]-/[BMIM] + [BF4]-.The [BMIM] + [PF6] /[BF4]-have better extracting ability to remove DBTO2 than DBT,possibly due to the larger polarity of DBTO2 and stronger interactions

  18. Direct Electrochemistry of a GCE Modified with HRP/Gel-MWCNTs in Ionic Liquid [BMIM] BF4%基于明胶-碳纳米管的辣根过氧化物酶修饰电极在离子液体中的直接电化学

    Institute of Scientific and Technical Information of China (English)

    姚慧; 王燕; 董元; 孙迪; 张严化

    2012-01-01

    制备了明胶(Gel)-多壁碳纳米管(MWCNTs)纳米复合物,将其修饰在玻碳电极表面,再吸附辣根过氧化物酶(HRP),制得明胶-多壁碳纳米管-辣根过氧化物酶修饰电极(Gel-MWCNTs-HRP/GCE).该修饰电极在PBS中的循环伏安图上出现了一对峰形良好、几乎对称的氧化还原峰,式量电位为-0.356 V(vs.SCE),表明包埋在Gel-MWCNTs中的HRP与电极之间发生了直接电子传递.当扫速在20 ~ 180 mV/s时,氧化峰电流(Ipa)与还原峰电流(Ipc)均与扫速成正比,表明电极过程是受电子传递速率控制的表面传质过程.运用循环伏安法研究了修饰电极的电化学特性,探讨了工作电位、pH值、干扰物质等对修饰电极的影响.实验结果表明,HRP在修饰电极表面能有效和稳定地进行直接电子转移,并保持了其对过氧化氢(H2O2)的生物催化活性.进一步研究发现,在含有亲水性离子液体1-丁基-3-甲基咪唑四氟硼酸([BMIM]BF4)的溶液中,修饰电极对H2O2显示出更灵敏的催化活性,其线性范围为2.0×10-7~0.13 mol/L,检出限(S/N =3)为2.3×10-8 mol/L.该电极具有灵敏度高、重现性及稳定性好、使用寿命较长等优点,同时还显示了较好的抗干扰能力.%A novel hydrogen peroxide biosensor was constructed based on horseradish peroxidase (HRP) immobilized onto glass carbon electrode (GCE) , which was modified with the nanocomposite of gelatin and multi-walled carbon nanotubes ( MWCNTs ). The electrochemistry and electrocatalysis of the modified biosensor were investigated. A pair of well-defined and nearly symmetrical redox peaks with a formal potential of -0.356 Y(vs. SCE) in PBS were observed, which attribute to the direct electron transfer between the entrapped HRP and the electrode. The redox peak current was proportional to scan rate in the range of 20 -180 mV/s, indicating that the process was affected by e-lectronic transfer electrode rate control surface of mass transfer process

  19. Experimentally determining the exchange parameters of quasi-two-dimensional Heisenberg magnets

    International Nuclear Information System (INIS)

    Though long-range magnetic order cannot occur at temperatures T>0 in a perfect two-dimensional (2D) Heisenberg magnet, real quasi-2D materials will invariably possess nonzero inter-plane coupling Jperpendicular driving the system to order at elevated temperatures. This process can be studied using quantum Monte Carlo calculations. However, it is difficult to test the results of these calculations experimentally since for highly anisotropic materials in which the in-plane coupling is comparable with attainable magnetic fields Jperpendicular is necessarily very small and inaccessible directly. In addition, because of the large anisotropy, the Neel temperatures are low and difficult to determine from thermodynamic measurements. Here, we present an elegant method of assessing the calculations via two independent experimental probes: pulsed-field magnetization in fields of up to 85 T, and muon-spin rotation. We successfully demonstrate the application of this method for nine metal-organic Cu-based quasi-2D magnets with pyrazine (pyz) bridges. Our results suggest the superexchange efficiency of the [Cu(HF2)(pyz)2]X family of compounds (where X can be ClO4, BF4, PF6, SbF6 and AsF6) might be controlled by the tilting of the pyz molecule with respect to the 2D planes

  20. Pulse radiolysis study of salt effects on reactions of aromatic radical cations with Cl-

    International Nuclear Information System (INIS)

    The effect of quaternary ammonium salts on the decays of the radical cations of biphenyl, trans-stilbene, anthracene and pyrene generated by pulse radiolysis in chlorohydrocarbons has been investigated. The decays, which are due to neutralization reactions with Cl-, are retarded by the addition of salts having non-nucleophilic PF6-, BF4- and ClO4-, whereas the radical cations are rapidly quenched by salts having I- and BPh4-. The retarding effect of the salts is attributed to the formation of ion pairs between the reacting ions and the counter-ions from the salts. The rate constants for the neutralization reactions in 1,2-dichloroethane have been determined for the free-ion and ion-paired states; the latter state is attained by the addition of Bu4NPF6. The rate constant determined in the absence of the salt for Pysup(radical)+ is one order of magnitude smaller than those for the others. The salt effect is also smallest on the reaction of Pysup(radical)+. The charge delocalisation of the large aromatic radical cation may be responsible for the exceptional results for Pysup(radical)+. The largest salt effect was observed on the reaction of Ph2CH+, a charge-localized carbenium ion investigated for comparison. The solvent effect on the neutralization reactions is also discussed. (author)

  1. Synthesis and properties of trimethyl-TSF containing alloys of the TMTSF2 family

    DEFF Research Database (Denmark)

    Johannsen, Ib; Bechgaard, Klaus; Jacobsen, C. S.;

    1985-01-01

    Cation-radical salts of the general formula (TriMTSFzTMTSF1-z)2 (X=PF6, ClO4, z ranging from 0 to 0.3) were isostructural. The incorporation of TriMTSF resulted only in minor changes in the transport properties, but the superconducting ground state was completely suppressed...

  2. EFFECT OF WATER ON THE CONDUCTIVITY OF PPQ (ClO4) COMPLEX

    Institute of Scientific and Technical Information of China (English)

    ZHANG Chi; LU Fengcai

    1993-01-01

    The preparation of conducting PPQ film was first reported in the previous paper[1]. It is very interesting that this film is highly sensitive to moisture in air. The hydration and dehydration of the film are accompanied by change not only in color but also in conductivity and UV-visible spectrum. The conducting PPQ is reduced to PPQ and loses its conductivity after being soaked in water.

  3. Experimental and Theoretical Investigation of a Series of Novel Dimanganese(III) μ-Hydroxo Bisporphyrins: Magneto-Structural Correlation and Effect of Metal Spin on Porphyrin Core Deformation.

    Science.gov (United States)

    Sil, Debangsu; Bhowmik, Susovan; Khan, Firoz Shah Tuglak; Rath, Sankar Prasad

    2016-04-01

    The synthesis, structure, and properties of a new family of five ethane-bridged dimanganese(III) μ-hydroxo bisporphyrins with the same core structure but different counteranions are reported here. Additions of 10% Brønsted acids such as HI, HBF4, HSbF6, HPF6, and HClO4 to a dichloromethane solution of the dichloro dimanganese(III) bisporphyrin produces complexes having a remarkably bent μ-hydroxo group with I3(-), BF4(-), SbF6(-), PF6(-), and ClO4(-) as counteranions, respectively. The X-ray structures of all complexes have been determined, which have revealed the presence of two equivalent high-spin manganese(III) centers with equally distorted porphyrin rings in the complexes, in sharp contrast with the case for the diiron(III) μ-hydroxo bisporphyrin analogues. (1)H NMR spectra have shown highly deshielded meso resonances, unlike the case for the diiron(III) analogues, where the meso resonances are highly shielded. The variable-temperature magnetic data have been subjected to a least-squares fit which provides a moderate antiferromagnetic coupling through the hydroxo bridge between two zero-field split Mn(III) centers with coupling constant (J) values ranging from -29.5 to -38.6 cm(-1). Fairly good correlations are observed for J with Mn-O(H) distances and Mn-O(H)-Mn angles for all the complexes except for that having an I3(-) counteranion. DFT calculations support the stabilization of two equivalent high-spin Mn(III) porphyrin cores in the complexes and have also explored the role of metal spin in controlling porphyrin ring deformation. Unlike diiron(III) μ-hydroxo bisporphyrin complexes, the dimanganese(III) analogues do not have easily accessible spin states of the metal attainable by subtle environmental perturbations and, therefore, can only stabilize the high-spin state with a variety of counteranions. PMID:27002790

  4. Syntheses, structures and properties of silver(I) complexes with flexible 1,3,5-tris(pyridylmethoxyl)benzene ligands

    International Nuclear Information System (INIS)

    Five new silver(I) complexes [Ag2(L2)2](BF4)2.CH3CN.CH3OH (1), [Ag(L2)(CF3SO3)] (2), [Ag(L3)]ClO4.CH3OH (3), [Ag2(L3)2](CF3SO3)2.CH3CN.CH3OH.H2O (4) and [Ag(L3)]PF6.2CH3CN (5) [L2=1,3,5-tris(2-pyridylmethoxyl)benzene, L3=1,3,5-tris(3-pyridylmethoxyl)benzene] were synthesized and characterized by single crystal X-ray diffraction analyses. In complexes 1-5, ligands L2 and L3 show different conformations and act as three-connectors, while the Ag(I) atom serves as three-connecting node to result in the formation of 2D and 3D frameworks. Complexes 1 and 2 with different counteranions have similar 2D network structure with the same (4,82) topology. Complex 3 has a 3D structure with (10,3)-a topology while complexes 4 and 5 have the same 2D (6,3) topological structure. The results showed that the structure of organic ligands and counteranions play subtle but important role in determining the structure of the complexes. In addition, the photoluminescence and anion-exchange properties of the complexes were investigated in the solid state at room temperature. - Graphical abstract: Five new silver(I) coordination frameworks with different topology were obtained and their structures were determined by single crystal X-ray diffraction studies. The influence of counteranion and ligand on the structure of complexes was discussed, the photoluminescence and anion-exchange properties were reported.

  5. Excess heat capacities of (binary + ternary) mixtures containing [emim][BF4] and organic liquids

    International Nuclear Information System (INIS)

    Highlights: • The CPE and (CPE)ijk data have been measured over entire composition range at four temperatures. • The observed data have been fitted to Redlich–Kister equation. • The observed data have been analyzed in terms of Graph theory. • The values determined by Graph theory compare well with experimental values. - Abstract: The excess heat capacities, CPE and (CPE)ijk (calculated from the measured molar heat capacities, Cp data) of binary 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + pyrrolidin-2-one or 1-methylpyrrolidin-2-one or pyridine (j); pyrrolidin-2-one (i) + pyridine (j) and ternary 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + pyrrolidin-2-one or 1-methylpyrrolidin-2-one (j) + pyridine (k) mixtures have been measured as a function of composition at T = (293.15, 298.15, 303.15 and 308.15) K and 0.1 MPa using micro differential scanning calorimeter. The (CPE)ijk values for the present ternary mixtures are positive over entire range of composition. The CPE and (CPE)ijk data have been fitted to Redlich–Kister equation to compute binary and ternary adjustable parameters along with their standard deviations. The topology of the constituent molecules (Graph theory) has been utilized to obtain the expressions that describe well the CPE and (CPE)ijk data of the present mixtures. It has been observed that Graph theory describes well the CPE and (CPE)ijk data of the binary as well as ternary mixtures

  6. Electrochemical Reduction of 2-Nitroanisole in Ionic Liquid BMIm-BF4: Synthesis of 2-Anisidine

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A new electrochemical synthesis of 2-anisidine from 2-nitroanisole has been developed in room-temperature ionic liquid (RTIL), which was carded out under mild and safe conditions, where the volatile, toxic solvents, catalysts, as well as any additional supporting electrolyte were avoided. The maximal yield of 2-anisidine reached 51.3% on Cu-graphite couple electrodes under potentiostatic electrolysis at -1.0 V (vs. SCE) until 6 F·mol-1 of charge was passed at 50℃, which offers a new and clean route to synthesis of 2-anisidine. The reduction behavior of 2-nitroanisole was studied in RTIL by cycle voltammertry. The RT1L could be recycled.

  7. Liquid-Liquid Equilibrium in Quaternary System [bmim][PF6] + Water + 1-Methylimidazole + 1-Chlorobutane

    Czech Academy of Sciences Publication Activity Database

    Bendová, Magdalena; Klusoň, P.; Sedláková, Zuzana; Wagner, Zdeněk; Černá, I.; Vašinová, J.

    Wageningen : De Vlinderstichting, 2008, s. 1. ISBN N. [13th International Symposium on Solubility Phenomena and Related Equilibrium Processes. Trinity College Dublin (IE), 28.07.2008-31.07.2008] R&D Projects: GA ČR GA104/07/0444; GA ČR GP104/06/P066; GA AV ČR IAA400720710 Institutional research plan: CEZ:AV0Z40720504 Keywords : liquid-liquid equilibrium * ionic liquids * thermodynamics Subject RIV: CF - Physical ; Theoretical Chemistry

  8. Liquid-Liquid Equilibrium in Ternary Systems 1-Chlorobutane + 1-Methylimidazole + Water / [bmim][PF6

    Czech Academy of Sciences Publication Activity Database

    Bendová, Magdalena; Klusoň, Petr; Sedláková, Zuzana; Černá, I.; Vašinová, J.

    - : -, 2009, s. 61. ISBN N. [Encontro Nacional de Química Física / 1st Iberian Meeting on Ionic Liquids /9./. Aveiro (PT), 15.06.2009-16.06.2009] R&D Projects: GA ČR GA104/07/0444; GA ČR GP104/06/P066; GA AV ČR IAA400720710 Institutional research plan: CEZ:AV0Z40720504 Keywords : liquid-liquid equilibrium * ionic liquids * extraction Subject RIV: CF - Physical ; Theoretical Chemistry

  9. Rapid and simultaneous determination of tetrafluoroborate, thiocyanate and hexafluorophosphate by high-performance liquid chromatography using a monolithic column and direct conductivity detection.

    Science.gov (United States)

    Yang, Ling; Yu, Hong; Wang, Yaqin

    2010-01-01

    A method was developed for fast and simultaneous determination of tetrafluoroborate (BF(4)(-)), thiocyanate (SCN(-)) and hexafluorophosphate (PF(6)(-)) by high-performance liquid chromatography using a silica-based monolithic column and direct (non-suppressed) conductivity detection. Chromatographic separation was performed on a Chromolith Speed ROD RP-18e column with tetrabutylammonium hydroxide (TBA) + citric acid + acetonitrile as eluent. The effects of the types of eluent, TBA concentration, acetonitrile volume fraction, eluent pH, column temperature and flow rate on the retention of anions were investigated. The optimized chromatographic conditions were selected. Under the optimal conditions, the baseline separation of BF(4)(-), SCN(-) and PF(6)(-) was achieved without any interference by other anions (F(-), Cl(-), Br(-), I(-), NO(3)(-), ClO(3)(-) and SO(4)(2-)). The detection limit (S/N = 3) was 0.42, 0.46 and 1.42 mg L(-1) for BF(4)(-), SCN(-) and PF(6)(-), respectively. The present method was successfully applied to the determination of BF(4)(-), SCN(-) and PF(6)(-) in ionic liquids. PMID:20702939

  10. Designing New Electrolytes for Lithium Ion Batteries Using Superhalogen Anions

    CERN Document Server

    Srivastava, Ambrish Kumar

    2016-01-01

    The electrolytes used in Lithium Ion Batteries (LIBs) such as LiBF4, LiPF6 etc. are Li-salts of some complex anions, BF4-, PF6- etc. The investigation shows that the vertical detachment energy (VDE) of these anions exceeds to that of halogen, and therefore they behave as superhalogen anions. Consequently, it might be possible to design new electrolytic salts using other superhalogen anions. We have explored this possibility using Li-salts of various superhalogen anions such as BO2-, AlH4-, TiH5- and VH6- as well as hyperhalogen anions, BH4-y(BH4)y-(y = 1 to 4). Our density functional calculations show that Li-salts of these complex anions possess similar characteristics as those of electrolytic salts in LIBs. Note that they all are halogen free and hence, non-toxic and safer than LiBF4, LiPF6 etc. In particular, LiB4H13 and LiB5H16 are two potential candidates for electrolytic salt due to their smaller Li-dissociation energy ({\\Delta}E) than those of LiBF4, LiPF6 etc. We have also noticed that {\\Delta}E of Li...

  11. Insights into the strong in-vitro anticancer effects for bis(triphenylphosphane)iminium compounds having perchlorate, tetrafluoridoborate and bis(chlorido)argentate anions.

    Science.gov (United States)

    Folda, Alessandra; Scalcon, Valeria; Ghazzali, Mohamed; Jaafar, Mohammed H; Khan, Rais Ahmad; Casini, Angela; Citta, Anna; Bindoli, Alberto; Rigobello, Maria Pia; Al-Farhan, Khalid; Alsalme, Ali; Reedijk, Jan

    2015-12-01

    Three new compounds containing the bis(triphenylphosphane)iminium cation (PPN(+)) with ClO4(-), BF4(-) and [AgCl2](-) as counter anions have been synthesized and structurally characterized. The two derivatives with ClO4(-) and BF4(-) were found to be isostructural by single crystal X-ray diffraction. Interestingly, the three compounds show extremely potent antiproliferative effects against the human cancer cell line SKOV3. To gain insights into the possible mechanisms of biological action, several intracellular targets have been considered. Thus, DNA binding has been evaluated, as well as the effects of the compounds on the mitochondrial function. Furthermore, the compounds have been tested as possible inhibitors of the seleno-enzyme thioredoxin reductase. PMID:26384162

  12. Tuning the optical properties of 2-thienylpyridyl iridium complexes through carboranes and anions.

    Science.gov (United States)

    Zhu, Lin; Tang, Xiao; Yu, Qi; Lv, Wen; Yan, Hong; Zhao, Qiang; Huang, Wei

    2015-03-16

    2-Thienylpyridyl iridium(III) complexes containing an o-, m-, or p-carboranylvinyl-2,2'-bipyridine ligand and various counteranions (denoted o-PF6, m-BF4, m-PF6, m-SbF6, m-ClO4, m-OTf, m-NO3, m-BPh4, m-F, m-Cl, and p-PF6) were synthesized by using C-formyl carboranes as starting materials. The solid-state structures of o-PF6, m-PF6, m-ClO4, and m-BF4 showed that the cations form twisted cavities in which the anions are fixed by multiple hydrogen bonds. Anion-hydrogen interactions were investigated for nine m-carborane-based complexes with different counteranions. All carborane-based iridium(III) complexes show similar phosphorescence yields in solution but significantly different emission in the solid state. Anion-exchange titration and theoretical calculations revealed the relationships between structures and optical properties. The size of the anion and C-H⋅⋅⋅X anion-hydrogen bonds strongly influence the phosphorescence quantum yield in the solid state. In particular, the Ccar-H⋅⋅⋅X hydrogen bonds between the carboranyl unit and the anion play an important role in solid-state phosphorescence. Complex p-PF6 was successfully applied in phosphorescence-lifetime bioimaging owing to its low toxicity and near-infrared emission. PMID:25663604

  13. Overlayer-mediated superconductivity of Bechgaard-salt single crystals

    International Nuclear Information System (INIS)

    Thin films of superconducting (TMTSF)2ClO4 (where TMTSF = tetramethyltetraselenafulvalene) have been prepared by simply immersing crystals of (TMTSF)2PF6 in dichloromethane solutions of nBu4N+-ClO4-. The mechanism of this unprecedented, highly efficient, ion-exchange process is examined in this communication, while the resistance and magnetoresistance of these layers are studied as a function of temperature. The morphologies of the films are studied by energy dispersive spectrometry. (orig.)

  14. Zinc(II) and Cadmium(II) complexes with N4-coordinate pyrazole based ligand: Syntheses, characterization and structure

    Science.gov (United States)

    Solanki, Ankita; Sadhu, Mehul H.; Kumar, Sujit Baran; Mitra, Partho

    2014-11-01

    A series of six new mononuclear zinc(II) complexes of the type [Zn(X)(dbdmp)]Y (1-6) (X = N3-/NCO-/NCS-, Y = ClO4-/PF6-, and dbdmp = N,N-diethyl-N‧,N‧-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1,2-diamine), two binuclear cadmium(II) complexes [{Cd(dbdmp)}2(μ-N3)2](Y)2 (7-8) and three mononuclear cadmium(II) complexes [Cd(NCO)(dbdmp)]Y (Y = ClO4-/PF6-) (9-10) and [Cd(NCS)2(dbdmp)] (11) have been synthesized and characterized by physico-chemical methods. Crystal structures of the complexes [Zn(N3)(dbdmp)]ClO4 (1), [{Cd(dbdmp)}2(μ-N3)2](ClO4)2 (7), [Cd(NCO)(dbdmp)]ClO4 (9) and [Cd(NCS)2(dbdmp)] (11) have been solved by single crystal X-ray diffraction studies and showed that [Zn(N3)(dbdmp)]ClO4 (1) and [Cd(NCO)(dbdmp)]ClO4 (9) have distorted trigonal bipyramidal geometry, [Cd(NCS)2(dbdmp)] (11) and [(dbdmp)Cd(μ-N3)]2(ClO4)2 (7) have distorted octahedral geometry.

  15. Syntheses, characterization and electrochemical and spectroscopic properties of ruthenium-iron complexes of 2,3,5,6-tetrakis(2-pyridyl)pyrazine and ferrocene-acetylide ligands.

    Science.gov (United States)

    Wen, Hui-Min; Wang, Jin-Yun; Zhang, Li-Yi; Shi, Lin-Xi; Chen, Zhong-Ning

    2016-06-28

    Heterodimetallic Ru-Fe complexes [(tppz)(PPh3)2RuL](ClO4) (L = C[triple bond, length as m-dash]CFc, [](ClO4); C[triple bond, length as m-dash]C-C6H4-C[triple bond, length as m-dash]CFc), [](ClO4); C[triple bond, length as m-dash]C-C6H4-C6H4-C[triple bond, length as m-dash]CFc, [](ClO4)) were synthesized by the reactions of [(tppz)(PPh3)2RuCl](ClO4) (tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine) with ferrocence-acetylide ligands and characterized by ESI-MS, and (1)H and (31)P NMR spectroscopies. The structure of [](PF6) was determined by X-ray crystallography. The electrochemical studies show that compounds [](ClO4)-[](ClO4) possess two widely separated anodic peaks, ascribable to one-electron oxidation of Fc and Ru(II), respectively. This assignment is further corroborated by the results of UV-vis-NIR, XPS, and theoretical calculation studies. Compound [](ClO4) exhibits significant RuFe metal-metal interactions across the Ru-C[triple bond, length as m-dash]C-Fc backbone. As revealed by electrochemical, spectroscopic and theoretical computational studies, one-electron oxidized species [](ClO4)2 is between the electronically delocalized and valence-trapped state and shows a typical Robin-Day class II mixed-valence behavior. PMID:27273611

  16. Assembly of Heterometallic Rigid-Rod Complexes and Coordination Oligomers from Gold(I) Metalloligands.

    Science.gov (United States)

    Cámara, Verónica; Barquero, Natalia; Bautista, Delia; Gil-Rubio, Juan; Vicente, José

    2015-07-01

    The reactions of TpylC6H4C≡CAuL (Tpyl = 2,2':6',2″-terpyridin-4'-yl; L = PPh3, CNXy; Xy = 2,6-dimethylphenyl) with MX2·nH2O (M = Fe, X = ClO4; M = Co, X = BF4; M = Zn, X = TfO, ClO4) in a 2:1 molar ratio give complexes [M(TpylC6H4C≡CAuL)2]X2. Similarly, the reactions of PPN[(TpylC6H4C≡C)2Au] (PPN = (Ph3P)2N) with an equimolar amount of MX2·nH2O give coordination oligomers [M{(TpylC6H4C≡C)2Au}]nXn (M = Fe, Zn, X = ClO4; M = Co, X = BF4). The complexes and oligomers have been isolated and characterized. The crystal structures of [Fe(TpylC6H4C≡CAuCNXy)2](ClO4)2 and [Co(TpylC6H4C≡CAuPPh3)2](BF4)2 have been determined by X-ray diffraction. The hydrodynamic sizes of complexes [M(TpylC6H4C≡CAuPPh3)2]X2 and coordination oligomers [M{(TpylC6H4C≡C)2Au}]nXn have been studied by NMR diffusion spectroscopy and dynamic light scattering measurements. PMID:26087239

  17. Second virial coefficient of bmimBF4/triton X-100/ cyclohexane ionic liquid microemulsion as investigated by microcalorimetry.

    Science.gov (United States)

    Li, Na; Zhang, Shaohua; Zheng, Liqiang; Gao, Yan'an; Yu, Li

    2008-04-01

    The second virial coefficient of the ionic liquid (IL) microemulsion was obtained for the first time using microcalorimetry. The heat of dilution of the microemulsion solutions was measured by isothermal titration microcalorimetry (ITC), and the second virial coefficient was derived from the heat of dilution and the number density of the IL microemulsion solutions on the basis of a hard-sphere interaction potential assumption and as a function of the second-order polynomial. The validity of the second virial coefficient was confirmed by the percolation behavior of different ionic liquid microemulsion solutions of Triton X-100 in cyclohexane with or without added salts. The information obtained from the second virial coefficient shows that the interactions between ionic liquid microemulsion droplets are much stronger than those for traditional microemulsions, which may be attributed to the relatively larger size of the microemulsion droplets. PMID:18312017

  18. Charge-Transfer Excitations in the Model Superconductor HgBa$_2$CuO$_{\\bf 4+\\delta}$

    OpenAIRE

    L. Lu; Zhao, X.; Chabot-Couture, G.; Hancock, J. N.; Kaneko, N; Vajk, O. P.; Yu, G.; Grenier, S.; Kim, Y. J.; Casa, D.; Gog, T.; Greven, M.

    2005-01-01

    We report a Cu $K$-edge resonant inelastic x-ray scattering (RIXS) study of charge-transfer excitations in the 2-8 eV range in the structurally simple compound HgBa$_2$CuO$_{4+\\delta}$ at optimal doping ($T_{\\rm c} = 96.5 $ K). The spectra exhibit a significant dependence on the incident photon energy which we carefully utilize to resolve a multiplet of weakly-dispersive ($ < 0.5$ eV) electron-hole excitations, including a mode at 2 eV. The observation of this 2 eV excitation suggests the exi...

  19. Differential Pathogenicity of Two Feline Leukemia Virus Subgroup A Molecular Clones, pFRA and pF6A

    OpenAIRE

    Phipps, Andrew J.; Chen, Hang; Hayes, Kathleen A.; Roy-Burman, Pradip; Mathes, Lawrence E.

    2000-01-01

    F6A, a molecular clone of subgroup A feline leukemia virus (FeLV) is considered to be highly infectious but weakly pathogenic. In recent studies with a closely related subgroup A molecular clone, FRA, we demonstrated high pathogenicity and a strong propensity to undergo recombination with endogenous FeLV (enFeLV), leading to a high frequency of transition from subgroup A to A/B. The present study was undertaken to identify mechanisms of FeLV pathogenesis that might become evident by comparing...

  20. Electrochemical Investigation of Li-Al Anodes in Oligo (ethylene glycol) Dimethyl ether/LiPF6

    Energy Technology Data Exchange (ETDEWEB)

    Y Zhou; X Wang; H Lee; K Nam; X Yang; O Haas

    2011-12-31

    LiPF{sub 6} dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight 5 g mol{sup -1} was investigated as a new electrolyte (OEGDME5, 1 M LiPF{sub 6}) for metal deposition and battery applications. At 25 C a conductivity of .48 x 1{sup -3} S cm{sup -1} was obtained and at 85 C, 3.78 x 1{sup -3} S cm{sup -1}. The apparent activation barrier for ionic transport was evaluated to be 3.7 kJ mol{sup -1}. OEGDME5, 1 M LiPF{sub 6} allows operating temperature above 1 C with very attractive conductivity. The electrolyte shows excellent performance at negative and positive potentials. With this investigation, we report experimental results obtained with aluminum electrodes using this electrolyte. At low current densities lithium ion reduction and re-oxidation can be achieved on aluminum electrodes at potentials about 28 mV more positive than on lithium electrodes. In situ X-ray diffraction measurements collected during electrochemical lithium deposition on aluminum electrodes show that the shift to positive potentials is due to the negative Gibbs free energy change of the Li-Al alloy formation reaction.

  1. Study on the competition between density waves, singlet, and triplet pairing superconductivity in an organic conductor (TMTSF)2PF6

    International Nuclear Information System (INIS)

    We study the effect of the dimerization of molecules and the effect of magnetic field on the phase competition in quasi-one-dimensional organic superconductors (TMTSF)2X by applying the random phase approximation method. We conclude the following: (i) Due to the decrease of the dimerization, which corresponds to applying the pressure and cooling, spin and charge density wave states are suppressed and give way to a superconducting state. (ii) Applying the magnetic field favors the spin triplet f-wave pairing with spins parallel to the magnetic field due to the cooperation between the magnetic field and the long range off-site interactions

  2. A Facile Approach of Diels-Alder Reaction in Imidazolium-based Ionic Liquids at Room Temperature

    Directory of Open Access Journals (Sweden)

    Nur Liyana Sakinah Johari

    2014-09-01

    Full Text Available A Diels-Alder reaction between anthracene and 1-p-tolyl-2,5-dione was conducted in imidazolium-based ionic liquids. Imidazolium cation was utilised with counter anions, [BF4] and [PF6], as the solvents to carry out the desired Diels-Alder reaction. In this work, the diene and dienophile were introduced into the ionic liquids for 72 hours at room temperature. The desired cycloadduct was prepared by a green chemistry procedure in high yield. The expected cycloadduct was characterized on the MS as well as FTIR and NMR spectroscopy. Herein we report, only the [Bmim][BF4] ionic liquid gave the desired cycloadduct in 86 % yield compared to [Bmim][PF6].

  3. Adsorption, Thermodynamic and Quantum Chemical Studies of 1-hexyl-3-methylimidazolium Based Ionic Liquids as Corrosion Inhibitors for Mild Steel in HCl

    Directory of Open Access Journals (Sweden)

    Motsie E. Mashuga

    2015-06-01

    Full Text Available The inhibition of mild steel corrosion in 1 M HCl solution by some ionic liquids (ILs namely, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate [HMIM][TfO], 1-hexyl-3-methylimidazolium tetrafluoroborate [HMIM][BF4], 1-hexyl-3-methylimidazolium hexafluorophosphate [HMIM][PF6], and 1-hexyl-3-methylimidazolium iodide [HMIM][I] was investigated using electrochemical measurements, spectroscopic analyses and quantum chemical calculations. All the ILs showed appreciably high inhibition efficiency. At 303 K, the results of electrochemical measurements indicated that the studied ILs are mixed-type inhibitors. The adsorption studies showed that all the four ILs adsorb spontaneously on steel surface with [HMIM][TfO], [HMIM][BF4] and [HMIM][I] obeying Langmuir adsorption isotherm, while [HMIM][PF6] conformed better with Temkin adsorption isotherm. Spectroscopic analyses suggested the formation of Fe/ILs complexes. Some quantum chemical parameters were calculated to corroborate experimental results.

  4. Use of Ionic Liquids in Recycle of Palladium Catalysts for Synthesis of Polyketone

    Institute of Scientific and Technical Information of China (English)

    TIAN Jing; GUO Jintang; ZHANG Xuemei; ZHANG Xin; XU Yongshen

    2008-01-01

    Room temperature ionic liquids as solvents for palladium-catalyzed copolymerization of carbon monoxide and styrene were prepared by reaction of aqueous lead tetrafluoroborate with correspond-ing chloride or bromide salts. The recyclability of palladium composite catalyst in various ionic liquids was investigated.[Pd(bipy)2][BF4]2 showed a lower catalytic activity than [Pd(bipy)2][PF6]2 in similar conditions, although the catalytic activity of each composite catalyst in ionic liquids still existed after 4 successive recycles. It was shown the catalytic activity of palladium composite catalyst was higher than that of the catalyst formed in situ from palladium acetate, 2,2'-bipyridyl, and HA (A=PF6-, BF4-) in ionic liquids. The effects of volume of ionic liquids, reaction time, and the dosage of benzoquinone on the copolymerization were also studied.

  5. Solvation of the fluorine containing anions and their lithium salts in propylene carbonate and dimethoxyethane.

    Science.gov (United States)

    Chaban, Vitaly

    2015-07-01

    Electrolyte solutions based on the propylene carbonate (PC)-dimethoxyethane (DME) mixtures are of significant importance and urgency due to emergence of lithium-ion batteries. Solvation and coordination of the lithium cation in these systems have been recently attended in detail. However, analogous information concerning anions (tetrafluoroborate, hexafluorophosphate) is still missed. This work reports PM7-MD simulations (electronic-structure level of description) to include finite-temperature effects on the anion solvation regularities in the PC-DME mixture. The reported result evidences that the anions appear weakly solvated. This observation is linked to the absence of suitable coordination sites in the solvent molecules. In the concentrated electrolyte solutions, both BF4(-) and PF6(-) prefer to exist as neutral ion pairs (LiBF4, LiPF6). PMID:26067106

  6. First Claisen Rearrangement Reaction in Ionic Liquids with Microwave Heating

    Institute of Scientific and Technical Information of China (English)

    XU Li-Wen; LI Fu-Wei; XIA Chun-Gu

    2003-01-01

    @@ We have demonstrated the first use of the common ionic liquids, [1] bmimBr, bmimBF4 and bmimPF6 as an environmentally benign solvent for the simple Claisen rearrangement under microwave irradiation. In many cases, the re action was carried out in toxic solvents of high boiling point. [2] Here we reported the first example of Claisen rear rangement reaction in green solvents, ionic liquids, under microwave irradiation.

  7. Electroreduction of Copper Dichloride Powder to Copper Nanoparticles in an Ionic Liquid

    OpenAIRE

    2014-01-01

    There were a large number of ionic liquids electrodeposition reported in the literature; but were still in the laboratory stage some problems in the practical application of electrodeposition remain such as easily reacted with moisture in the air (AlCl3 ionic liquid), high cost, and corrosive (dialkylimidazolium cation and BF4−, PF6− ionic liquid). In addition to the above shortcomings, low solubility of many metal salts in ionic liquids limits the practical application. In order to solve the...

  8. Extraction of arsenic from a soil in the blackfoot disease endemic area with ionic liquids

    Science.gov (United States)

    Liao, Chang-Yu; Peng, Ching-Yu; Wang, Hong-Chung; Kang, Hsu-Ya; Paul Wang, H.

    2011-10-01

    Speciation of arsenic extracted with room temperature ionic liquids (RTILs) ([bmim][BF 4] (1-butyl-3-methylimidazolium tetrafluoroborate) and [bmim][PF 6] (1-butyl-3-methylimidazolium hexafluorophosphate)) from an As-humic acid (As-HA) complex contaminated soil (As-HA/soil) in a blackfoot disease endemic area has been studied by X-ray absorption (near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS)) spectroscopy. About 45% of arsenic in the As-HA/soil can be extracted with [bmim][BF 4] while the relatively less hydrophilic [bmim][PF 6] extracts 25% of arsenic. The extracted arsenic in the [bmim][BF 4] and [bmim][PF 6] from the As-HA/soil possesses mainly As(III) species, suggesting that at least two reaction paths may be involved in the extraction process: (1) splitting of As-HA and (2) reduction of As(V) to As(III). The refined EXAFS spectra also indicate that the As(III) extracted in the RTILs possesses the AsO 2- structure, which has the As-O bond distances of 1.77-1.79 Å and coordination numbers of 4.0-4.2.

  9. Extraction of arsenic from a soil in the blackfoot disease endemic area with ionic liquids

    International Nuclear Information System (INIS)

    Speciation of arsenic extracted with room temperature ionic liquids (RTILs) ([bmim][BF4] (1-butyl-3-methylimidazolium tetrafluoroborate) and [bmim][PF6] (1-butyl-3-methylimidazolium hexafluorophosphate)) from an As-humic acid (As-HA) complex contaminated soil (As-HA/soil) in a blackfoot disease endemic area has been studied by X-ray absorption (near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS)) spectroscopy. About 45% of arsenic in the As-HA/soil can be extracted with [bmim][BF4] while the relatively less hydrophilic [bmim][PF6] extracts 25% of arsenic. The extracted arsenic in the [bmim][BF4] and [bmim][PF6] from the As-HA/soil possesses mainly As(III) species, suggesting that at least two reaction paths may be involved in the extraction process: (1) splitting of As-HA and (2) reduction of As(V) to As(III). The refined EXAFS spectra also indicate that the As(III) extracted in the RTILs possesses the AsO2- structure, which has the As-O bond distances of 1.77-1.79 A and coordination numbers of 4.0-4.2.

  10. Heterometallic modular metal-organic 3D frameworks assembled via new tris-β-diketonate metalloligands: nanoporous materials for anion exchange and scaffolding of selected anionic guests.

    Science.gov (United States)

    Carlucci, Lucia; Ciani, Gianfranco; Maggini, Simona; Proserpio, Davide M; Visconti, Marco

    2010-11-01

    The modular engineering of heterometallic nanoporous metal-organic frameworks (MOFs) based on novel tris-chelate metalloligands, prepared using the functionalised β-diketone 1,3-bis(4'-cyanophenyl)-1,3-propanedione (HL), is described. The complexes [M(III)L(3)] (M=Fe(3+), Co(3+)) and [M(II)L(3)](NEt(4)) (M=Mn(2+), Co(2+), Zn(2+), Cd(2+)) have been synthesised and characterised, all of which exhibit a distorted octahedral chiral structure. The presence of six exo-oriented cyano donor groups on each complex makes it a suitable building block for networking through interactions with external metal ions. We have prepared two families of MOFs by reacting the metalloligands [M(III)L(3)] and [M(II)L(3)](-) with many silver salts AgX (X=NO(3)(-), BF(4)(-), PF(6)(-), AsF(6)(-), SbF(6)(-), CF(3)SO(3)(-), tosylate), specifically the [M(III)L(3)Ag(3)]X(3)·Solv and [M(II)L(3)Ag(3)]X(2)·Solv network species. Very interestingly, all of these network species exhibit the same type of 3D structure and crystallise in the same trigonal space group with similar cell parameters, in spite of the different metal ions, ionic charges and X(-) counteranions of the silver salts. We have also succeeded in synthesising trimetallic species such as [Zn(x)Fe(y)L(3)Ag(3)](ClO(4))((2x+3y))·Solv and [Zn(x)Cd(y)L(3)Ag(3)](ClO(4))(2)·Solv (with x+y=1). All of the frameworks can be described as sixfold interpenetrated pcu nets, considering the Ag(+) ions as simple digonal spacers. Each individual net is homochiral, containing only Δ or Λ nodes; the whole array contains three nets of type Δ and three nets of type Λ. Otherwise, taking into account the presence of weak Ag-C σ bonds involving the central carbon atoms of the β-diketonate ligands of adjacent nets, the six interpenetrating pcu networks are joined into a unique non-interpenetrated six-connected frame with the rare acs topology. The networks contain large parallel channels of approximate hexagonal-shaped sections that represent 37

  11. Determining diffusion coefficients of ionic liquids by means of field cycling nuclear magnetic resonance relaxometry

    International Nuclear Information System (INIS)

    Field Cycling Nuclear Magnetic Resonance (FC NMR) relaxation studies are reported for three ionic liquids: 1-ethyl-3- methylimidazolium thiocyanate (EMIM-SCN, 220–258 K), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4, 243–318 K), and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6, 258–323 K). The dispersion of 1H spin-lattice relaxation rate R1(ω) is measured in the frequency range of 10 kHz–20 MHz, and the studies are complemented by 19F spin-lattice relaxation measurements on BMIM-PF6 in the corresponding frequency range. From the 1H relaxation results self-diffusion coefficients for the cation in EMIM-SCN, BMIM-BF4, and BMIM-PF6 are determined. This is done by performing an analysis considering all relevant intra- and intermolecular relaxation contributions to the 1H spin-lattice relaxation as well as by benefiting from the universal low-frequency dispersion law characteristic of Fickian diffusion which yields, at low frequencies, a linear dependence of R1 on square root of frequency. From the 19F relaxation both anion and cation diffusion coefficients are determined for BMIM-PF6. The diffusion coefficients obtained from FC NMR relaxometry are in good agreement with results reported from pulsed- field-gradient NMR. This shows that NMR relaxometry can be considered as an alternative route of determining diffusion coefficients of both cations and anions in ionic liquids

  12. Structural influence on the photochromic response of a series of ruthenium mononitrosyl complexes.

    Science.gov (United States)

    Cormary, Benoit; Ladeira, Sonia; Jacob, Kane; Lacroix, Pascal G; Woike, Theo; Schaniel, Dominik; Malfant, Isabelle

    2012-07-16

    In mononitrosyl complexes of transition metals two long-lived metastable states corresponding to linkage isomers of the nitrosyl ligand can be induced by irradiation with appropriate wavelengths. Upon irradiation, the N-bound nitrosyl ligand (ground state, GS) turns into two different conformations: isonitrosyl O bound for the metastable state 1 (MS1) and a side-on nitrosyl conformation for the metastable state 2 (MS2). Structural and spectroscopic investigations on [RuCl(NO)py(4)](PF(6))(2)·1/2H(2)O (py = pyridine) reveal a nearly 100% conversion from GS to MS1. In order to identify the factors which lead to this outstanding photochromic response we study in this work the influence of counteranions, trans ligands to the NO and equatorial ligands on the conversion efficiency: [RuX(NO)py(4)]Y(2)·nH(2)O (X = Cl and Y = PF(6)(-) (1), BF(4)(-) (2), Br(-)(3), Cl(-) (4); X = Br and Y = PF(6)(-) (5), BF(4)(-) (6), Br(-)(7)) and [RuCl(NO)bpy(2)](PF(6))(2) (8), [RuCl(2)(NO)tpy](PF(6)) (9), and [Ru(H(2)O)(NO)bpy(2)](PF(6))(3) (10) (bpy = 2,2'-bipyridine; tpy = 2,2':6',2"-terpyridine). Structural and infrared spectroscopic investigations show that the shorter the distance between the counterion and the NO ligand the higher the population of the photoinduced metastable linkage isomers. DFT calculations have been performed to confirm the influence of the counterions. Additionally, we found that the lower the donating character of the ligand trans to NO the higher the photoconversion yield. PMID:22757756

  13. Conductivities of AlCl3/Ionic Liquid Systems and Their Application in Electrodeposition of Aluminium

    Institute of Scientific and Technical Information of China (English)

    岳贵宽; 吕兴梅; 朱艳丽; 王慧; 张香平; 张锁江

    2008-01-01

    Solubilities and conduetivities of anliydrons AlCl3 in six kinds of ionic liquids (ILs) were measured. Among the sixkinds of ILs [bmim]Cl, [bmim]Br, [bmim]BF4, [bmim]PF6, [emim][EtSO4] and [bmim][HSO4], anhydrous AlCl3 could bedissolved in the first five kinds but was hardly dissolved in [bmim][HSO4]. The results showed that the nominal solubilities ofAlCl3 in ILs increased in the order of [bmim][HSO4] < [bmim]PF6 < [emim][EtSO4] <[bmim]BF4<[bmim]Cl<[bmim]Br.Conduetivities of the AlCl3/ILs systems depended apparently on the nominal molar ratio of AlCl3 to ILs. The conduetivities ofAlCl3/[bmim]Cl, AlCl3/[bmim]Br and AlCl3/[bmim]PF6 systems had a similar tendency as a fimetion of the nominal molarratio, that is, as the molar ratio was increased, conductivities increased first and then decreased, with the maximumconductivity obtained at approximately 0.9:1, 1.0:1 and 0.5:1, respectively. Conduetivities of the AlCl3/[bmim]BF4 exhibited adentate change and decreased with the molar ratio of AlCl3 to [bmim]BF4 increasing in general. With the increasing of theanhydrous AlCl3 amount in [emim][EtSO4], conductivity of AlCl3/[emim][EtSO4] monotonically decreased. AlCl3/[bmim]Clsystem was chosen as the electrolyte for the electrodeposition of Al. Preliminary experimental results showed that dense,adherent and homogeneous Al coatings could be electrodeposited on stainless steel by means of constant potential techniqueand the surface coverage was quite satisfactory.

  14. Ionic liquids increase the catalytic efficiency of a lipase (Lip1) from an antarctic thermophilic bacterium.

    Science.gov (United States)

    Muñoz, Patricio A; Correa-Llantén, Daniela N; Blamey, Jenny M

    2015-01-01

    Lipases catalyze the hydrolysis and synthesis of triglycerides and their reactions are widely used in industry. The use of ionic liquids has been explored in order to improve their catalytic properties. However, the effect of these compounds on kinetic parameters of lipases has been poorly understood. A study of the kinetic parameters of Lip1, the most thermostable lipase from the supernatant of the strain ID17, a thermophilic bacterium isolated from Deception Island, Antarctica, and a member of the genus Geobacillus is presented. Kinetic parameters of Lip1 were modulated by the use of ionic liquids BmimPF6 and BmimBF4. The maximum reaction rate of Lip1 was improved in the presence of both salts. The highest effect was observed when BmimPF6 was added in the reaction mix, resulting in a higher hydrolytic activity and in a modulation of the catalytic efficiency of the enzyme. However, the catalytic efficiency did not change in the presence of BmimBF4. The increase of the reaction rates of Lip1 promoted by these ionic liquids could be related to possible changes in the Lip1 structure. This effect was measured by quenching of tryptophan fluorescence of the enzyme, when it was incubated with each liquid salt. In conclusion, the hydrolytic activity of Lip1 is modulated by the ionic liquids BmimBF4 and BmimPF6, improving the reaction rate and the catalytic efficiency of this enzyme when BmimPF6 was used. This effect is probably due to changes in the structure of Lip1 induced by the presence of these ionic liquids, stimulating its catalytic activity. PMID:25425150

  15. One-dimensional Chain Topology in [Ag(C6H6NCl)2](ClO4),Generated through Weak Interaction between Molecules

    Institute of Scientific and Technical Information of China (English)

    孙道峰; 曹荣; 梁玉仓; 洪茂椿; 苏伟平

    2001-01-01

    The mononuclear complex [Ag(C6H6NC1)2](C1O4) has been prepared and structurally analyzed by single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group C2/c with unit cell parameters: a=15.5314(2), b=8.0247(8),c=15.3701 (2)A. β =118.832(2)°, V=1678.2(3)A3, Z=4, Mr=462.46, Dc=1.830Mg/m3, F(000)=912,μt (MoKa) = 1.694cm-1. The final R and wR are 0.0472 and 0.1272 for 1484 observed reflections with I≥3σ (Ⅰ). The Ag atom is coordinated by two nitrogen atoms of 4-chloromethyl-pyridine in a linear coordination geometry. Each molecule is further linked by the weak interaction between the C1 and Ag atoms to form a one-dimensional chain structure with Ag-C1 distance of 3.240(A).

  16. Thermochemical Properties of RE(Gly) 4Im( ClO4) 3· 2H2O(RE = La, Pr, Nd, Sm, Eu)

    Institute of Scientific and Technical Information of China (English)

    何水样; 刘向荣; 宋迪生; 胡荣祖

    2001-01-01

    The enthalpies of solution in water for five new light rare earth ternary complexes RE(Gly)4Im(ClO4)3@ 2H2O (gE =La, Pr, Nd, Sm, Eu; Gly-glycine; Im-imidazole) were measured by means of a Calvet microcalorimeter. The empirical formula of enthalpy of solution (Asol H), relative apparent molar enthalpy ( φLi ), relative partial molar enthalpy ( Li )and enthalpy of dilution (AdilH1,2) were drawn up by the data of entalpies of solution of these complexes. From three plots of the values of standard enthalpy of solution AsolHΘm, φLi,Li) versus the values of ionic radius (r) of the light rare earth elements, the grouping effect of lanthanide was observed, showing that the coordination bond between rare earth ion and ligand possesses a certain extent of the property of a covalent bond. The standard enthalpies of solution in water of similar complexes, Ce(Gly)4Im(ClO4)3@2H2O were estimated according to the plot of AsolHΘm, versus r.

  17. On anodic stability and decomposition mechanism of sulfolane in high-voltage lithium ion battery

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Influence of lithium salts on the anodic stability of sulfolane has been investigated. • Oxidation decomposition mechanisms of LiPF6/Sulfolane electrolyte have been well understood by theoretical and experimental methods. • Decomposition products of the electrolyte can be found on the electrode surface and in the interfacial electrolyte. - Abstract: In this work, we investigated the anodic stability and decomposition mechanism of sulfolane (SL). The anodic stability of SL-based electrolyte with different lithium salts on Pt and LiNi0.5Mn1.5O4 electrodes was found to decrease as follows: LiPF6/SL > LiBF4/SL > LiClO4/SL. The oxidation potential of 1M LiPF6/SL electrolyte on both Pt and electrodes is about 5.0V vs Li/Li+. The presence of PF6- and another SL solvent dramatically alters the decomposition mechanism of SL. Oxidation decomposition of SL-SL cluster is the most favorable reaction in LiPF6/SL electrolyte. The dimer products with S-O-R group were detected by IR spectra on the charged LiNi0.5Mn1.5O4 electrode surface and in the electrolyte near the electrode surface, and were found to increase the interfacial reaction resistance of the LiNi0.5Mn1.5O4 electrode

  18. Comparative study on lithium borates as corrosion inhibitors of aluminum current collector in lithium bis(fluorosulfonyl)imide electrolytes

    Science.gov (United States)

    Park, Kisung; Yu, Sunghun; Lee, Chulhaeng; Lee, Hochun

    2015-11-01

    Lithium bis(fluorosulfonyl)imide (LiFSI) is a promising salt that can possibly overcome the limitations of lithium hexafluorophosphate (LiPF6) in current Li-ion batteries (LIBs). Aluminum (Al) corrosion issue, however, is a major bottleneck for the wide use of LiFSI. This study investigates lithium borate salts as Al corrosion inhibitors in LiFSI electrolytes. Through a systematic comparison among lithium tetrafluoroborate (LiBF4), lithium bis(oxalato)borate (LiBOB), and lithium difluoro(oxalato)borate (LiDFOB), and LiPF6, the inhibition ability of the additives is revealed to be in the following order: LiDFOB > LiBF4 ≈ LiPF6 > LiBOB. In particular, the inhibition effect of LiDFOB is outstanding; the anodic behavior of Al in 0.8 M LiFSI + 0.2 M LiDFOB ethylene carbonate (EC)-based electrolyte is comparable to that of corrosion-free 1 M LiPF6 solution. The superior inhibition ability of LiDFOB is attributed to the formation of a passive layer composed of Al-F, Al2O3, and B-O species, as evidenced by X-ray photoelectron spectroscopy (XPS) measurements. A LiCoO2/graphite cell with 0.8 M LiFSI + 0.2 M LiDFOB electrolyte exhibits a rate capability comparable to a cell with 1 M LiPF6 solution, whereas a cell with 0.8 M LiFSI solution without LiDFOB suffers from poor power performance resulting from severe Al corrosion.

  19. Synthesis, structures and reactivity of ruthenium nitrosyl complexes containing Kläui's oxygen tripodal ligand.

    Science.gov (United States)

    Ip, Ho-Fai; Yi, Xiao-Yi; Wong, Wai-Yeung; Williams, Ian D; Leung, Wa-Hung

    2011-11-01

    Ruthenium nitrosyl complexes containing the Kläui's oxgyen tripodal ligand L(OEt)(-) ([CpCo{P(O)(OEt)(2)}(3)](-) where Cp = η(5)-C(5)H(5)) were synthesized and their photolysis studied. The treatment of [Ru(N^N)(NO)Cl(3)] with [AgL(OEt)] and Ag(OTf) afforded [L(OEt)Ru(N^N)(NO)][OTf](2) where N^N = 4,4'-di-tert-butyl-2,2'-bipyridyl (dtbpy) (2·[OTf](2)), 2,2'-bipyridyl (bpy) (3·[OTf](2)), N,N,N'N'-tetramethylethylenediamine (4·[OTf](2)). Anion metathesis of 3·[OTf](2) with HPF(6) and HBF(4) gave 3·[PF(6)](2) and 3·[BF(4)](2), respectively. Similarly, the PF(6)(-) salt 4·[PF(6)](2) was prepared by the reaction of 4·[OTf](2) with HPF(6). The irradiation of [L(OEt)Ru(NO)Cl(2)] (1) with UV light in CH(2)Cl(2)-MeCN and tetrahydrofuran (thf)-H(2)O afforded [L(OEt)RuCl(2)(MeCN)] (5) and the chloro-bridged dimer [L(OEt)RuCl](2)(μ-Cl)(2) (6), respectively. The photolysis of complex [2][OTf](2) in MeCN gave [L(OEt)Ru(dtbpy)(MeCN)][OTf](2) (7). Refluxing complex 5 with RNH(2) in thf gave [L(OEt)RuCl(2)(NH(2)R)] (R = tBu (8), p-tol (9), Ph (10)). The oxidation of complex 6 with PhICl(2) gave [L(OEt)RuCl(3)] (11), whereas the reduction of complex 6 with Zn and NH(4)PF(6) in MeCN yielded [L(OEt)Ru(MeCN)(3)][PF(6)] (12). The reaction of 3·[BF(4)](2) with benzylamine afforded the μ-dinitrogen complex [{L(OEt)Ru(bpy)}(2)(μ-N(2))][BF(4)](2) (13) that was oxidized by [Cp(2)Fe]PF(6) to a mixed valence Ru(II,III) species. The formal potentials of the RuL(OEt) complexes have been determined by cyclic voltammetry. The structures of complexes 5,6,10,11 and 13 have been established by X-ray crystallography. PMID:21927766

  20. Coordination of 3,3'- bipyridazine with bivalent copper, palladium and platinum

    International Nuclear Information System (INIS)

    Bis(ligand) complexes of the diimine 3,3'-bipyridazine (L) with bivalent copper, palladium and platinum are described. Green and violet forms of [CuL-2] [BF-4]2 were obtained, and the electronic and vibrational spectra suggest coordinated fluoroborate groups in the violet species. In the green complex a tetragonal structure is indicated. Coordination of perchlorate in [PdL2] [ClO4]2 is also indicated but not in [PtL2] [ClO4]2. Structure determination of the latter complex reveals a strictly planar PtN4 moiety, and in fact the whole complex cation is approximately planar. Reduced interligand repulsions, compared to those operative in bis(ligand) complexes of 2,2'-bipyridine, are believed to allow the essentially planar conformation. The structure of [PtL2] [ClO4]2 was determined at 295 K by single-crystal X-ray diffraction methods, and was refined to a residual of 0.033 for 1942 'observed' independent reflections. Crystalographic data are also provided. 18 refs., 3 tab., 4 figs

  1. Transition metal complexes with thiosemicarbazide-based ligands. Part46. Synthesis and physico-chemical characterization of mixed ligand cobalt(III-complexes with salicylaldehyde semi-, thiosemi- and isothiosemicarbazone and pyridine

    Directory of Open Access Journals (Sweden)

    VUKADIN M. LEOVAC

    2003-12-01

    Full Text Available Mixed ligand octahedral cobalt(III complexes with the tridentate salicylaldehyde semi-, thiosemi- and isothiosemicarbazone and pyridine of general formula [CoIII(L11-3(py3]X (H2L1 = salicylaldehyde semicarbazone, X = [CoIICl3(py]-, ClO4- . H2O, I- . 0.5 I2; H2L2 = salicylaldehyde thiosemicarbazone, X = [CoIICl3(py]-, [CoIIBr3(py]-, ClO4- . H2O, I3-; H2L3 = salicylaldehyde S-methylisothiosemicarbazone, X = [ CoIIBr3(py ]-, ClO4- . H2O, BF4- were synthesized. The tridentate coordination of all the three dianionic forms of the ligands involves the phenol oxygen, hydrazine nitrogen and the chalcogen (O or S in case of salicylaldehyde semi-, thiosemicarbazone and the terminal nitrogen atom in the case of isothiosemicarbazone. For all the complexes, a meridial octahedral arrangement is proposed, which is a consequence of the planarity of the chelate ligand. The compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility, IR and electronic absorption spectra. The thermal decomposition of the complexes was investigated by thermogravimetry, coupled TG-MS measurements and DSC.

  2. Excess molar enthalpies for [emim][BF4] + pyrrolidin-2-one or 1-methyl pyrrolidin-2-one + pyridine or water mixtures

    International Nuclear Information System (INIS)

    Highlights: • The HE and HijkE data have been measured over entire composition range at 298.15 K. • The observed data have been fitted to Redlich–Kister equation. • The observed data have been analyzed in terms of Graph and PFP theories. • The values calculated by Graph theory compare well with experimental values. -- Abstract: Excess molar enthalpies, HijkE of ternary 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + Pyrrolidin-2-one (j) + Pyridine or Water (k); 1-ethyl-3-methylimidazolium tetrafluoroborate (i) 1-methyl pyrrolidin-2-one (j) + Pyridine or Water (k) and HE of Pyrrolidin-2-one (i) + Pyridine or Water (j); 1-methyl pyrrolidin-2-one (i) + Pyridine (j); 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + Water (j) mixtures have been measured over entire mole fraction range at 298.15 K. The HijkE value for 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + Pyrrolidin-2-one (j) + Water (k); 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + 1-methyl pyrrolidin-2-one (j) + Pyridine or Water (k) are positive over whole range of composition and for 1-ethyl-3-methylimidazolium tetrafluoroborate (i) + Pyrrolidin-2-one (j) + Pyridine (k) mixture, the sign of HijkE values varies with change in composition of the components. The observed data have been analyzed in terms of (i) Graph; and (ii) Prigogine–Flory–Patterson (PFP) theories. Results indicate that HE and HijkE values obtained by Graph theory are in good agreement with experimental data. The PFP theory correctly predict sign as well as magnitude of HE values for the binary mixtures. However, theory fails to predict the sign of HijkE values for the ternary mixtures

  3. Negative quantum Hall effect in field-induced spin-density-wave states: Dependence on shape of the quasi-one-dimensional Fermi surface

    Science.gov (United States)

    Kishigi, Keita; Hasegawa, Yasumasa

    2009-08-01

    The successive transitions of the field-induced spin-density wave, which is labeled by the quantum number N of the Hall conductivity and the nesting vector, are known to depend on the shape of the quasi-one-dimensional Fermi surface. We study the condition for the appearance of the negative N states, where the quantized Hall conductivity changes the sign. We obtain the phase diagram for the negative N states in the parameter space of the higher harmonics in the Fermi surface ( tb' , t3 , and t4 ) to be stabilized with and without the periodic anion potential V in the perpendicular direction to the conducting axis, which are the cases in (TMTSF)2ClO4 and (TMTSF)2PF6 , respectively. The negative N phase is shown to be stabilized for the smaller values of t3 and t4 in the case of the finite V . Comparing with the experiment by Matsunaga [J. Phys. IV 131, 269 (2005)], where the quantum Hall effect is observed in (TMTSF)2ClO4 with various cooling rates, we obtain the parameter regions of t3 and t4 for (TMTSF)2ClO4 ( 0.06≲t3/tb'≲0.23 , 0≲t4/tb'≲0.08 , and V/tb'≲2.0 ).

  4. Group contribution and parachor analysis of experimental data on densities and surface tension for six ionic liquids with the [PF6] anion

    Czech Academy of Sciences Publication Activity Database

    Klomfar, Jaroslav; Součková, Monika; Pátek, Jaroslav

    2015-01-01

    Roč. 385, January (2015), s. 62-71. ISSN 0378-3812 R&D Projects: GA ČR GA13-00145S Institutional support: RVO:61388998 Keywords : ionic liquid * density * surface tension * odd-even effect Subject RIV: BJ - Thermodynamics Impact factor: 2.200, year: 2014

  5. Measurements and group contribution analysis of 0.1 MPa densities for still poorly studied ionic liquids with the [PF6] and [NTf2] anions

    Czech Academy of Sciences Publication Activity Database

    Součková, Monika; Klomfar, Jaroslav; Pátek, Jaroslav

    2014-01-01

    Roč. 77, October (2014), s. 31-39. ISSN 0021-9614 R&D Projects: GA ČR GA13-00145S; GA ČR GA101/09/0010 Institutional support: RVO:61388998 Keywords : ionic liquid * density * group contribution method * bis(trifluoromethylsulfonyl)imide anion * hexafluorophosphate anion Subject RIV: BJ - Thermodynamics Impact factor: 2.679, year: 2014 http://www.sciencedirect.com/science/article/pii/S0021961414001335

  6. Conductivity and thermopower studies of bis-tetramethyltetraselenafulvalenium hexafluorophosphide, bis-tetramethyltetrathiafulvalenium hexafluorophosphide, and their solid solutions, (TMTSF1-xTMTTFx)2PF6

    DEFF Research Database (Denmark)

    Mortensen, Kell; Engler, E. M.

    1984-01-01

    attributed to the small transverse transfer integral tb associated with the TMTTF molecule, which leads to large on-site Coulomb repulsion. The parallel transfer integrals ta appear to be very similar for the two constituent molecules. A slight x dependence of S, appearing below approximately 100 K, is...... attributed to enhanced one-dimensionality when the amount of TMTTF is increased. Close to and below the spin-density-wave ordering temperature, more marked x dependences appear, indicative of impurities. The x=0.85 salt behaves generally similar to the pristine TMTTF material, though dominated by additional...

  7. Preparation of Ionic Liquids and Their Application in Hydrogenation of Aromatic Nitriles

    Institute of Scientific and Technical Information of China (English)

    LIN,Qi; CHEN,Li; XIE,Yi-Peng; ZHENG,Hong-Jie; LI,Xian-Jun; CHEN,Hua

    2004-01-01

    @@ On the basis of their characteristic polar nature, phase behavior and lack of vapour pressure, ionic liquids are considered as green solvents and have attracted significant attention as an alternative reaction medium for homogeneous catalysis.[1] However, the "greenness" of typical ionic liquids used in the literature consisted of halogen-containing anions (such as [AlCl4]-, [BF4]- and [PF6]-) was limited in some sense, due to the serious environment concerns if the hydrolysis stability of the anion is poor (e.g. for [AlCl4]-and [PF6]-) or thermal stability of used ionic liquid is undesired. In both cases, the additional effort is needed to avoid the liberation of toxic and corrosive HF or HCl into the environment.

  8. Measurement of activity coefficients at infinite dilution for hydrocarbons in imidazolium-based ionic liquids and QSPR model

    Institute of Scientific and Technical Information of China (English)

    ZHU Jiqin; YU Yanmei; CHEN Jian; FEI Weiyang

    2007-01-01

    The separations of olefin/paraffin,aromatic/aliphatic hydrocarbons or olefin isomers using ionic liquids instead of volatile solvents have interested many researchers.Activity coefficients γ∞ at infinite dilution of a solute in ionic liquid are generally used in the selection of solvents for extraction or extractive distillation.In fact,the measurement of γ∞ by gas-liquid chromatography is a speedy and costsaving method.Activity coefficients at infinite dilution of hydrocarbon solutes,such as alkanes,hexenes,alkylbenzenes,styrene,in 1-allyl-3-methylimidazolium tetrafluoroborate ([AMIM][BF4]) and 1-butyl-3-methyl imidazolium hexafluorophosphate ([BMIM][PF6]), 1-isobutenyl-3-methylimidazolium tetrafluoroborate ([MPMIM][BF4]) and [MPMIM][BF4]-AgBF4 have been determined by gas-liquid chromatography using ionic liquids as stationary phase.The measurements were carried out at different temperatures from 298 to 318 K.The separating effects of these ionic liquids for alkanes/hexane,aliphatic hydrocarbons/benzene and hexene isomers have been discussed.The hydrophobic parameter,dipole element,frontier molecular orbital energy gap and hydration energy of these hydrocarbons were calculated with the PM3 semi-empirical quantum chemistry method.The quantitative relations among the computed structure parameters and activity coefficients at infinite dilution were also developed.The experimental activity coefficient data are consistent with the correlated and predicted results using QSPR models.

  9. Recoiled ions from polyatomic cluster impacts on organic and inorganic targets

    Science.gov (United States)

    Diehnelt, C. W.; Van Stipdonk, M. J.; Schweikert, E. A.

    1998-08-01

    We report the observation of a polyatomic cluster constituent, fluorine in this case, recoiling from the projectile upon impact with a surface. The clusters (NaF) nNa + ( n=1, 2, and 4), PF 6-, BF 4-, and SiF 5-, with incident kinetic energies of 12-28 keV, were impacted on Au, SiO 2, and α-cyano-4-hydroxycinnamic acid targets. The Au surface gave the highest F - yield when compared to the "light" SiO 2 surface, for the same incident cluster. This supports previous MD predications of polyatomic cluster constituents "splashing" upon impact with a surface.

  10. Solvation free energies in [bmim]-based ionic liquids: Anion effect toward solvation of amino acid side chain analogues

    Science.gov (United States)

    Latif, Muhammad Alif Mohammad; Micaêlo, Nuno; Abdul Rahman, Mohd Basyaruddin

    2014-11-01

    Stochastic molecular dynamics simulations were performed to investigate the solvation free energy of 15 neutral amino acid side chain analogues in aqueous and five, 1-butyl-3-methylimidazolium ([BMIM])-based ionic liquids. The results in aqueous were found highly correlated with previous experimental and simulation data. Meanwhile, [BMIM]-based RTILs showed better solvation thermodynamics than water to an extent that they were capable of solvating molecules immiscible in water. Non-polar analogues showed stronger solvation in hydrophobic RTIL anions such as [PF6]- and [Tf2N]- while polar analogues showed stronger solvation in the more hydrophilic RTIL anions such as [Cl]-, [TfO]- and [BF4]-.

  11. Electrochemical characterization of electrolytes and electrodes for lithium-ion batteries. Development of a new measuring method for electrochemical investigations on electrodes with the electrochemical quartz crystal microbalance (EQCM); Elektrochemische Charakterisierung von Elektrolyten und Elektroden fuer Lithium-Ionen-Batterien. Entwicklung einer neuen Messmethode fuer elektrochemische Untersuchungen an Elektroden mit der EQCM

    Energy Technology Data Exchange (ETDEWEB)

    Moosbauer, Dominik Johann

    2010-11-09

    In this work the conductivities of four different lithium salts, LiPF6, LiBF4, LiDFOB, and LiBOB in the solvent mixture EC/DEC (3/7) were investigated. Furthermore, the influence of eight ionic liquids (ILs) as additives on the conductivity and electrochemical stability of lithium salt-based electrolytes was studied. The investigated salts were the well-known lithium LiPF6 and LiDFOB. Conductivity studies were performed over the temperature range (238.15 to 333.15) K. The electrochemical stabilities of the solutions were determined at aluminum electrodes. The salt solubility of LiBF4 and LiDFOB in EC/DEC (3/7) was measured with the quartz crystal microbalance (QCM), a method developed in our group. Moreover, a method to investigate interactions between the electrolyte and electrode components with the electrochemical quartz crystal microbalance (EQCM) was developed. First, investigations of corrosion and passivation effects on aluminum with different lithium salts were performed and masses of deposited products estimated. Therefore, the quartzes were specially prepared with foils. Active materials of cathodes, in this work lithium iron phosphate (LiFePO4), were also investigated with the EQCM by a new method. [German] In dieser Arbeit wurden die Leitfaehigkeiten von vier unterschiedlichen Salzen, LiPF6, LiBF4, LiDFOB und LiBOB in dem Loesemittelgemisch EC/DEC (3/7) untersucht. Des Weiteren wurde der Einfluss von acht Ionischen Fluessigkeiten (ILs) als Additive fuer Lithium-Elektrolyte auf die elektrochemische Stabilitaet und die Leitfaehigkeit studiert. Die untersuchten Salze waren LiPF6 und LiDFOB. Die Leitfaehigkeitsmessungen wurden in einem Temperaturbereich von (238,15 bis 333,15) K durchgefuehrt. Die elektrochemischen Stabilitaeten der Elektrolyte fanden an Aluminium statt. Mit einer an der Arbeitsgruppe entwickelten neuen Methode wurden zudem die Salzloeslichkeiten von LiBF4 und LiDFOB in EC/DEC (3/7) mit der Quarzmikrowaage (QCM) bestimmt. Weiterhin wurden

  12. The preparation of carbon dots/ionic liquids-based electrolytes and their applications in quasi-solid-state dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Highlights: ► A facile means to generate carbon dots/ionic liquids (ILs) – were demonstrated. ► The carbon dots/ILs blend were used for fabricating quasi-solid-state DSSCs. ► Cells exhibited good stability in room temperature without any further sealing. -- Abstract: A facile means to generate carbon dots/ionic liquids (ILs) blend using ionic liquid-assisted electrochemical exfoliation was demonstrated. Two kinds of ILs, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), were used in this work. Transmission electron microscopy and UV–vis spectrum were employed to characterize the formed carbon dots/ILs. The carbon dots/ILs were used for fabricating quasi-solid-state dye-sensitized solar cells (DSSCs), where 1-butyl-3-methylimidazolium iodide and LiI/I2 were added to enhance the performance of DSSCs. Effects of the varied contents of components in the complex on the performance of DCCSs have been studied in detail at ambient temperature. The electrochemical impedance spectroscopy showed that the introduction of carbon dots into ionic liquids can enhance the electrical properties by facilitating charge transfer processes of the electrolytes. The overall energy-conversion efficiency (η) was 2.71% and 2.41% for carbon dots/[bmim][PF6] and carbon dots/[bmim][BF4] based blend electrolytes, respectively. A 82% enhancement in η was obtained by introduction of carbon dots into [bmim][PF6] comparing with pure [bmim][PF6] (η = 1.49%). In addition, the cells exhibited good stability under continuous illumination in room temperature without any further sealing

  13. Effect of Lithium Bis(trifluoromethylsulfonyl)imide on the High-temperature Behavior of LiFePO4 Positive Electrode%二(三氟甲基磺酰)亚胺锂对磷酸铁锂正极高温行为的影响

    Institute of Scientific and Technical Information of China (English)

    车海英; 杨军; 吴凯; 王久林; 努丽燕娜

    2011-01-01

    The effect of lithium salts in electrolytes on the high-temperature performance of LiFePO4 electrode is investigated systematically and the related mechanism is revealed. Differential scanning calorimetry measurements show that lithium bis(trifluorornethylsulfonyl)imide (LiTFSI) and LiBF4 are more favorable for the use at high temperature than LiPF6 because of their water insensitivities and excellent thermal stabilities. Inductively coupled plasma is used to examine the dissolving degree of ferrous ions from LiFePO4 in the different electrolytes at 55℃. It is found that little ferrous ions can be dissolved from LiFePO4 in LiTFSI and fluorine-free lithium salt electrolytes. On the contrary, it is quite serious in LiPF6 electrolyte. In addition, FePO4 is easier to release iron ions than LiFePO4 in the LiPF6 electrolyte. The experimental results of cyclic voltammetry and light microscope indicate that a small amount of LiBF4 can inhibit the corrosion of aluminum foil current collector from LiTFSI. The electrolyte containing mixed salts of LiTFSI and LiBF4 significantly improves the high-temperature performance of LiFePCVLi cell. The discharge capacity is still 147.7 mAh/g after 40 cycles at 55℃ and 1 C rate.%系统研究了电解质锂盐对磷酸铁锂电极高温性能的影响,并探讨了相关的作用机理.差示扫描量热仪测试显示,与LiPF6相比,二(三氟甲基磺酰)亚胺锂(LiTFSI)和LiBF4具有对水份稳定且热稳定性好的优点,更适合高温条件下使用.应用等离子体发射光谱考察LiFePO4在55℃和不同电解液体系中铁离子溶出程度,结果表明,在LiTFSI和无氟锂盐电解液中LiFePO4的铁很少溶出,而在LiPF6电解液中却溶出严重,且FePO4的铁溶出量高于LiFePO4.循环伏安和光学显微镜测试结果显示少量LiBF4的加入能有效抑制LiTFSI对集流体铝箔的腐蚀.以LiTFSI和LiBF4作为混合锂盐配成的电解液能显著改善LiFePO4/Li电池的高温电化学性能,在55

  14. Comprehensive Insights into the Reactivity of Electrolytes Based on Sodium Ions.

    Science.gov (United States)

    Eshetu, Gebrekidan Gebresilassie; Grugeon, Sylvie; Kim, Huikyong; Jeong, Sangsik; Wu, Liming; Gachot, Gregory; Laruelle, Stephane; Armand, Michel; Passerini, Stefano

    2016-03-01

    We report a systematic investigation of Na-based electrolytes that comprise various NaX [X=hexafluorophosphate (PF6 ), perchlorate (ClO4 ), bis(trifluoromethanesulfonyl)imide (TFSI), fluorosulfonyl-(trifluoromethanesulfonyl)imide (FTFSI), and bis(fluorosulfonyl)imide (FSI)] salts and solvent mixtures [ethylene carbonate (EC)/dimethyl carbonate (DMC), EC/diethyl carbonate (DEC), and EC/propylene carbonate (PC)] with respect to the Al current collector stability, formation of soluble degradation compounds, reactivity towards sodiated hard carbon (Nax -HC), and solid-electrolyte interphase (SEI) layer formation. Cyclic voltammetry demonstrates that the stability of Al is highly influenced by the nature of the anions, solvents, and additives. GC-MS analysis reveals that the formation of SEI telltales depends on the nature of the linear alkyl carbonates and the battery chemistry (Li(+) vs. Na(+) ). FTIR spectroscopy shows that double alkyl carbonates are the main components of the SEI layer on Nax -HC. In the presence of Na salts, EC/DMC and EC/DEC presented a higher reactivity towards Nax -HC than EC/PC. For a fixed solvent mixture, the onset temperature follows the sequence NaClO4 PF6 PF6

  15. Synthesis of fluorene-based polyelectrolytes tethering different counterions for single-component white light-emitting electrochemical cells

    Science.gov (United States)

    Yang, Sheng-Hsiung; Tsai, Chia-Sheng; Liu, Bo-Cun; Su, Hai-Ching

    2013-09-01

    A series of polyfluorene (PF) electrolytes bearing Br-, BF4 -, or PF6 - counterions were synthesized and characterized. 2,1,3-benzoselenadiazole moieties were incorporated into polymer main chains to produce single-component white lightemitting polymers. The thermal stability of Br-containing ionic PF was decreased because of the Hofmann elimination occurred at higher temperature. By replacing Br- with BF4 - or PF6 - counterions, the thermal stability of polymers was significantly improved. The emission intensity around 550 nm was decreased for ionic polyelectrolytes. The optimized spin-coated light-emitting electrochemical cell (LEC) with the configuration of ITO/PEDOT/polymer/Ag showed a maximum luminescence efficiency of 1.56 lm/W at a low operation bias of 3 V. The single-component LEC device exhibited pure white light emission with CIE'1931 coordinates approaching (0.33, 0.33) and high color rendering index (CRI < 85), referring to its potential use in solid-state-lighting application.

  16. Density and viscosity of three (2,2,2-trifluoroethanol + 1-butyl-3-methylimidazolium) ionic liquid binary systems

    International Nuclear Information System (INIS)

    Highlights: • Densities and viscosities from 278.15 to 333.15 K are reported for three binary (2,2,2-trifluoroethanol + an IL) systems. • TFE + [bmim][BF4] system presents positive VE values except for the highest mole fractions of TFE, at the highest temperatures. • TFE + [bmim][PF6] presents negative VE values except at the low TFE mole fractions for the lowest temperatures. • TFE + [bmim][NTf2] presents negative VE values for all the mole fractions and temperatures studied. • The three systems present negative viscosity deviations becoming less negative with increasing temperature. -- Abstract: Densities and viscosities were determined for binary mixtures of 2,2,2-trifluoroethanol (TFE) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) or 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([bmim][NTf2]) over the entire range of composition. The experimental measurements were carried out at temperatures ranging from 278.15 K to 333.15 K, at atmospheric pressure. The densities and viscosities of the pure ionic liquids and their mixtures with TFE were described successfully by an empirical third-order polynomial and by the Vogel–Fulcher–Tammann equation, respectively. In addition, excess molar volumes and viscosity deviations were determined from densities and viscosities of mixtures, respectively, and fitted by using the Redlich–Kister equation

  17. Strongly luminous tetranuclear gold(I) complexes supported by tetraphosphine ligands, meso- or rac-bis[(diphenylphosphinomethyl)phenylphosphino]methane.

    Science.gov (United States)

    Tanase, Tomoaki; Otaki, Risa; Nishida, Tomoko; Takenaka, Hiroe; Takemura, Yukie; Kure, Bunsho; Nakajima, Takayuki; Kitagawa, Yasutaka; Tsubomura, Taro

    2014-02-01

    A series of tetragold(I) complexes supported by tetraphosphine ligands, meso- and rac-bis[(diphenylphosphinomethyl)phenylphosphino]methane (meso- and rac-dpmppm) were synthesized and characterized to show that the tetranuclear Au(I) alignment varies depending on syn- and anti-arrangements of the two dpmppm ligands with respect to the metal chain. The structures of syn-[Au4 (meso-dpmppm)2X]X'3 (X = Cl; X' = Cl (4 a), PF6 (4 b), BF4 (4 c)) and syn-[Au4 (meso-dpmppm)2]X4 (X = PF6 (4 d), BF4 (4 e), TfO (4 f); TfO = triflate) involved a bent tetragold(I) core with a counter anion X incorporated into the bent pocket. Complexes anti-[Au4 (meso-dpmppm)2]X4 (X = PF6 (5 d), BF4 (5 e), TfO (5 f)) contain a linearly ordered Au4 string and complexes syn-[Au4 (rac-dpmppm)2X2]X'2 (X = Cl, X' = Cl (6 a), PF6 (6 b), BF4 (6 c)) and syn-[Au4 (rac-dpmppm)2]X4 (X = PF6 (6 d), BF4 (6 e), TfO (6 f)) consist of a zigzag tetragold(I) chain supported by the two syn-arranged rac-dpmppm ligands. Complexes 4 d-f, 5 d-f, and 6 d-f with non-coordinative large anions are strongly luminescent in the solid state (λmax = 475-515 nm, Φ = 0.67-0.85) and in acetonitrile (λmax = 491-520 nm, Φ = 0.33-0.97); the emission was assigned to phosphorescence from (3) [dσ*σ*σ* pσσσ] excited state of the Au4 centers on the basis of DFT calculations as well as the long lifetime (a few μs). The emission energy is predominantly determined by the HOMO and LUMO characters of the Au4 centers, which depend on the bent (4), linear (5), and zigzag (6) alignments. The strong emissions in acetonitrile were quenched by chloride anions through simultaneous dynamic and static quenching processes, in which static binding of chloride ions to the Au4 excited species should be the most effective. The present study demonstrates that the structures of linear tetranuclear gold(I) chains can be modified by utilizing the stereoisomeric tetraphosphines, meso- and rac-dpmppm, which may

  18. Solubilities of p-coumaric and caffeic acid in ionic liquids and organic solvents

    International Nuclear Information System (INIS)

    Highlights: ► New solubility data of p-coumaric and caffeic acid in ionic liquids and organic solvents. ► Normal melting point temperature and enthalpy of fusion of p-coumaric and caffeic acid. ► Thermogravimetric analysis for p-coumaric and caffeic acid. ► Correlation with UNIQUAC and NRTL. -- Abstract: The solubilities of two cinnamic acid derivatives, namely p-coumaric acid and caffeic acid, in six 1-alkyl-3-methyl imidazolium based ionic liquids composed of the PF6−, BF4−, TFO− and TF2N− anions, and in two organic solvents, t-pentanol and ethyl acetate, have been measured at the temperature range of about (303 to 317) K. The p-coumaric acid was found to be more soluble than caffeic acid in all studied solvents. Higher solubilities of both acids were observed in the ionic liquids composed of the BF4− and TFO− anions. The increase of the alkyl chain length on the cation invokes a decrease in solubility in the case of hydrophilic ionic liquids composed of BF4− anion, while in the case of hydrophobic ones composed of PF6− anion an increase in the solubility is observed. Between the two organic solvents t-pentanol is better solvent than ethyl acetate for both acids. Moreover, using the van’t Hoff equations the apparent Gibbs energy, enthalpy, and entropy of solution were calculated. Finally, successful correlation of the experimental data was achieved with the UNIQUAC and the NRTL activity coefficient models, while poor predictions of the solubility of the two acids in the organic solvents were obtained with two UNIFAC models

  19. Antileishmanial activity of ruthenium(II)tetraammine nitrosyl complexes.

    Science.gov (United States)

    Pereira, José Clayston Melo; Carregaro, Vanessa; Costa, Diego Luís; da Silva, João Santana; Cunha, Fernando Q; Franco, Douglas Wagner

    2010-09-01

    The complexes trans-[Ru(NO)(NH(3))(4)L](X)(3) (X = BF(4)(-), PF(6)(-) or Cl(-) and L = N-heterocyclic ligands, P(OEt)(3), SO(3)(-2)), and [Ru(NO)Hedta)] were shown to exhibit IC(50pro) in the range of 36 (L = imN) to 5000 microM (L = imC). The inhibitory effects of trans-[Ru(NO)(NH(3))(4)imN](BF(4))(3) and of the Angeli's salt on the growth of the intramacrophage amastigote form studied were found to be similar while the trans-[Ru(NH(3))(4)imN(H(2)O)](2+) complex was found not to exhibit any substantial antiamastigote effect. The trans-[Ru(NO)(NH(3))(4)imN](BF(4))(3) compound, administered (500 nmol kg(-1) day(-1)) in BALB/c mice infected with Leishmania major, was found to exhibit a 98% inhibition on the parasite growth. Furthermore, this complex proved to be at least 66 times more efficient than glucantime in in vivo experiments. PMID:20598778

  20. Structural insights into the counterion effects on the manganese(iii) spin crossover system with hexadentate Schiff-base ligands.

    Science.gov (United States)

    Wang, Shi; Xu, Wu-Tan; He, Wen-Rui; Takaishi, Shinya; Li, Yong-Hua; Yamashita, Masahiro; Huang, Wei

    2016-04-01

    A series of new salts [Mn(5-MeO-sal-N-1,5,8,12)]Y (Y = ClO4 for 1, Y = BF4 for 2, Y = NO3 for 3 and Y = CF3SO3 for 4) based on the six-coordinated mononuclear manganese(iii) Schiff-base complex cation [Mn(5-MeO-sal-N-1,5,8,12)](+), has been investigated to determine the impact of counter anion effects, intramolecular ligand distortion and intermolecular supramolecular structures on the spin crossover (SCO) behavior. The SCO in salt 1 has resulted in a crystallographic observation of the coexistence of high-spin (HS, S = 2) and low-spin (LS, S = 1) manganese(iii) complex cations in equal proportions around 100 K. At room temperature, the two crystallographically distinct manganese centers are both close to the complete HS state. Only one of the two slightly different units undergoes SCO in the temperature range 300-180 K, whereas the other remains in the HS state down to 20 K. For salts 2 and 3, crystal structural analysis indicates change in the anion from ClO4(-) to BF4(-) and NO3(-) was led to the close arrangement of the cations and the stacking between phenyl groups from the ligands. With CF3SO3(-) as the counterion, although the cations and the anions separate clearly in one direction, the close arrangement of cations in other directions precludes the spin transformation of the Mn(iii) cations. Magnetic measurements on 2-4 indicate that the manganese(iii) complex cations remain in the HS state in the temperature range 2-300 K. PMID:26927027

  1. Heterohexanuclear (Cu3Fe3) Complexes of Substituted Hexaazatrinaphthylene (HATN) Ligands: Twofold BF4- Association in the Solid and Stepwise Oxidation (3 e) or Reduction (2 e) to Spectroelectrochemically Characterized Species

    Czech Academy of Sciences Publication Activity Database

    Roy, S.; Sarkar, B.; Duboc, C.; Fiedler, Jan; Sarper, O.; Lissner, F.; Mobin, S. M.; Lahiri, G. K.; Kaim, W.

    2009-01-01

    Roč. 15, č. 28 (2009), s. 6932-6939. ISSN 0947-6539 R&D Projects: GA MŠk OC 139; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503 Keywords : copper * EPR spectroscopy * ferrocene compounds * heterocycles * spectroelectrochemistry Subject RIV: CG - Electrochemistry Impact factor: 5.382, year: 2009

  2. After-effects of electron capture of 57Co in Fe(ClO4)2x6H2O and Fe(BF4)2x6H2O

    International Nuclear Information System (INIS)

    Moesbauer emission and absorption spectra of ferrous hexahydrates show no difference in the phase transformation temperature but the quadrupole splitting of ferrous ions is by 13% less in the emission case. Probably, this can be attributed to the autoradiolysis of water ligands resulting in the formation of a metastable state of the molecule. Time delayed coincidence Moessbauer measurements show the lifetime of this state to be in the order of 10-8-10-7s. (author)

  3. A New Series of Complexes Possessing Rare “Tertiary” Sulfonamide Nitrogen-to-Metal Bonds of Normal Length: fac-[Re(CO)3(N(SO2R)dien)]PF6 Complexes with Hydrophilic Sulfonamide Ligands

    OpenAIRE

    Abhayawardhana, Pramuditha L.; Marzilli, Patricia A.; Fronczek, Frank R.; Marzilli, Luigi G.

    2014-01-01

    Tertiary sulfonamide nitrogen-to-metal bonds of normal length are very rare. We recently discovered such a bond in one class of fac-[Re(CO)3(N(SO2R)(CH2Z)2)]n complexes (Z = 2-pyridyl) with N(SO2R)dpa ligands derived from di-(2-picolyl)amine (N(H)dpa). fac-[M(CO)3(N(SO2R)(CH2Z)2)]n agents (M = 186/188Re, 99mTc) could find use as radiopharmaceutical bioconjugates when R is a targeting moiety. However, the planar, electron-withdrawing 2-pyridyl groups of N(SO2R)dpa destabilize the ligand to bas...

  4. NMR study of the quasi one dimensional organic metal (perylene)2(AsF6)0,75(PF6)0,35x0,85CH2Cl2

    OpenAIRE

    Wieland, Jürgen; Haeberlen, Ulrich; Schweitzer, Dieter; Keller, Heimo J.

    1987-01-01

    Measurements of the temperature and frequency dependences of the proton spin lattice relaxation rate and of the proton and carbon Knight shifts in the title compound are presented. The results are interpreted in terms of a quasi-one dimensional microscopic conduction electron mobility and of the local unpaired spin densities at the carbon sites of the perylene donor molecules.

  5. Cu(II complexes of an ionic liquid-based Schiff base [1-{2-(2-hydroxy benzylidene amino ethyl}-3-methyl­imidazolium]Pf6: Synthesis, characterization and biological activities

    Directory of Open Access Journals (Sweden)

    Saha Sanjoy

    2015-01-01

    Full Text Available Two Cu(II complexes of an ionic liquid based Schiff base 1-{2-(2-hydroxybenzylideneamino ethyl}-3-methylimidazolium hexaflurophosphate, were prepared and characterized by different analytical and spectroscopic methods such as elemental analysis, magnetic susceptibility, UV-Vis, IR, NMR and mass spectroscopy. The Schiff base ligand was found to act as a potential bidentate chelating ligand with N, O donor sites and formed 1:2 metal chelates with Cu(II salts. The synthesized Cu(II complexes were tested for biological activity.

  6. Superconductivity in the family of organic salts based on the tetramethyltetraselenafulvalene (TMTSF) molecule: (TMTSF)2X (X = Cl04, PF6, AsF6, SbF6, TaF6)

    International Nuclear Information System (INIS)

    Resistivity measurements along the high-conductivity axis of (TMTSF)2Cl04, (TMTSF)2TaF6 and (TMTSF)2SbF6 are reported for various hydrostatic pressures up to 12.5 kbar, and for transverse magnetic fields of up to 50 kG, in the temperature range 100 mK-4 K. These measurements show that all three compounds have a superconducting phase transition near 1 K when sufficient pressure is applied. (TMTSF)2SbF6 and (TMTSF)2TaF6 become superconducting for pressures above 10 kbar and 11 kbar respectively. At lower pressures a metal-insulator phase transition is observed which is probably associated with a spin density wave (SDW) instability. A superconducting phase transition is observed in (TMTSF)2Cl04 at much lower pressures (2X salts. (author)

  7. Ion exchange synthesis and thermal characteristics of some $[\\text{N}^{+}_{2222}]$ based ionic liquids

    Indian Academy of Sciences (India)

    Vasishta D Bhatt; Kuldip Gohil

    2013-11-01

    Eight salts were obtained by reacting tetraethylammonium cation $[\\text{N}^{+}_{2222}]$ with inorganic anions like BF$^{-}_{4}$, NO$^{-}_{3}$, NO$^{-}_{2}$, SCN-, BrO$^{-}_{3}$, IO$^{-}_{3}$, PF$^{-}_{6}$ and HCO$^{-}_{3}$ using ion exchange method. These ionic liquids (ILs) were characterized using thermal methods, infrared spectroscopy and densitometry. Thermophysical properties such as density, coefficient of volume expansion, heat of fusion, heat capacity and thermal energy storage capacity were determined. Thermal conductivity of the samples was determined both in solid and liquid phases. Owing to high values of thermal energy storage capacity coupled with handsome liquid phase thermal conductivity, ILs under investigation were recommended as materials for thermal energy storage (TES) as well as heat transfer applications.

  8. Anion Solvation in Carbonate Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhengcheng

    2015-11-16

    With the correlation between Li+ solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. As of now, most studies are dedicated to the solvation of Li+, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. As a mirror effort to prior Li+ solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate, PF6–, and tetrafluoroborate, BF4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.

  9. The Anion Effect on Li+ Ion Coordination Structure in Ethylene Carbonate Solutions

    CERN Document Server

    Jiang, Bo; Shen, Yuneng; Yang, Xueming; Yuan, Kaijun; Vetere, Valentina; Mossa, Stefano; Skarmoutsos, Ioannis; Zhang, Yufan; Zheng, Junrong

    2016-01-01

    Rechargeable lithium ion batteries are an attractive alternative power source for a wide variety of applications. To optimize their performances, a complete description of the solvation properties of the ion in the electrolyte is crucial. A comprehensive understanding at the nanoscale of the solvation structure of lithium ions in nonaqueous carbonate electrolytes is, however, still unclear. We have measured by femtosecond vibrational spectroscopy the orientational correlation time of the CO stretching mode of Li+-bound and Li+-unbound ethylene carbonate molecules, in LiBF4, LiPF6, and LiClO4 ethylene carbonate solutions with different concentrations. Surprisingly, we have found that the coordination number of ethylene carbonate in the first solvation shell of Li+ is only two, in all solutions with concentrations higher than 0.5 M. Density functional theory calculations indicate that the presence of anions in the first coordination shell modifies the generally accepted tetrahedral structure of the complex, all...

  10. Magnetically rotational reactor for absorbing benzene emissions by ionic liquids

    Institute of Scientific and Technical Information of China (English)

    Yangyang; Jiang; Chen; Guo; Huizhou; Liu

    2007-01-01

    A magnetically rotational reactor (MRR) has been developed and used in absorbing benzene emissions. The MRR has a permanent magnet core and uses magnetic ionic liquid [bmim]FeCl4 as absorbent. Benzene emissions were carried by N2 into the MRR and were absorbed by the magnetic ionic liquid. The rotation of the permanent magnet core provided impetus for the agitation of the magnetic ionic liquid, enhancing mass transfer and making benzene better dispersed in the absorbent. 0.68 g benzene emissions could be absorbed by a gram of [bmim]FeCl4, 0.27 and 0.40 g/ghigher than that by [bmim]PF6 and [bmim]BF4, respectively. The absorption rate increased with increasing rotation rate of the permanent magnet.

  11. Ionic liquid-based hydrothermal synthesis and luminescent properties of CaF2:Ce3+/Mn2+ nanocrystals

    International Nuclear Information System (INIS)

    CaF2:Ce3+/Mn2+ sub-micro cubes and nanospheres were successfully prepared through an ionic liquid-based hydrothermal method. OmimPF6 and OmimBF4 were utilized to introduce a new fluoride source and act as templates. The effects of ionic liquid amount and species on the morphologies and sizes of the nanocrystals have been studied. The photoluminescence properties of CaF2:Ce3+/Mn2+ sub-micro cubes have been discussed, and the results show that the emission intensity of Mn2+ ions can be enhanced by co-doping with Ce3+ ions through an efficient resonance-type energy transfer process.

  12. Activity and stability of feruloyl esterase A from Aspergillus niger in ionic liquid systems

    DEFF Research Database (Denmark)

    Zeuner, Birgitte; Riisager, Anders; Meyer, Anne S.

    solvents that favour synthesis over hydrolysis, i.e. systems with low water content such as organic solvents or ionic liquids (ILs). The esterification of sinapic acid with glycerol catalysed by FAE A from Aspergillus niger (AnFaeA) in a series of ILs containing 15% (v/v) buffer showed that An......FaeA stability – and hence activity – was highly dependent on the anion nature: AnFaeA was stable and active for more than 2 hours in [PF6]--based ILs, but rapidly lost activity in [BF4]--based systems. This effect can be explained in terms of hydrogen bonding capacity of the two anions: As predicted by the......], but this is the first report on FAE stability in ILs [2]. COSMO-RS, which is now widely used for solvent screening in the complex IL systems [3], may be a valuable tool for fast enzyme stability predictions and/or solvent screening in the future....

  13. Compatibility and thermal stability studies on plasticized PVC/PMMA blend polymer electrolytes complexed with different lithium salts

    Directory of Open Access Journals (Sweden)

    R. Nimma Elizabeth

    2005-03-01

    Full Text Available The lithium salt (x (X= LiAsF6, LiPF6, LiN(C2F5SO22 , LiN(CF3SO22, LiBF4 was complexed with a host of poly(vinyl chloride (PVC/ poly(methyl methacrylate (PMMA blend polymer and plasticized with a combination of ethylene carbonate (EC and propylene carbonate(PC. The polymer electrolyte films were prepared for constant PVC/PMMA blend ratio. The electrochemical stability and thermal stability of the solid polymer electrolytes were reported. The role of PMMA to the phenomena occurring at the interface between the electrolyte and the lithium metal electrode was explored.

  14. Probing structural patterns of ion association and solvation in mixtures of imidazolium ionic liquids with acetonitrile by means of relative (1)H and (13)C NMR chemical shifts.

    Science.gov (United States)

    Marekha, Bogdan A; Kalugin, Oleg N; Bria, Marc; Idrissi, Abdenacer

    2015-09-21

    Mixtures of ionic liquids (ILs) with polar aprotic solvents in different combinations and under different conditions (concentration, temperature etc.) are used widely in electrochemistry. However, little is known about the key intermolecular interactions in such mixtures depending on the nature of the constituents and mixture composition. In order to systematically address the intermolecular interactions, the chemical shift variation of (1)H and (13)C nuclei has been followed in mixtures of imidazolium ILs 1-n-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4), 1-n-butyl-3-methylimidazolium hexafluorophosphate (BmimPF6), 1-n-butyl-3-methylimidazolium trifluoromethanesulfonate (BmimTfO) and 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimTFSI) with molecular solvent acetonitrile (AN) over the entire composition range at 300 K. The concept of relative chemical shift variation is proposed to assess the observed effects on a unified and unbiased scale. We have found that hydrogen bonds between the imidazolium ring hydrogen atoms and electronegative atoms of anions are stronger in BmimBF4 and BmimTfO ILs than those in BmimTFSI and BmimPF6. Hydrogen atom at position 2 of the imidazolium ring is substantially more sensitive to interionic hydrogen bonding than those at positions 4-5 in the case of BmimTfO and BmimTFSI ILs. These hydrogen bonds are disrupted upon dilution in AN due to ion dissociation which is more pronounced at high dilutions. Specific solvation interactions between AN molecules and IL cations are poorly manifested. PMID:26278514

  15. Non-covalent interactions in ionic liquid ion pairs and ion pair dimers: a quantum chemical calculation analysis.

    Science.gov (United States)

    Marekha, Bogdan A; Kalugin, Oleg N; Idrissi, Abdenacer

    2015-07-14

    Ionic liquids (ILs) being composed of bulky multiatomic ions reveal a plethora of non-covalent interactions which determine their microscopic structure. In order to establish the main peculiarities of these interactions in an IL-environment, we have performed quantum chemical calculations for a set of representative model molecular clusters. These calculations were coupled with advanced methods of analysis of the electron density distribution, namely, the quantum theory of atoms in molecules (QTAIM) and the non-covalent interaction (NCI; J. Am. Chem. Soc., 2010, 132, 6499) approaches. The former allows for profound quantitative characterization of non-covalent interactions between atoms while the latter gives an overview of spatial extent, delocalization, and relative strength of such interactions. The studied systems consist of 1-butyl-3-methylimidazolium (Bmim(+)) cations and different perfluorinated anions: tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)), trifluoromethanesulfonate (TfO(-)), and bis(trifluoromethanesulfonyl)imide (TFSI(-)). IL ion pairs and ion pair dimers were considered as model structures for the neat ILs and large aggregates. Weak electrostatic hydrogen bonding was found between the anions and the imidazolium ring hydrogen atoms of cations. Weaker but still appreciable hydrogen bonding was also noted for hydrogen atoms adjacent to the imidazolium ring alkyl groups of Bmim(+). The relative strength of the hydrogen bonding is higher in BmimTfO and BmimBF4 ILs than in BmimPF6 and BmimTFSI, whereas BmimTfO and BmimTFSI reveal higher sensitivity of hydrogen bonding at the different hydrogen atoms of the imidazolium ring. PMID:26059822

  16. Structural characterization and DFT study of V(IV)O(acac)2 in imidazolium ionic liquids.

    Science.gov (United States)

    Mota, Andreia; Hallett, Jason P; Kuznetsov, Maxim L; Correia, Isabel

    2011-09-01

    We report the structural characterization of vanadyl acetylacetonate in imidazolium room temperature ionic liquids--bbimNTf(2), bmimNTf(2), C(3)OmimNTf(2), bm(2)imNTf(2), bmimPF(6), bmimOTf, bmimBF(4), bmimMeCO(2), bmimMeSO(4), bmimMe(2)PO(4) and bmimN(CN)(2)--and organic solvents. The complex was characterized by visible electronic (Vis) and EPR spectroscopies. VO(acac)(2) shows solvatochromism in the selected ionic liquids and behaves as in organic solvents, evidencing coordination of the ionic liquid anion in the solvents with higher coordinating ability. The Lewis basicity order obtained for the IL anions was: PF(6)(-) < NTf(2)(-) < OTf(-)≈ MeCO(2)(-) < MeSO(4)(-) < BF(4)(-)≈ N(CN)(2)(-) < Me(2)PO(4)(-). The solvent effect on the spectroscopic data was tentatively examined using linear solvation energy relationships based on the Kamlet-Taft solvent scale (α, β and π*), however no suitable correlation was found with all data. The EPR characterization showed the presence of two isomers in bmimOTf, bmimMeCO(2) and bmimMe(2)PO(4), suggesting coordination of the ionic liquid anions in both equatorial and axial positions. The full geometry optimization of cis-/trans-VO(acac)(2)(OTf)(-) and cis-/trans-VO(acac)(2)(OTf)(mmim) structures was done at the B3P86/6-31G* level of theory. The calculations confirm that the anion OTf(-) is able to coordinate to VO(acac)(2) with the trans isomer being more stable than the cis by 4.8 kcal mol(-1). PMID:21789301

  17. Mixed ionic liquids/graphene-supported platinum nanoparticles as an electrocatalyst for methanol oxidation

    International Nuclear Information System (INIS)

    Graphical abstract: A kind of mixed ionic liquids (ILs) of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4], IL1) and hexafluorophosphate ([bmim][PF6], IL2) was introduced to the functionalization of graphene (GN) nanosheets, which was used to the synthesis of platinum nanoparticles (Pt NPs) to obtain the Pt/IL1-IL2/GN nanocomposite. The as-prepared Pt/IL1-IL2/GN composites exhibited highly electrocatalytic activity (764.3 mA mg − 1Pt at 0.6 V vs. SCE) and stability toward methanol oxidation, demonstrating their promising potential as the anode catalyst for direct methanol fuel cells (DMFCs). - Highlights: • Pt/mixed ionic liquids/graphene composite catalyst was easily synthesized. • The special phase equilibrium characteristics exerted by the peculiar interactions between different ILs can promote the homogeneous growth of small Pt nanoparticles. • The as-made catalyst exhibited enhanced electro-catalytic performance for methanol oxidation. - Abstract: A kind of mixed ionic liquids (ILs) of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4], IL1) and hexafluorophosphate ([bmim][PF6], IL2) was introduced to the functionalization of graphene (GN) nanosheets, which was used to the synthesis of platinum nanoparticles (Pt NPs) to obtain the Pt/IL1-IL2/GN nanocomposite. The interaction between mixed ILs and GN achieved a stable performance due to the excellent electronic and interfacial property of the fabricated nanocomposites, which was favorable for effective loading of Pt NPs on the IL1-IL2/GN support. The as-prepared Pt/IL1-IL2/GN composites exhibited highly electrocatalytic activity (764.3 mA mg−1Pt at 0.6 V vs. SCE) and stability toward methanol oxidation, demonstrating their promising potential as the anode catalyst for direct methanol fuel cells (DMFCs)

  18. Study of 6- cyclic -perimeter hydrocarbon ruthenium complexes bearing functionalized pyridyl diketones: Isolation of complexes with 2-N∩O and 4-N∩O bonding modes of ligands

    Indian Academy of Sciences (India)

    Saphidabha L Nongbri; Babulal Das; Mohan Rao Kollipara

    2012-11-01

    Chelating mono- and di-pyridyl functionalized -diketones, viz. 1-phenyl-3-(2-pyridyl) propane-1,3-dione (pppdH) and 1,3-di(2-pyridyl)propane-1,3-dione (dppdH) ligands yielded new water soluble 6-arene ruthenium(II) complexes of the formulation [(6-arene)Ru(2-N-O-pppdH)Cl]+ (arene = C6H6 1, pPrC6H4Me 2, C6Me6 3) and [(6-arene)2Ru2(4-N-O-dppd)Cl2]+ (arene = C6H6 4, -PrC6H4Me 5, C6Me6 6), as their (complexes 1-4, 6) PF6 salt or (complex 5) BF4 salt. The complexes were obtained by treatment of respective precursors, [(6-arene)Ru(-Cl)Cl]2 (arene = C6H6, -PrC6H4Me, C6Me6) in 1:2 and 1:1 molar ratio with pppdH and dppdH in the presence of NH4PF6/NH4BF4. All the complexes have been characterized on the basis of FT-IR and NMR spectroscopic data as well as by elemental analysis. Molecular structures of representative complexes 2, 5 and 6 have been confirmed by single crystal X-ray diffraction studies. The `O-C-C-C-O' fragment of the coordinated ligand (pppdH) is neutral in complexes 1-3 and that of the dppdH ligand existed as a neutral as well as concomitantly uninegative fashion in complexes 4-6 due to the delocalization of -electrons.

  19. Application of a group contribution equation of state for the thermodynamic modeling of binary systems (gas + ionic liquids) with bis[(trifluoromethyl)sulfonyl]imide anion

    International Nuclear Information System (INIS)

    The properties of ionic liquids (ILs) can be modified by appropriate selection of cations and anions. Even if an infinite number of ionic liquids can be generated, only a limited number of families of anions and cations are used. The group contribution equation of state (GC-EoS) is a promising method for calculating the phase behavior of systems with ILs. If the parameters of the characteristic functional group of a IL family are fitted by using data of a reduced number of ILs of the family, then the phase behavior of all the ILs of the same family can be predicted using exclusively the data of the pure components. Previously, the parameters of the IL families with an imidazolium-based cation and the anions PF6, BF4NO3, and Tf2N were fitted to experimental data , and some ternary systems (CO2 + organics + ionic liquid [bmim][BF4]) were also modeled . In this work, the GC-EoS was used to calculate phase behavior of gases {(CO2, O2, or SO2) + ionic liquids} with Tf2N anion and cations of the families 2,3-dimethyl-imidazolium, 1-alkyl-1-methyl-pyrrolidinium, and 1-alkyl-3-methyl-pyridinium. The GC-EoS was able to reproduce experimental data with deviations of the same order of experimental uncertainty. With the correlated parameters it will be possible to predict the phase behavior of systems with ILs of the families considered in this work.

  20. LiODFB: A unique lithium salt for lithium ion battery%可用于锂离子电池的新型锂盐:LiODFB

    Institute of Scientific and Technical Information of China (English)

    谢辉; 唐致远; 李中延

    2007-01-01

    介绍一种新型的可用于锂离子电池的锂盐:LiODFB(lithium oxalyldifluoroborate).LiODFB独特的化学结构,使其结合了双乙二酸硼酸锂(LiBOB)及四氟硼酸锂(LiBF4)的优势.与LiBOB相比,LiODFB在碳酸酯中的溶解性和溶剂的黏度有了明显改善,从而使锂离子电池具有更好的低温性能和倍率放电性能.而与LiBF4相比,LiODFB能促进稳定固态电解液界面(solid electrolyte interface,SEI)的形成,改善了锂离子电池的高温性能.该种新型锂盐还具有以下优点:与金属锂的化学稳定性好,在高电位下能够很好地使铝箔得到钝化和提高锂离子电池安全性能及抗过充的能力.这些性能使得LiODFB成为一种极有可能替代LiPF6的新型锂盐.

  1. Structural Interactions within Lithium Salt Solvates: Cyclic Carbonates and Esters

    Energy Technology Data Exchange (ETDEWEB)

    Seo, D. M.; Afroz, Taliman; Allen, Joshua L.; Boyle, Paul D.; Trulove, Paul C.; De Long, Hugh C.; Henderson, Wesley A.

    2014-11-13

    Only limited information is available regarding the manner in which cyclic carbonate and ester solvents coordinate Li+ cations in electrolyte solutions for lithium batteries. One approach to gleaning significant insight into these interactions is to examine crystalline solvate structures. To this end, eight new solvate structures are reported with ethylene carbonate, γ-butyrolactone and γ-valerolactone: (EC)3:LiClO4, (EC)2:LiClO4, (EC)2:LiBF4, (GBL)4:LiPF6, (GBL)1:LiClO4, (GVL)1:LiClO4, (GBL)1:LiBF4 and (GBL)1:LiCF3SO3. The crystal structure of (EC)1:LiCF3SO3 is also re-reported for comparison. These structures enable the factors which govern the manner in which the ions are coordinated and the ion/solvent packing—in the solid-state—to be scrutinized in detail.

  2. 5 and 6 - cyclic -perimeter hydrocarbon platinum group metal complexes of 3-(2-pyridyl)pyrazole derived ligands with a pendant nitrile group: Syntheses, spectral and structural studies

    Indian Academy of Sciences (India)

    Gloria Sairem; Venkateswara Rao Anna; Peng Wang; Bbulal Das; Mohan Rao Kollipara

    2012-03-01

    Reaction of two equivalents 4-{(3-(pyridine-2-yl) 1H-pyrazole-1-yl}methyl benzonitrile (L1) and 3-{(3-(pyridine-2-yl)1H-pyrazole-1-yl}methyl benzonitrile (L2) with one equivalent of [(6-arene)Ru(- Cl)Cl]2 and [Cp∗M(-Cl)Cl]2 in methanol yielded mononuclear complexes of the formulae [(6-arene)Ru(L1/L2)Cl]BF4{arene =C6H6 (1, 6); C10H14 (2, 7); C6Me6 (3, 8)} and [Cp∗M(L1/L2)Cl]PF6/BF4 {Cp∗= 5-C5Me5, M=Rh (4, 8); Ir (5, 10)}. These complexes are characterized by IR, 1H NMR and identities of the structure are established by single crystal XRD studies of some of the representative complexes. It is confirmed from the spectral studies that the nitrile group is not taking part in complexation; instead it remains as a free pendant group only.

  3. Translational diffusion in mixtures of imidazolium ILs with polar aprotic molecular solvents.

    Science.gov (United States)

    Marekha, Bogdan A; Kalugin, Oleg N; Bria, Marc; Buchner, Richard; Idrissi, Abdenacer

    2014-05-22

    Self-diffusion coefficients of cations and solvent molecules were determined with (1)H NMR in mixtures of 1-n-butyl-3-methylimidazolium (Bmim(+)) tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)), trifluoromethanesulfonate (TfO(-)), and bis(trifluoromethylsulfonyl)imide (TFSI(-)) with acetonitrile (AN), γ-butyrolactone (γ-BL), and propylene carbonate (PC) over the entire composition range at 300 K. The relative diffusivities of solvent molecules to cations as a function of concentration were found to depend on the solvent but not on the anion (i.e., IL). In all cases the values exhibit a plateau at low IL content (x(IL) < 0.2) and then increase steeply (AN), moderately (γ-BL), or negligibly (PC) at higher IL concentrations. This behavior was related to the different solvation patterns in the employed solvents. In BmimPF6-based systems, anionic diffusivities were followed via (31)P nuclei and found to be higher than the corresponding cation values in IL-poor systems and lower in the IL-rich region. The inversion point of relative ionic diffusivities was found around equimolar composition and does not depend on the solvent. At this point, a distinct change in the ion-diffusion mechanism appears to take place. PMID:24792375

  4. Synthesis and Characterization of New Trinuclear Copper Complexes.

    Science.gov (United States)

    Ghiladi, Reza A; Rheingold, Arnold L; Siegler, Maxime A; Karlin, Kenneth D

    2012-07-01

    This report describes our approach towards modelling the copper cluster active sites of nitrous oxide reductase and the multicopper oxidases/oxygenases. We have synthesized two mesitylene-based trinucleating ligands, MesPY1 and MesPY2, which employ bis(2-picolyl)amine (PY1) and bis(2-pyridylethyl)amine (PY2) tridentate copper chelates, respectively. Addition of cuprous salts to these ligands leads to the isolation of tricopper(I) complexes [(Mes-PY1)Cu(I) (3)(CH(3)CN)(3)](ClO(4))(3)·0.25Et(2)O (1) and [(Mes-PY2)Cu(I) (3)](PF(6))(3) (3) Each of the three copper centers in 1 is most likely four-coordinate, with ligated acetonitrile as the fourth ligand; by contrast, the copper centers in 3 are three-coordinate, as determined by X-ray crystallography The synthesis of [(Mes-PY1)Cu(II) (3)(CH(3)CN)(2)(CH(3)OH)(2)](ClO(4))(6)·(CH(3)OH) (2) was accomplished by addition of three equivalents of the copper(II) salt, Cu(ClO(4))(2)·6H(2)O, to the ligand. The structure of 2 shows that two of the copper centers are tetracoordinate (with MeCN solvent ligation), but have additional weak axial (fifth ligand) interactions with the perchlorate anions; the third copper is unique in that it is coordinated by two MeOH solvent molecules, making it overall five-coordinate. For complexes 2 and 3, one copper ion center is located on the opposite side of the mesitylene plane as the other two. These observations, although in the solid state, must be taken into account for future studies where intramolecular tricopper(I)/O(2) (or other small molecules of interest) interactions in solution are desirable. PMID:22773847

  5. Preparation and Crystal Structures of Silver(I), Mercury(II), and Lead(II) Complexes of Oxathia-Tribenzo-Macrocycles

    International Nuclear Information System (INIS)

    An investigation of the coordination behavior of sulfur-containing mixed-donor tribenzo-macrocycles L1-L3 (L1: 20-membered O3S2, L2: 20-membered O2S3, and L3: 23-membered O4S2) with d10-metal (Ag+, Hg2+, and Pb2+) salts is reported. The X-ray structures of five complexes (1-5) with different structural types and stoichiometries, including mono- to dinuclear species have been determined. Reactions of L2 and L3 with the silver(I) salts (PF6- and SCN-) afforded two dinuclear 2:2 (metal-to-ligand) complexes with different arrangements: a sandwich-type cyclic dinuclear complex [Ag2(L2)2](PF6)2·3CH2Cl2 (1) and a linear dinuclear complex [Ag2(L3)2(SCN)2] (2), in which two monosilver(I) complex units are linked by an Ag-Ag contact. Reactions of L1 and L2 with mercury(II) salts (SCN- and Cl-) gave a mononuclear 1:1 complexes [Hg(L1)(SCN)2] (3) and [Hg(L2)Cl2] (4) with anion coordination in both cases. L2 reacts with lead(II) perchlorate to yield a mononuclear sandwich-type complex [Pb(L2)2(ClO4)2] (5), giving an overall metal coordination geometry of eight with a square antiprism arrangement. From these results, the effects of the donor variation and the anion-coordination ability on the resulting topologies of the soft metal complexes are discussed

  6. Extraction of lithium from salt lake brine using room temperature ionic liquid in tributyl phosphate

    International Nuclear Information System (INIS)

    Highlights: • We proposed a new system for Li recovery from salt lake brine by extraction using an ionic liquid. • Cation exchange was proposed to be the mechanism of extraction followed in ionic liquid. • This ionic liquid system shown considerable extraction ability for lithium and the single extraction efficiency of lithium reached 87.28% under the optimal conditions. - Abstract: Lithium is known as the energy metal and it is a key raw material for preparing lithium isotopes which have important applications in nuclear energy source. In this work, a typical room temperature ionic liquid (RTILs), 1-butyl-3-methyl-imidazolium hexafluorophosphate ([C4mim][PF6]), was used as an alternative solvent to study liquid/liquid extraction of lithium from salt lake brine. In this system, the ionic liquid, NaClO4 and tributyl phosphate (TBP) were used as extraction medium, co-extraction reagent and extractant respectively. The effects of solution pH value, phase ratio, ClO4− amount and other factors on lithium extraction efficiency had been investigated. Optimal extraction conditions of this system include the ratio of TBP/IL at 4/1 (v/v), O/A at 2:1, n(ClO4−)/n(Li+) at 2:1, the equilibration time of 10 min and unadjusted pH. Under the optimal conditions, the single extraction efficiency of lithium was 87.28% which was much higher than the conventional extraction system. Total extraction efficiency of 99.12% was obtained by triple-stage countercurrent extraction. Study on the mechanism revealed that the use of ionic liquid increased the extraction yield of lithium through cation exchange in this system. Preliminary results indicated that the use of [C4mim][PF6] as an alternate solvent to replace traditional organic solvents (VOCs) in liquid/liquid extraction was very promising

  7. Stretchable Self-Healing Polymeric Dielectrics Cross-Linked Through Metal-Ligand Coordination.

    Science.gov (United States)

    Rao, Ying-Li; Chortos, Alex; Pfattner, Raphael; Lissel, Franziska; Chiu, Yu-Cheng; Feig, Vivian; Xu, Jie; Kurosawa, Tadanori; Gu, Xiaodan; Wang, Chao; He, Mingqian; Chung, Jong Won; Bao, Zhenan

    2016-05-11

    A self-healing dielectric elastomer is achieved by the incorporation of metal-ligand coordination as cross-linking sites in nonpolar polydimethylsiloxane (PDMS) polymers. The ligand is 2,2'-bipyridine-5,5'-dicarboxylic amide, while the metal salts investigated here are Fe(2+) and Zn(2+) with various counteranions. The kinetically labile coordination between Zn(2+) and bipyridine endows the polymer fast self-healing ability at ambient condition. When integrated into organic field-effect transistors (OFETs) as gate dielectrics, transistors with FeCl2 and ZnCl2 salts cross-linked PDMS exhibited increased dielectric constants compared to PDMS and demonstrated hysteresis-free transfer characteristics, owing to the low ion conductivity in PDMS and the strong columbic interaction between metal cations and the small Cl(-) anions which can prevent mobile anions drifting under gate bias. Fully stretchable transistors with FeCl2-PDMS dielectrics were fabricated and exhibited ideal transfer characteristics. The gate leakage current remained low even after 1000 cycles at 100% strain. The mechanical robustness and stable electrical performance proved its suitability for applications in stretchable electronics. On the other hand, transistors with gate dielectrics containing large-sized anions (BF4(-), ClO4(-), CF3SO3(-)) displayed prominent hysteresis due to mobile anions drifting under gate bias voltage. This work provides insights on future design of self-healing stretchable dielectric materials based on metal-ligand cross-linked polymers. PMID:27099162

  8. Spectroscopic studies on the inhibitory effects of ionic liquids on lipase activity

    Science.gov (United States)

    Fan, Yunchang; Dong, Xing; Li, Xiaojing; Zhong, Yingying; Kong, Jichuan; Hua, Shaofeng; Miao, Juan; Li, Yan

    2016-04-01

    The effects of ionic liquids (ILs) on the lipase activity were studied by UV-Vis spectroscopy and the IL-lipase interaction mechanism at the molecular level was investigated by fluorescence technique. Experimental results indicated that the lipase activity was inhibited by ILs and the degree of inhibition highly depended on the chemical structures of ILs. The inhibitory ability of the Cl-- and Br--based ILs increased with increasing the alkyl chain length in the IL cation. Thermodynamic parameters, enthalpy change (ΔH) and entropy change (ΔS) were obtained by analyzing the fluorescence behavior of lipase with the addition of ILs. Both ΔH and ΔS were positive suggesting hydrophobicity was the major driven force for the Cl-- and Br--based ILs. For the BF4--, CF3SO3--, ClO4-- and N(CN)2--based ILs, hydrogen bonding was the main driven force. For a more comprehensive understanding of the effects of ILs on lipase activity, the roles of hydrophobicity and hydrogen bonding must be considered simultaneously. A regression-based equation was developed to describe the relationship of the inhibitory ability of ILs and their hydrophobicity and hydrogen bonding ability.

  9. Highly porous lithium-ion conducting solvent-free poly(vinylidene fluoride-co-hexafluoropropylene)/poly(ethyl methacrylate) based polymer blend electrolytes for Li battery applications

    International Nuclear Information System (INIS)

    Plasticised polymer blend electrolytes based on poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-co-HFP) and poly(ethyl methacrylate) (PEMA) were prepared for different lithium salts LiX (X = ClO4, CF3SO3, BF4 and N[CF3SO2]2) using facile solution casting. To confirm the structures and complexations of the electrolyte films, the prepared electrolytes were subjected to XRD and FTIR analysis. TG–DTA was used to ascertain the thermal stability of the electrolytes, and the porous nature of the electrolytes was identified using scanning electron microscopy via ion-hopping conduction. AC impedance analysis was performed for all the electrolyte samples at various temperatures from 303 to 363 K. The results suggest that among the various lithium salts, LiN[CF3SO2]2-based electrolytes exhibited the highest ionic conductivity (0.918 × 10−3 S cm−1). The temperature dependence of the ionic conductivity also complies with the VTF relation

  10. 共萃剂ClO4-作用下磷酸三丁酯分离盐湖卤水锂镁%Lithium and Magnesium Separation from Salt Lake Brine by Tributyl Phosphate under Action of Co-extraction Reagent ClO4-

    Institute of Scientific and Technical Information of China (English)

    杨立新; 邬赛祥; 刘肖丽; 何靖; 陈文光

    2013-01-01

    采用磷酸三丁酯(TBP)作为萃取剂、NaClO4作为共萃剂从高镁锂比盐湖卤水中提取锂,考察了萃取温度、溶液pH值、相比和ClO4-用量等因素对Li+萃取率的影响.结果表明,卤水一次萃取的最佳操作条件为:萃取时间10 min,温度25℃,Vo/Vw=2.0,n(ClO4) /n(Li+)=2.0,pH=5~8,Li+和Mg2+的最高萃取率分别为65.41%和13.31%,锂镁分离系数达到12.32.用水在Vw/Vo=1.0、50℃时进行反相萃取,Li+的反萃率达到81.52%,此时镁锂质量比由45.61下降至8.45.锂镁离子萃取过程呈放热效应,金属离子的萃入对TBP中H的化学位移没有影响,但会导致P=O双键的红外伸缩振动吸收峰从1280 cm-1移至1264 cm-1.25℃时用斜率法测定K+萃合物的组成接近2LiClO4·5TBP,反萃液经深度除镁后可制备碳酸锂.%Aiming at salt lake brine with a high ratio of magnesium/lithium, extracting lithium was researched via the extractant tributyl phosphate ( TBP) as well as the co-extraction reagent NaC104, and the effects of temperature, solution pH value, phase ratio, CIO-4 amount and other factors on Li+ extraction rate have been investigated in detail. The optimum operating conditions of a single extraction from brine are the following: the extraction time of 10 min, temperature of 25 ℃, Vo/Vw=2.0, n(C1O-4)/n(Ii+)= 2.0 and pH value in a range of 5—8. Under these conditions, the highest extraction rate for Li+ and Mg2+ was 65.41% and 13. 31% , respectively, and the Li/Mg separation coefficient reached 12. 32. Reversed phase extraction was carried out with water in Vw/V0 = 1.0 and 50℃ , the stripping rate of Li+ reached 81. 52% , and the mass ratio of Mg/Ii decreased from 45. 61 to 8.45. The extraction process of Li+ and Mg2+ presented exothermic effect, metal ions extracted into the organic phase had no effect on the chemical shifts of H in TBP, but made the IR stretching vibration frequencies of P =O double bond shift to 1264 cm-1 from 1280 cm-1. The composition of extracted complex of Li+ was close to 2LiClO4 ? 5 TBP determined by the slope method at 25 ℃ and Li2CO3 was prepared by the strip liquor after demagnesium deeply.

  11. Study of the hydrolysis of protactinium (V), at tracer scale, by solvent extraction method with thenoyl-tri-fluoro-acetone (TTA) as chelating agent. Characterization of the partition of TTA in the system TTA / H2O / toluene / Na+ / H+ / ClO4-

    International Nuclear Information System (INIS)

    Hydrolysis of protactinium (V) according to the reactions: PaO(OH)2+ +H2O ↔ PaO(OH)2+ + H+ (K2] PaO(OH)2+ +2H2O ↔ PaO(OH)5 + H+ (K3) has been studied, at tracer scale, by solvent extraction method, with thenoyl-tri-fluoro-acetone (TTA) as chelating agent. A previous study concerning the partition of TTA between two immiscible phases (corresponding to TTA/toluene/Na+/H+/ClO4- system) has allowed a complete characterization of this system (partition constants, standard thermodynamic values, TTA hydration degree in toluene). Owing to specific properties of protactinium (V) (sorption onto various materials, formation of colloids), an extremely rigorous protocol has been established, protocol which could be used for other hydrolysable elements. Hydrolysis constants were deduced from a systematic study of partition of Pa(V) as a function TTA and proton concentration, ionic strength and temperature. Extrapolations to zero ionic strength were performed using SIT model and the specific interaction coefficients ε(i,j) as well as the Pitzer parameters β(0) and β(1) were determined. Standard thermodynamic data relative to hydrolysis equilibriums of Pa(V) were also estimated. (author)

  12. A mixed Ni(II) ionic complex containing V-shaped water trimer: Synthesis, spectral, structural and thermal properties of {[Ni(2,2′-bpy)3][Ni(2-cpida)(2,2′ -bpy)]} (ClO4).3H2O

    Indian Academy of Sciences (India)

    Nallasamy Palanisami; Kabali Senthilkumar; Mohan Gopalakrishnan; Il-Shik Moon

    2015-05-01

    A mixed Ni(II) ionic complex of {[Ni(2,2′-bpy)3][Ni(2-cpida)(2,2′-bpy)]}(ClO4).3H2O (1) (2-H3cpida = N-(2-carboxyphenyl)iminodiacetic acid, 2,2′-bpy = 2,2′-bipyridyl) has been synthesized and characterized by infrared, ultraviolet and fluorescence spectroscopy, elemental and thermogravimetric analysis. The molecular structure of compound 1, as determined by single-crystal X-ray diffraction studies, showed all the three carboxylate groups are in monodendate mode. Compound 1 consists of a discrete mononuclear [Ni(2,2′-bpy)3]2+ cation, a [Ni(2-cpida)(2,2′-bpy)]− anion, a ClO$^{−}_{4}$ anion and three lattice water molecules. The H-bonding interaction between three lattice water molecule forms a V-shaped trimer (H2O)3 which gives rise to a 1-D polymeric structure in the solid state.

  13. Detoxification of lignocellulosic prehydrolyzate using imidazolium-based ionic liquid%咪唑类离子液体对木质纤维预水解液的脱毒

    Institute of Scientific and Technical Information of China (English)

    杨金龙; 荣亚运; 高露; 朱均均; 徐勇; 勇强; 欧阳嘉; 余世袁

    2016-01-01

    Aiming at the effect of inhibitors on yeast ethanol fermentation during the fuel ethanol biorefinery process, a new green detoxification technology-ionic liquid extraction was developed for detoxification of the prehydrolyzate obtained from washed acid-catalyzed steam-exploded corn stover (ASC). The extractive performances of two kinds of imidazolium-based ionic liquids (alkylimidazolium hexafluorophosphate [Cnmim][PF6](n=4,6,8) and alkylimidazolium tetrafluoroborate [Cnmim][BF4](n=6,8)) for the ASC prehydrolyzate were investigated and compared. The results indicated that the extraction efficiency of the inhibitors decreased with the increase of alkyl chain length on the cation of ionic liquids. Ionic liquid with4BF− anion had much higher extraction efficiency for the inhibitors than those with6PF− anion because of the stronger effective charge in4BF−. Compared to the extraction efficiency of sugars and inhibitors, [C8mim][BF4] was selected as the extractant for detoxification of the ASC prehydrolyzate. Its detoxification results indicated that 85.13% of 5-hydroxymethylfurfural, 53.22% of formic acid, 47.53% of acetic acid and 65.05% of total phenols could be removed, while the loss of sugars was less than 6%.%针对燃料乙醇生物炼制过程中抑制物对酵母乙醇发酵的抑制作用,以水洗稀酸蒸汽爆破预处理玉米秸秆得到的预水解液为研究对象,采用新型绿色脱毒技术——离子液体进行萃取脱毒,研究比较了两种咪唑类离子液体[烷基咪唑六氟磷酸盐离子液体[Cnmim][PF6](n=4,6,8)和烷基咪唑四氟硼酸盐离子液体[Cnmim][BF4](n=6,8)]对预水解液的萃取性能。结果表明,随着咪唑类离子液体阳离子烷基链长度的增加,离子液体对抑制物的萃取性能下降,具有更强电负性的阴离子为4BF−的离子液体比阴离子为6PF−的离子液体萃取效率更高。通过比较糖与抑制物的萃取率,最终选择[C8mim][BF4]作为

  14. Contribution to the characterization of room temperature ionic liquids under ionizing irradiation

    International Nuclear Information System (INIS)

    Room-Temperature Ionic Liquids are potentially interesting for nuclear fuel treatment. Within this framework, ionic liquids stability towards ionizing radiations (α, β or γ) is determining their potential application. The aim of this work is to assess a better understanding of ionic liquids behaviour under radiolysis. Ionic liquids chosen in these studies are constituted with BuMeIm+ (or Bu3MeN+) cation associated with various anions: Tf2N-, TfO-, PF6- and BF4-. Moreover, development of suitable chemical analysis tools crucial for characterization of these compounds has been realized. Ionic liquids stability has been mainly studied under γ irradiation, but also under electron beam or heavy particles irradiations. Ionic liquids degradation under radiolysis has been determined with two complementary approaches. The first one aims at understanding radio-induced degradation mechanisms with radical species analysis by Electron Paramagnetic Resonance spectroscopy (EPR). The second one aims at characterizing stable radiolysis products formed in liquid and gaseous phases. Studies were conducted with several analytical techniques: Electro Spray Ionisation Mass Spectrometry (ESI-MS), High Pressure Liquid Chromatography (HPLC, HPLC/UV-VIS, HPLC/ESI-MS), Gas Analysis Mass Spectrometry (Gas MS) and Gas Chromatography hyphenated with Mass Spectrometry (GC/MS). Firstly, the ionic liquid [Bu3MeIm][Tf2N] has been studied under γ irradiation. Radiolytic stability has been quantitatively assessed for high doses of radiations and a proposal of degradation scheme has been proposed on the basis of radio-induced radicals and radiolysis products analysis. Those data have been compared to those obtained for the γ radiolysis of the ionic liquid [Bu3MeN][Tf2N], enabling to assess cation influence on ionic liquids radiolysis. Secondly, degradation under γ irradiation of ionic liquids [BuMeIm][X] (X- Tf2N-, TfO-, PF6-, BF4-) has been quantitatively and qualitatively compared. Those data

  15. Ionic Liquids Assisted Synthesis of ZnO Nanostructures: Controlled Size,Morphology and Antibacterial Properties

    Institute of Scientific and Technical Information of China (English)

    R.Rajiv Gandhi; S.Gowri; J.Suresh; M.Sundrarajan

    2013-01-01

    Systematic analysis about the exploitation of imidazolium based ionic liquids (ILs),[BMIM] BF4 [IL1],[EMIM] BF4 [IL2] and [BMIM] PF6 [IL3] as the morphological template on the basic sol-gel method adopted synthesis of nanostructured zinc oxide (ZnO) is presented.X-ray diffraction (XRD),particle size analysis (PSA) and scanning electron microscopy (SEM) have been employed for the characterization of structure and morphology of the synthesized ZnO particles.Well-defined capsule like shaped morphology with lower nanosize is observed for the ZnO nanoparticles with IL1 than those with IL2 and IL3.This confirms that IL1 served as an effective templating material due to their unique properties.Especially the effective aggregation of ZnO particles with a self-organized frame of IL1 was the essential factor to produce the lower nanosized ZnO with capsule shaped structure.The synthesized ZnO samples with IL2 and IL3 fabricated the flake like shaped and rod like shaped morphologies in the range of nanoscale.The formed ZnO nanoparticles with IL2 exhibit higher nanosize than the ZnO nanoparticles produced by IL1,owing to shorter length of alkyl group in its cation which restricts steric effect and permits the nanoparticles to grow longer.Even though IL3 produced the discrete ZnO nanorods,the hydrophobic nature of IL3 created the higher nanosize than the ZnO nanoparticles formed by other two ionic liquids.Antibacterial properties of the synthesized ZnO nanostructures were investigated against Staphylococcus aureus (gram positive) and Escherichia coli (gram negative) bacteria by Agar diffusion test method.Microbial experiments indicate that the synthesized ZnO samples show a wide spectrum of antimicrobial activities and performed better against S.aureus than E.coli with the same concentration of ZnO.

  16. Electron oxidation of graphite by fluorospecies

    International Nuclear Information System (INIS)

    The fluoride-ion affinity (A/sub F-/) of phosphorus pentafluoride was determined to be 100 kcal/mole from the heats of reaction of the Lewis bases SF4 and ClO2F with PF5 near room temperature. The fluoride-ion affinity of boron trifluoride was determined to be 92 kcal/mole from the heat of reaction of ClO2F with BF3. The crystal structure of ClO2BF4 was determined and a precise lattice energy was calculated from this structure and used to determined A/sub F-/. Both PF5 and BF3 were found to react with graphite in the presence of fluorine gas to yield a variety of non-stoichiometric compounds. The fluoride-ion affinity of silicon tetrafluoride is not known, but it does not react with graphite and F2 except at high pressures. These and previous results suggested a threshold in oxidizing power of intercalating species below which the oxidative intercalation reaction would not occur. The reduction of C/sub x/PF6 by PF3 proved that the reaction is thermodynamically controlled to some extent. The displacement of PF5 in C/sub x/PF6 by BF3 (with a smaller A/sub F-/) suggested that two BF3 molecules may have a larger fluoride-ion affinity than one PF5 and that B2F7- may be a stable anion in graphite. Conductivity studies of PF/sub x/ and BF/sub y/ salts showed that a large drop in conductivity when the reaction reaches first stage is due in the most part to direct fluorination of carbon in graphite

  17. Spin-crossover complexes on the way to polymers

    International Nuclear Information System (INIS)

    The aim of this work was to combine in a study chemical and mechanical properties of polymers with exciting properties of coordination compounds exhibiting thermal and light induced spin transition. To simulate polymer effects around a spin-crossover complex, the alkyl-chain length of hexakis (1-alkyl tetrazole) iron(II) bis-(tetrafluoroborate) complexes {[Fe(ntz)6](BF4)2 with n = 1-10, 12, 16, 18} were varied. Samples with n 62 4 showed significant mechanical properties. The spin-transition behavior varied strongly within this series of complexes. Investigations of an isoequilibrium relationship (i.e. a DH - DS relation) within this series of compounds enabled elucidation of their magnetic features. To shed light on the electronic influence of different substituents on the alkyl side-chains of the ligand, iron(II) spin-transition complexes with halo-ethyltetrazole ligands {[Fe(X2tz)6](BF4)2 with X = F, C1, Br and I} were investigated and significant differences in their spin-transition temperature were observed. Actual polymers of iron(II)-coordination polymers of a,w-bis(tetrazol-1-yl) alkanes {[Fe(nditz)3]L2 with n = 4, 6, 8, 10, 12 and L = BF4, PF6} were synthesized. Despite contrary predictions these complex polymers exhibit spin-transition properties, which were furthermore found to be very sensitive to their structural properties. The above complexes and their ligands were synthesized and thoroughly characterized. NMR measurements of the ligands were performed and the assignment of these was supported by simulated NMR spectra. Extensive IR-band classification for the ligands and their complexes are given, supported by ab-initio calculations of the structure and infra-red absorption spectra of selected ligands. In addition to magnetic measurements and 57Fe Moessbauer spectroscopy, new methods to detect the spin transition behavior of iron(II) tetrazole complexes in the IR and far-IR region were developed and well-known techniques were improved. Due to its

  18. Mechanism and Product Characterization from the Electroreduction of Heterodinuclear Complexes [(C5Me5)ClM(.mu. - L)Re(CO)3X](PF6), M = Rh or Ir, L = 2,2''-azobispyridine or 2,2''-azobis(5-chloropyrimidine), X = Halide

    Czech Academy of Sciences Publication Activity Database

    Frantz, S.; Weber, M.; Scheiring, T.; Fiedler, Jan; Duboc, C.; Kaim, W.

    2004-01-01

    Roč. 357, - (2004), s. 2905-2914. ISSN 0020-1693 R&D Projects: GA MŠk OC D14.20; GA MŠk OC D15.10 Institutional research plan: CEZ:AV0Z4040901 Keywords : electrochemistry * High frequency * EPR spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 1.554, year: 2004

  19. Atacama perchlorate as an agricultural contaminant in groundwater: Isotopic and chronologic evidence from Long Island, New York

    Science.gov (United States)

    Böhlke, J.K.; Hatzinger, P.B.; Sturchio, N.C.; Gu, B.; Abbene, I.; Mroczkowski, S.J.

    2009-01-01

    Perchlorate (ClO4-) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO4- is past agricultural application of ClO4--bearing natural NO3- fertilizer imported from the Atacama Desert, Chile, but evidence for this hasbeenlargely circumstantial. Here we report ClO4- stable isotope data (??37Cl, ??18O, and ??17O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO4- contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO4- apparently was not affected by biodegradation within the aquifers. Synthetic ClO4- was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO4- was indicated in agricultural and urbanizing areas in groundwaters with apparent ages >20 years. In an agricultural area, ClO4- concentrations and ClO4-/NO3- ratios increased withgroundwaterage, possiblybecauseof decreasing application rates of Atacama NO3- fertilizers and/or decreasing ClO4- concentrations in Atacama NO 3- fertilizers in recent years. Because ClO 4-/NO3- ratios of Atacama NO 3- fertilizers imported in the past (???2 ?? 10-3 mol mol-1) were much higher than the ClO 4-/NO3- ratio of recommended drinking-water limits (7 ?? 10-5 mol mol-1 in New York), ClO4- could exceed drinkingwater limits even where NO3- does not, and where Atacama NO3- was only a minor source of N. Groundwater ClO4- with distinctive isotopic composition was a sensitive indicator of past Atacama NO3- fertilizer use on Long Island and may be common in other areas that received NO3- fertilizers from the late 19th century through the 20th century. ?? 2009 American Chemical Society.

  20. Tunable Electrochemical and Catalytic Features of BIAN- and BIAO-Derived Ruthenium Complexes.

    Science.gov (United States)

    Hazari, Arijit Singha; Das, Ankita; Ray, Ritwika; Agarwala, Hemlata; Maji, Somnath; Mobin, Shaikh M; Lahiri, Goutam Kumar

    2015-05-18

    This article deals with a class of ruthenium-BIAN-derived complexes, [Ru(II)(tpm)(R-BIAN)Cl]ClO4 (tpm = tris(1-pyrazolyl)methane, R-BIAN = bis(arylimino)acenaphthene, R = 4-OMe ([1a]ClO4), 4-F ([1b]ClO4), 4-Cl ([1c]ClO4), 4-NO2 ([1d]ClO4)) and [Ru(II)(tpm)(OMe-BIAN)H2O](2+) ([3a](ClO4)2). The R-BIAN framework with R = H, however, leads to the selective formation of partially hydrolyzed BIAO ([N-(phenyl)imino]acenapthenone)-derived complex [Ru(II)(tpm)(BIAO)Cl]ClO4 ([2]ClO4). The redox-sensitive bond parameters involving -N═C-C═N- or -N═C-C═O of BIAN or BIAO in the crystals of representative [1a]ClO4, [3a](PF6)2, or [2]ClO4 establish its unreduced form. The chloro derivatives 1a(+)-1d(+) and 2(+) exhibit one oxidation and successive reduction processes in CH3CN within the potential limit of ±2.0 V versus SCE, and the redox potentials follow the order 1a(+) Mulliken spin density distributions in paramagnetic intermediate states which reveal metal-based (Ru(II) → Ru(III)) oxidation and primarily BIAN- or BIAO-based successive reduction processes. The aqua complex 3a(2+) undergoes two proton-coupled redox processes at 0.56 and 0.85 V versus SCE in phosphate buffer (pH 7) corresponding to {Ru(II)-H2O}/{Ru(III)-OH} and {Ru(III)-OH}/{Ru(IV)═O}, respectively. The chloro (1a(+)-1d(+)) and aqua (3a(2+)) derivatives are found to be equally active in functioning as efficient precatalysts toward the epoxidation of a wide variety of alkenes in the presence of PhI(OAc)2 as oxidant in CH2Cl2 at 298 K, though the analogous 2(+) remains virtually inactive. The detailed experimental analysis with the representative precatalyst 1a(+) suggests the involvement of the active {Ru(IV)═O} species in the catalytic cycle, and the reaction proceeds through the radical mechanism, as also supported by the DFT calculations. PMID:25928272

  1. Life-Cycle Perspectives on Aquatic Ecotoxicity of Common Ionic Liquids.

    Science.gov (United States)

    Mehrkesh, Amirhossein; Karunanithi, Arunprakash T

    2016-07-01

    This study compares the aquatic ecotoxicity impacts of production- and use-phase release of five common ionic liquids (ILs). Integrating toxicity data, physical properties, and fate and transport parameters with the USEtox model, we report, for the first time, the freshwater ecotoxicity characterization factors for [Bmim](+)[Br](-), [Bmim](+)[Cl], [Bmim](+)[BF4](-), [Bmim](+)[PF6](-), and [BPy](+)[Cl](-) as 624, 748, 823, 927, and 1768 CTUe/kg, respectively. IL Production life cycle inventories were modeled and utilized to estimate their production-side ecotoxicity impacts. Literature on environmental aspects of ILs propagates either their green characteristics (no air emissions and high recyclability) or their nongreen aspects due to toxicity concerns of their release to water. This study adds a third dimension by showing that the upstream ecotoxicity impacts of producing ILs could outweigh the potential ecotoxicity impacts of direct release during use. Furthermore, for the studied ILs, an average of 83% of ecotoxicity impacts associated with their production can be linked to chemicals and materials released during the upstream synthesis steps, while only 17% of ecotoxicity impacts relate to life-cycle energy consumption. The findings underscore the need to develop sustainable synthesis routes, tight control over chemical releases during production, and careful selection of precursor materials and production processes. PMID:26599072

  2. Synthesis of gold nanoparticles by laser ablation of an Au foil inside and outside ionic liquids

    Science.gov (United States)

    Wender, Heberton; Andreazza, Marcos L.; Correia, Ricardo R. B.; Teixeira, Sérgio R.; Dupont, Jairton

    2011-03-01

    Stable gold nanoparticles (AuNPs) were prepared by simple laser ablation of an Au foil placed inside or outside four ionic liquids (ILs), without the addition of any external chemical reagent. Irregular spherical AuNPs with a diameter range of 5 to 20 nm were produced after laser ablation of an Au foil located inside or outside the ILs 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMI.BF4), 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI.PF6) and 1-(3-cyanopropyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ((BCN)MI.NTf2). Additionally, whereas laser ablation inside the IL 1-n-butyl-3-methylimidazolium dicyanamide BMI.N(CN)2 produced flower-like shaped nanoparticles of about 50 nm in size, ablation outside this IL presented similar results to the others ILs studied, as determined by TEM and UV-Vis. The size and shape of the prepared NPs were related to where NP nucleation and growth occurred, i.e., at the IL surface or within the IL. Indeed, the chemical composition of the IL/air interface and surface ion orientation played important roles in the stabilization of the AuNPs formed by laser ablation outside the ILs.

  3. Solubilities of some gases in four immidazolium-based ionic liquids

    International Nuclear Information System (INIS)

    Graphical abstract: Experimental apparatus based on the synthetic-volumetric method for measuring solubilities of gases in liquids. Highlights: • We constructed an apparatus for measuring solubilities of sparingly-soluble gases. • We measured solubilities of five gases in four immidazolium-based ionic liquids. • We calculated Henry’s constants for gases in the ionic liquids studied in this work. -- Abstract: The synthetic-volumetric method is used for rapidly measuring solubilities of sparingly-soluble gases in monoethylene glycol and in four ionic liquids. Known molar quantities of solute and solvent are charged into an equilibrium vessel. Measured quantities at equilibrium include: temperature, pressure, quantities of fluids, and volumes of the gas and liquid phases in the equilibrium vessel. These measurements enable calculation of equilibrium compositions using material balances. No sampling or chemical analyses are required. Solubilities are reported for carbon dioxide, krypton, oxygen, and hydrogen in monoethylene glycol, l-n-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4], l-n-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][Tf2N], or 1-ethyl-3-methylimidazolium acetate [EMIM][AC]. Solubilities were measured over the temperature range (298 to 355) K and for pressures up to about 7 MPa using two different pieces of equipment, both based on the volumetric method: a low-pressure glass apparatus and a high-pressure stainless-steel apparatus. Special emphasis is given to experimental reliability to assure consistent data

  4. Interfacial structure and orientation of confined ionic liquids on charged quartz surfaces.

    Science.gov (United States)

    Wang, Yong-Lei; Laaksonen, Aatto

    2014-11-14

    Atomistic molecular dynamics simulations have been performed to study microscopic ionic structures and orientational preferences of absorbed [BMIM] cations and four paired anions ([BF4], [PF6], [TFO] and [TF2N]) on quartz surfaces. Two chemically different quartz surface models were adopted: one is saturated with silanol Si(OH)2 groups, and the other one is covered by silane SiH2 groups, respectively. Simulation results reveal that dense ionic layers, characterized by distinct mass, number, charge and electron densities, are formed in quartz interfacial region. The orientational preferences of confined ionic groups are characterized with different features depending on the size and shape of anionic groups, and the quartz surface charge. The [BMIM] cations attach exclusively onto the negatively charged Si(OH)2 surface. The imidazolium rings lie preferentially perpendicular to Si(OH)2 surface, to which the directly connected methyl and butyl chains are oriented and elongated along Si(OH)2 surface, respectively. The anions are mainly absorbed on positively charged SiH2 surface. The main axes of asymmetric [TFO] and [TF2N] anions are perpendicular and parallel to SiH2 surface, respectively. Such distinct structural and orientational preferences of confined ionic groups attribute to the strong electrostatic interactions and the formation of hydrogen bonds between confined ionic species and quartz interfacial groups. PMID:25260202

  5. Physical and excess properties of a room temperature ionic liquid (1-methyl-3-octylimidazolium tetrafluoroborate) with n-alkoxyethanols (C1Em, m = 1 to 3) at T = (298.15 to 318.15) K

    International Nuclear Information System (INIS)

    Physical properties, such as densities, ρ, and refractive indices, n, for the binary mixtures of 1-methyl-3-octylimidazolium tetrafluoroborate [Omim][BF4] with ethylene glycol monomethyl ether (EGMME; C1E1), diethylene glycol monomethyl ether (DEGMME; C1E2), and triethylene glycol monomethyl ether (TEGMME; C1E3) have been measured over the whole composition range. Experimental densities were used to estimate excess molar volumes, VmE, apparent molar volumes, Vφ,i, partial molar volumes, V-barm,i, excess partial molar volumes, V-barm,iE, and their limiting values at infinite dilution, Vφ,i∞, V-barm,i∞, and V-barm,iE,∞, respectively. Volumetric results have been analyzed in the light of Prigogine-Flory-Patterson (PFP) statistical mechanical theory. Deviations in refractive indices Δφn have been calculated from experimental measurements of refractive indices, n. Excess properties are fitted to the Redlich-Kister polynomial equation to obtain the binary coefficients and the standard errors. The results are compared with those of binary mixtures of 1-methyl-3-octylimidazolium tetrafluoroborate containing alcohols reported in the literature or the binary mixtures of 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] with an alkoxyethanol reported in an earlier communication

  6. Effect of the Structure of Cations and Anions of Ionic Liquids on Separation of Aromatics from Hydrocarbon Mixtures

    Institute of Scientific and Technical Information of China (English)

    Liu Yansheng; Zhang Zhongxin; Zhang Guofu; Liu Zhichang; Hu Yufeng; Shi Quan; Ji Dejun

    2006-01-01

    The effects of the structure of typical cations and anions of ionic liquids on the separation of benzene and toluene from aromatic/paraffin mixtures were studied. The results showed that the corresponding separation factors were considerably larger than those of the traditional solvents (Benzene+Hexane+sulfolane), and that the ionic liquids could be used as novel solvents for the separation of aromatics from hydrocarbon mixtures. The key parameters governing the ability of ionic liquids for separating aromatics from hydrocarbon sources were investigated. It was found that the effectiveness of the ionic liquids, based on the same anion, changed in the cation order of [BIqu]+< [BPy]+< [BMIM]+. The selectivity of the ionic liquid toward aromatics decreased apparently with the increasing length of the substituted alkyl chain of its cationic head ring. The separation factors, based on the same cation, changed in the anion order of [Tf2N]-<[PF6]-<[BF4]-<[C2H5SO4]-. The solubilities of the aromatics were greater in the ionic liquids based on the former three anions than that in the ionic liquids involving [C2H5SO4]-.

  7. Probing the effects of the ester functional group, alkyl side chain length and anions on the bulk nanostructure of ionic liquids: a computational study.

    Science.gov (United States)

    Fakhraee, Mostafa; Gholami, Mohammad Reza

    2016-04-14

    The effects of ester addition on nanostructural properties of biodegradable ILs composed of 1-alkoxycarbonyl-3-alkyl-imidazolium cations ([C1COOCnC1im](+), n = 1, 2, 4) combined with [Br](-), [NO3](-), [BF4](-), [PF6](-), [TfO](-), and [Tf2N](-) were explored by using the molecular dynamics (MD) simulations and quantum theory of atoms in molecules (QTAIM) analysis at 400 K. Various thermodynamic properties of these ILs were extensively computed in our earlier work (Ind. Eng. Chem. Res., 2015, 54, 11678-11700). Nano-scale segregation analysis demonstrates the formation of a small spherical island-like hydrocarbon within the continuous ionic domain for ILs with short alkyl side chain ([C1COOC1C1im]), and a sponge-like nanostructure for the compound with long alkyl side chain ([C1COOC4C1im]). Ester-functionalized ILs with ethyl side chain ([C1COOC2C1im]) are the turning point between two different morphologies. Non-polar channels were observed for [C1COOC4C1im] ILs composed of smaller anions such as [Br] and [NO3], whereas clustering organization was found for the other anions. Formation of the spherical micelle-like nanostructure was seen for lengthened cations. Finally, the incorporation of an ester group into the alkyl side chain of the cation leads to stronger segregation between charged and uncharged networks, which consequently increased the possibility of self-assembly and micelle formation. PMID:27001746

  8. Anion effect on radiochemical stability of room-temperature ionic liquids under gamma irradiation

    International Nuclear Information System (INIS)

    Radiochemical stability of imidazolium-based ionic liquids constituted of the BuMeIm+ cation and associated with four commonly used anions (X-: Tf2N-, TfO-, PF6- and BF4-) has been investigated under gamma irradiation for high irradiation doses (up to 2.0 MGy). The anion effect has been examined by quantifying the radiolytic yields of disappearance for cation and anions and by identifying corresponding radiolysis products with several analytical techniques. On the one hand, a large number of radiolysis products are formed throughout the irradiation in ionic liquid solutions, resulting from reactions of primary generated species of cation and anion by indirect radiolysis. Primary generated species can react together throughout the irradiation by indirect radiolysis to form numerous radiolysis products in small quantities, indicating that several complex degradation pathways are involved for these radiation doses. This degradation pattern has been confirmed by identification of numerous gaseous radiolytic products. On the other hand, quantitative studies show that radiochemical stabilities of ionic liquids are in the same range of values as systems envisioned in nuclear fuel reprocessing with relatively low hydrogen yields. Indeed, this present work emphasizes the suitability of ionic liquids for applications in the nuclear fuel cycle. (authors)

  9. The Geometry and Structural Properties of the 4,8,12-Trioxa-4,8,12,12c-tetrahydrodibenzo[cd,mn]pyrene System in the Cationic State. Structures of a Planar Organic Cation with Various Monovalent- and Divalent Anions

    DEFF Research Database (Denmark)

    Krebs, Frederik C; Laursen, Bo W.; Johannsen, Ib;

    1999-01-01

    The geometry of the 4,8,12-trioxa-4,8,12,12c- tetrahydrodibenzo[cd,mn]pyrene system in the cationic state was established by X-ray structural resolution of the salts formed between the cationand various anions. The geometry was found to be planar for the 4,8,12-trioxa-4,8,12,12c- tetrahydrodibenzo...... [cd,mn]pyrenylium and 2,6,10-tri (tert-butyl)-4,8,12-trioxa-4,8,12,12c-tetrahydrodibenzo[cd,mn]pyre nylium cations with the monovalentanions I-, BF4-, PF6- AsF6-, HNO3. NO3- and CF3SO3-, and the divalent anions S2O62- and Mo6Cl142-. The salts were found to crystallize in distinct space groups...... following a characteristic pattern. Mixed cation-anion stacking resulted in space groups with high symmetry: Pbca in three cases and R (3) over bar c in one; a temperature study of the latter was made at ten different temperatures. The formation of dimers of anions and cations resulted in lower...

  10. Electrochemical behavior of sebaconitrile as a cosolvent in the formulation of electrolytes at high potentials for lithium-ion batteries

    International Nuclear Information System (INIS)

    The electrochemical behavior of new high potential electrolyte containing sebaconitrile in LiPF6/EC:DMC or LiBF4 was studied on glassy carbon and LiCoO2, LiCoPO4 as positive electrode materials. The increase of sebaconitrile concentration in EC:DMC electrolyte provides better electrolyte stability at higher potentials on glassy carbon as observed by cyclic voltammetry. Promising electrochemical results showing good reversibility and insertion/deinsertion efficiency have been also obtained on LiCoPO4 electrode cycled up to 5.3 V vs Li+/Li as upper potential limit. However, the cycling of LiCoPO4 at higher potential (6 V vs Li+/Li) shows lower reversibility and efficiency of insertion/deinsertion process due to the oxidative decomposition of the electrolyte at high potentials. The surface analysis performed by X-ray photoelectron spectroscopy confirms the formation of a surface layer induced by electrolyte degradation on both types of positive electrodes, which hinder the Li diffusion. The layer composition and morphology vary as a function of electrolyte composition and type of electrode

  11. Liquid-liquid extraction to lithium isotope separation based on room-temperature ionic liquids containing 2,2'-binaphthyldiyl-17-crown-5

    International Nuclear Information System (INIS)

    A novel liquid-liquid extraction system was investigated for the selective separation of lithium isotopes using ionic liquids (ILs = C8mim+PF6-, C8mim+BF4-, and C8mim+NTf2-) as extraction solvent and 2,2'-binaphthyldiyl-17-crown-5 (BN-17-5) as extractant. The effects of the concentration of lithium salt, counter anion of lithium salt, initial pH of aqueous phase, extraction temperature, and time on the lithium isotopes separation were discussed. Under optimized conditions, the maximum single-stage separation factor α of 6Li/7Li obtained in the present study was 1.046 ± 0.002, indicating the lighter isotope 6Li was enriched in IL phase while the heavier isotope 7Li was concentrated in the solution phase. The formation of 1:1 complex Li(BN-17-5)+ in the IL phase was determined on the basis of slope analysis method. The large value of the free energy change (-ΔG° = 92.89 J mol-1) indicated the high separation capability of the Li isotopes by BN-17-5/IL system. Lithium in Li(BN-17-5)+ complex was stripped by 1 mol L-1 HCl solution. The extraction system offers high efficiency, simplicity, and green application prospect to lithium isotope separation. (author)

  12. Sulfone-carbonate ternary electrolyte with further increased capacity retention and burn resistance for high voltage lithium ion batteries

    Science.gov (United States)

    Xue, Leigang; Lee, Seung-Yul; Zhao, Zuofeng; Angell, C. Austen

    2015-11-01

    Safety and high energy density are the two focus issues for current lithium ion batteries. For safety, it has been demonstrated that sulfone electrolytes are much less flammable than the prevailing all-carbonate type, and they are also promising for high voltage batteries due to the high oxidization resistance. However, the high melting points and viscosities greatly restricted their application. Based on our previous work on use of fluidity-enhancing cosolvents to make binary sulfone-carbonate electrolytes, we report here a three-component system that is more conductive and should be even less flammable while additionally having better low temperature stability. The conductivity-viscosity relations have been determined for this electrolyte and are comparable to those of the "standard" carbonate electrolyte. The additional component also produces much improved capacity retention for the LiNi0.5Mn1.5O4 cathode. As with carbonate electrolytes, increase of temperature to 55 °C leads to rapid capacity decrease during cycling, but the capacity loss is due to the salt, not the solvent. The high discharge capacity observed at 25 °C when LiBF4 replaces LiPF6, is fully retained at 55 °C.

  13. Effect of Counterion on the Solvatochromic Properties of Heteroleptic Chelate Copper(II Complexes

    Directory of Open Access Journals (Sweden)

    Hamid Golchoubian

    2013-01-01

    Full Text Available A series of heteroleptic chelate copper(II complexes of the type [Cu(L(acac]X where acac = acetylacetonate; L = N,N′-1,6-bis(2-fluorophenyl-2,5-diazahexane; X=CIO4-, BPh4-, PF6-, and BF4- have been prepared and characterized by elemental analyses, IR and UV-Vis spectroscopies, and molar conductance measurements. The prepared complexes are fairly soluble in a large number of organic solvents and show positive solvatochromism. Among the complexes [Cu(L(acac]ClO4, it is demonstrated the most solvatochromism. A multiparametric equation has been utilized to explain the solvent effect on the d-d transition of the complexes using SPSS/PC software. To explore the mechanism of interaction between solvent molecules and the complexes, different solvent parameters such as DN, AN, α, ET(30, π*, and β using stepwise multiple linear regression (SMLR method were employed. The results demonstrated that the donor power of the solvent plays the most important role in the solvatochromism of the compounds.

  14. Spin-crossover studies on a series of 1-D chain and dinuclear iron(II) triazine-dipyridylamine compounds

    International Nuclear Information System (INIS)

    Four isostructural one-dimensional polymeric iron(II) spin crossover materials containing the ligand 2-chloro-4,6-bis(dipyrid-2-ylamino)-1,3,5-triazine (cddt) have been synthesized and magnetically and structurally characterized. The polymeric material Fe(NCS)2(cddt)·n(guest) (1), self assembles into three crystallographically distinct phases; the compounds 1b and 1c, [Fe(NCS)2(cddt)]·2(CH3OH), are polymorphs, however, 1a, [Fe(NCS)2(cddt)]·1/2(CHCl3)·(H2O) contains a different solvent system. Each phase shows very different magnetic behavior; phases 1a and 1b remain high spin over all temperatures, whilst phase 1c undergoes a half spin crossover between 225 and 125 K. The structural consequences of the spin transition in 1c have been followed using variable temperature synchrotron powder X-ray diffraction techniques. Variation of the chalcogenide ligand in the complex [Fe(NCSe)2(cddt)]·2(CH3OH), 2, leads to a full one-step spin crossover with a T1/2 of 200 K. Structural analysis of 1c below the transition temperature reveals alternating, crystallographically distinct, HS and LS iron(II) centers (HS: high spin, LS: low spin) along the chain, and structural analysis of 2 below the transition temperature reveals all LS iron(II) centers. Also reported are the structural characterizations of two dinuclear materials, containing the ligand 2,4,6-tris(dipyridin-2-ylamino)-1,3,5-triazine (tdt), of the formula [Fe(tdt)(X)2]2·(ClO4)·(solvent) (X = H2O, Cl- for 3a, 3b) which are analogous to those recently reported by Gamez et al. In addition, the structural characterizations are described for dinuclear materials, containing the ligand cddt, of the formula [Fe(cddt)(Cl)(X)]2·(Y)2·n(solvent) (X: H2O or NCCH3, Y: ClO4-, BF4- 4a, 4b and 4d) and for a cobalt(II) analogue, [Co(cddt)(Cl)(H2O)]2·(BF4)2·n(solvent) (4c)

  15. Fe(II) Spin Transition Materials Including an Amino-Ester 1,2,4-Triazole Derivative, Operating at, below, and above Room Temperature.

    Science.gov (United States)

    Dîrtu, Marinela M; Naik, Anil D; Rotaru, Aurelian; Spinu, Leonard; Poelman, Dirk; Garcia, Yann

    2016-05-01

    A new family of one-dimensional Fe(II) 1,2,4-triazole spin transition coordination polymers for which a modification of anion and crystallization solvent can tune the switching temperature over a wide range, including the room temperature region, is reported. This series of materials was prepared as powders after reaction of ethyl-4H-1,2,4-triazol-4-yl-acetate (αEtGlytrz) with an iron salt from a MeOH/H2O medium affording: [Fe(αEtGlytrz)3](ClO4)2 (1); [Fe(αEtGlytrz)3](ClO4)2·CH3OH (2); [Fe(αEtGlytrz)3](NO3)2·H2O (3); [Fe(αEtGlytrz)3](NO3)2 (4); [Fe(αEtGlytrz)3](BF4)2·0.5H2O (5); [Fe(αEtGlytrz)3](BF4)2 (6); and [Fe(αEtGlytrz)3](CF3SO3)2·2H2O (7). Their spin transition properties were investigated by (57)Fe Mossbauer spectroscopy, superconducting quantum interference device (SQUID) magnetometry, and differential scanning calorimetry (DSC). The temperature dependence of the high-spin molar fraction derived from (57)Fe Mössbauer spectroscopy in 1 reveals an abrupt single step transition between low-spin and high-spin states with a hysteresis loop of width 5 K (Tc(↑) = 296 K and Tc(↓) = 291 K). The properties drastically change with modification of anion and/or lattice solvent. The transition temperatures, deduced by SQUID magnetometry, shift to Tc(↑) = 273 K and Tc(↓) = 263 K for (2), Tc(↑) = 353 K and Tc(↓) = 333 K for (3), Tc(↑) = 338 K and Tc(↓) = 278 K for (4), T(↑) = 320 K and T(↓) = 305 K for (5), Tc(↑) = 106 K and Tc(↓) = 92 K for (6), and T(↑) = 325 K and T(↓) = 322 K for (7). Annealing experiments of 3 lead to a change of the morphology, texture, and magnetic properties of the sample. A dehydration/rehydration process associated with a spin state change was analyzed by a mean-field macroscopic master equation using a two-level Hamiltonian Ising-like model for 3. A new structural-property relationship was also identified for this series of materials [Fe(αEtGlytrz)3](anion)2·nSolvent based on Mössbauer and DSC

  16. Macrocyclic nickel(II) complexes: Synthesis, characterization, superoxide scavenging activity and DNA-binding

    Science.gov (United States)

    Ramadan, Abd El-Motaleb M.

    2012-05-01

    A new series of nickel(II) complexes with the tetraaza macrocyclic ligand have been synthesized as possible functional models for nickel-superoxide dismutase enzyme. The reaction of 5-amino-3-methyl-1-phenylpyrazole-4-carbaldehyde (AMPC) with itself in the presence of nickel(II) ion yields, the new macrocyclic cationic complex, [NiL(NO3)2], containing a ligand composed of the self-condensed AMPC (4 mol) bound to a single nickel(II) ion. A series of metathetical reactions have led to the isolation of a number of newly complexes of the types [NiL]X2; X = ClO4 and BF4, [NiLX2], X = Cl and Br (Scheme 1). Structures and characterizations of these complexes were achieved by several physicochemical methods namely, elemental analysis, magnetic moment, conductivity, and spectral (IR and UV-Vis) measurements. The electrochemical properties and thermal behaviors of these chelates were investigated by using cyclic voltammetry and thermogravimetric analysis (TGA and DTG) techniques. A distorted octahedral stereochemistry has been proposed for the six-coordinate nitrato, and halogeno complexes. For the four-coordinate, perchlorate and fluoroborate, complex species a square-planar geometry is proposed. The measured superoxide dismutase mimetic activities of the complexes indicated that they are potent NiSOD mimics and their activities are compared with those obtained previously for nickel(II) complexes. The probable mechanistic implications of the catalytic dismutation of O2rad - by the synthesized nickel(II) complexes are discussed. The DNA-binding properties of representative complexes [NiLCl2] and [NiL](PF4)2 have been investigated by the electronic absorption and fluorescence measurements. The results obtained suggest that these complexes bind to DNA via an intercalation binding mode and the binding affinity for DNA follows the order: [NiLCl2] □ [NiL](PF4)2.

  17. Encapsulated discrete octameric water cluster, 1D water tape, and 3D water aggregate network in diverse MOFs based on bisimidazolium ligands

    Science.gov (United States)

    Shi, Ruo-Bing; Pi, Min; Jiang, Shuang-Shuang; Wang, Yuan-Yuan; Jin, Chuan-Ming

    2014-08-01

    Four new metal-organic frameworks, [Zn(2-mBIM)2(SO3CF3)2·(H2O)4] (1), [Zn(BMIE)(1,4-BDC)]·(H2O)3 (2), [Cd(BIM)2(OH)(H2O)2(PF6)]·(H2O)4 (3), and [Cd(PA-BIM)2 (ClO4)2]·11.33H2O (4) (2-mBIM = bis(2-methylimidazol-1-yl)methane, BMIE = 1,2-bis[1-(2-methylimidazole)-diethoxy]ethane, BIM = bis(imidazol-1-yl)methane, and PA-BIM = 1,1-bis [(2-phenylazo)imidazol-1-yl]methane) have been prepared and structurally characterized. Complex 1 exhibits an infinite 1D cationic beaded-chain structure, which encapsulated discrete octameric water clusters that are comprised of a chair-like hexameric water cluster with two extra water molecules dangling on two diagonal vertices of the chair. Complex 2 forms a 1D infinite zigzag metal-organic chain structure with a 1D T4(0)A(4) water tape. Complexes 3 show a 2D grid-like sheet structure with the 1D water tape T4(0)A(0)2(0) motif. Complex 4 is a porous 3D MOF with tetrahedron-coordinated Cd(II) centers and trans-conformation PA-BIM ligands. These holes are occupied by a fascinating three-dimensional water clathrate network, which consists of cage-shaped structural tetradecameric water cluster (H2O)14 units and six independent bridged water molecules. The results suggest that the bisimidazolium ligands and anions play crucial roles in the formation of the different host structures and different guest water aggregations. Additionally, the thermal stabilities and photoluminescence spectra of the complexes have been discussed.

  18. Studies on the extraction and separation of lanthanide ions with a synergistic extraction system combined with 1,4,10,13-tetrathia-7,16-diazacyclooctadecane and lauric acid.

    Science.gov (United States)

    Masuda, Y; Zhang, Y; Yan, C; Li, B

    1998-05-01

    1,4,10,13-Tetrathia-7,16-diazacyclooctadecane (ATCO) and its binary extraction system containing lauric acid were studied extensively as extractants of lanthanide (M(3+)=La(3+), Ce(3+), Pr(3+), Nd(3+), Sm(3+), Eu(3+) and Gd(3+)) in 1,2-dichloroethane solution. The percentage extraction of Ce(3+) and Eu(3+) by ATCO were only measured to be less than 5% during a pH range 5.5-7.0 in NCS(-), ClO(4)(-) and PF(6)(-) mediums respectively, which indicates that ATCO alone has very low extractability to lanthanide, due to the bad fit of metal ions in its cavity. However, when lauric acid was added to the ATCO organic phase, because of forming rare earth adduct, the percentage extraction for lanthanide until Gd(3+) was enhanced in the binary system in comparison with that did not adopt the lauric acid within the pH range 6-7. The extraction species and extraction equilibrium constants logK(ex) were found to be CeLA(3)3HA, -8.5, EuLA(3)HA, -6.7, and GdLA(2)NO(3)2HA, -1.8, respectively. The separation factor between Eu(3+) and Ce(3+) was found to be 2.5, however, poor selectivity for lanthanide was observed. From Gd(3+) to Er(3+) and Lu(3+), the synergistic effect of the binary extraction system decreases with increasing atomic number. For gadolinium, the synergistic effect becomes much weaker than that of Ce(3+) and Eu(3+), no synergistic effect existed for erbium and lutetium. Thermodynamic data for synergistic solvent extraction are also reported in this paper. The order of organic phase stability constants of the extraction species is Sm (5.8)>Pr (5.7)>Eu (5.6)>Ce (5.3)>La (5.2)>Gd (2.8). PMID:18967144

  19. Synthesis and Crystal Structure of a Novel Tetranuclear Yttrium Complex With Proline Ligands at High pH Value%高pH下钇-L-脯氨酸四核配合物[Y4(HPrO)4(PRO)2 (μ3-OH)4 (H2O)7] (ClO4)6@6H2O的合成与晶体结构*

    Institute of Scientific and Technical Information of China (English)

    陈德; 张大顺; 李琳; 马宝清; 金天柱

    2000-01-01

    在水溶液中,调节pH至6.3,合成了高氯酸钇与L-脯氨酸的配合物[Y4(HPrO)4(PrO)2(μ3-OH)4(H2O)7](CIO4)6@6H2O单晶,并测定了其晶体结构.该晶体属菱形晶系,R3空间群,晶胞参数:a=b=c=12.786 3(15)A,α=β=γ=100.217(17)0,V=1977.0(4)A3,Z=1,最终偏差因子R1=0.086 9,wR2=0.220 3.每个晶胞以四个Y3+通过四个μ3-OH-离子、六个脯氨酸羧基桥联成四核簇状结构.其中三个Y3+每个均与三个μ3-OH、三个羧基氧原子、两个水分子配位,其配位数为8;另一个Y3+与三个μ3-OH、三个羧基氧原子、一个水分子配位,其配位数为7.

  20. 配位聚合物[Mn(4,4'-bpy)1.5(H2O)3](CIO4)·(4,4'-bpy)(L)·H2O的水热合成和晶体结构%Hydrothermal Synthesis and Crystal Structure of Coordination Polymer [Mn(4,4'-bpy)1.5(H2O)3] (ClO4)· (4,4'-bpy)(L)· H2O

    Institute of Scientific and Technical Information of China (English)

    黄妙龄

    2007-01-01

    The title compound, [Mn(4,4'-bpy)1.5(H2O)3](C1O4)·(4,4'-bpy)(L)· H2O(1), where L=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of triclinic, space group P(-1) with a=2.929 9(6) nm, b=1.0364(2) nm, c=8.222 0(1) nm, α=105.300(2)°, β=97.495(2)°,0.135 2. The Mn atoms are octahedrally coordinated by three N atoms of three 4,4'-bipyridine ligands and three O atoms of water. The complex shows a one-dimensional chain structure bridged by water and 4,4'-bipyridine molecules. CCDC: 615707.

  1. Synthesis, spectral and structural studies of water soluble arene ruthenium (II) complexes containing 2,2′-dipyridyl-N-alkylimine ligand

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Kaminsky, W.

    as a doublet at δ 1.31. The proton NMR spectra of complexes [1]PF 6 , [3]PF 6 and [5]PF 6 displayed a singlet resonance at around δ 4.02 assignable to methyl protons attached to nitrogen. Complexes [2]PF 6 , [4]PF 6 and [6]PF 6 displayed a... are diastereotopic, since the ruthenium atom is stereogenic due to coordination of four different ligand atoms. Similar spectrum pattern has been reported in some other p-cymene ruthenium (II) complexes [27,28]. The methyl protons of the isopropyl group resonate...

  2. Measurement of lithium ion transference numbers of electrolytes for lithium-ion batteries. A comparative study with five various methods.; Messung von Lithium-Ionen Ueberfuehrungszahlen an Elektrolyten fuer Lithium-Ionen Batterien. Eine vergleichende Studie mit fuenf verschiedenen Methoden

    Energy Technology Data Exchange (ETDEWEB)

    Zugmann, Sandra

    2011-03-30

    number and ideally activity coefficients. The new electrolyte lithium difluoromono(oxalato)borate LiDFOB in EC/DEC (3/7) was for example fully determined at 25 C in this work. In comparison with other salts (LiPF6 und LiBF4) it proves to be an appropriate electrolyte for lithium-ion batteries. It generates no HF by hydrolysis that avoids the use of environment friendly and cost-effective manganese spinels, and it much better soluble as lithium bis(oxalato)borate LiBOB. In addition LiDFOB protects aluminum from corrosion and is more thermal stable as the standard salt LiPF6.

  3. Development of Biosensors for Real Time Analysis of Perchlorate in Water

    OpenAIRE

    Frankenberger, William T.; Okeke, Benedict C.; Cheng, Quan Jason

    2006-01-01

    Perchlorate (ClO4 -) contamination of ground water is a widespread problem in the U.S., which can adversely affect human health and wildlife. Current methods for detecting and quantifying ClO4 - in water are time consuming, expensive, and subject to error due to complex procedures and various interferences. Thus, there is an urgent need to develop a method that can accurately detect and measure low concentrations of ClO4 - in the field. This study reports the construction of a ClO4 -- reducta...

  4. New tetradentate Schiff bases of 2-amino-3,5-dibromobenzaldehyde with aliphatic diamines and their metal complexes: Synthesis, characterization and thermal stability

    Science.gov (United States)

    Mohammadi, Khosro; Azad, Seyyedeh Sedigheh; Amoozegar, Ameneh

    2015-07-01

    The tetradentate Schiff base ligands (L1-L4), were synthesized by reaction between 2-amino-3,5-dibromobenzaldehyde and aliphatic diamines. Then, nickel and oxovanadium(IV) complexes of these ligands were synthesized and characterized by 1H NMR, Mass, IR, UV-Vis spectroscopy and thermogravimetry. The kinetic parameters of oxovanadium(IV) complexes were calculated from thermal studies. According to the results of thermogravimetric data, the thermal stability of oxovanadium(IV) complexes is as follow: VOL2(ClO4)2 >VOL4(ClO4)2 >VOL3(ClO4)2 >VOL1(ClO4)2

  5. Perchlorate Removal in groundwater by perchlorate reductases from the perchlorate respiring bacterium, perc1ace

    OpenAIRE

    Frankenberger, William

    2003-01-01

    [Note: See PDF for correct symbols.] Perchlorate (ClO4-) is an important energetic component of solid rocket fuel. The major source of ClO4- pollution is the military, space program and supporting industries. ClO4- is recalcitrant in the environment and is potentially toxic. The California Department of Health Services adopted an action level of 4 ppb for perchlorate in potable water. Microorganisms that reduce ClO4- to chloride and molecular oxygen have been isolated. For designing an effici...

  6. 锂盐型电力复合脂的导电性和摩擦学性能%Electrical Conductivities and Tribological Properties of Lithium Salts Conductive Grease

    Institute of Scientific and Technical Information of China (English)

    葛翔宇; 夏延秋; 冯欣; 宋玉旺; 樊小强

    2015-01-01

    以三种锂盐:四氟硼酸锂(LiBF4)、六氟磷酸锂(LiPF6)和双三氟甲烷磺酰亚胺锂(LiNTf2)作为锂基润滑脂导电剂制得了三种电力复合脂。分别采用 DDSJ-308A型电导率仪,GEST-121型体积表面电阻率测试仪和HLY-200A型回路电阻测试仪对电力复合脂的导电性进行了测试。并采用Optimol SRV-I型振荡往复摩擦磨损试验机对电力复合脂在室温下的摩擦学性能进行了测试。结果表明,三种锂盐可以提高润滑脂的导电性,还可以改善润滑脂的摩擦学性能。利用Micro-XAM3D 轮廓扫描仪测量了磨痕体积,采用扫描电子显微镜和PHI-5702型多功能X射线光电子能谱仪对磨损表面进行了表征和分析。分析结果表明,在摩擦过程中形成了包含吸附膜和化学反应膜的边界膜,使得减摩抗磨性能得到了改善。%Three kinds of conductive grease are prepared by adding three lithium salts, including lithium tetrafluoroborate (LiBF4), lithium hexafluorophosphate (LiPF6) and lithium bis (trifluoromethane sulfonamide) (LiNTf2) in lithium grease. The electrical conductive properties of the prepared conductive greases are evaluated by using a DDSJ-308A conductivity meter, a GEST-121 volume surface resistance tester and a HLY-200A circuit resistance tester, respectively. And the tribological behaviors of three kinds of lithium salts are investigated by an Optimol SRV-I oscillating reciprocating friction and wear tester at room temperature (RT). The results demonstrate that the addition of lithium salts can enhance the lithium grease conductivity and also dramatically improve the tribological properties of lithium grease, the wear volumes are valued by Micro-XAM3D noncontact surface mapping profiler, wear surface are characterized and analyzed based on scanning electron microscope (SEM) and PHI-5702 multifunctional X-ray photoelectron spectrometer (XPS). The results indicate the improvement of tribological properties

  7. High flash point electrolyte for use in lithium-ion batteries

    International Nuclear Information System (INIS)

    Highlights: → Substitution of linear carbonates in conventional electrolytes with adiponitrile allows the realization of high flash point electrolytes. → EC:ADN based electrolytes display a higher anodic stability than a conventional electrolyte based on EC:DEC. → Graphite and NCM electrodes used in combination with the EC:ADN based electrolyte display a performance comparable with that of conventional electrolytes. - Abstract: The high flash point solvent adiponitrile (ADN) was investigated as co-solvent with ethylene carbonate (EC) for use as lithium-ion battery electrolyte. The flash point of this solvent mixture was more than 110 deg. C higher than that of conventional electrolyte solutions involving volatile linear carbonate components, such as diethyl carbonate (DEC) or dimethyl carbonate (DMC). The electrolyte based on EC:ADN (1:1 wt) with lithium tetrafluoroborate (LiBF4) displayed a conductivity of 2.6 mS cm-1 and no aluminum corrosion. In addition, it showed higher anodic stability on a Pt electrode than the standard electrolyte 1 M lithium hexafluorophosphate (LiPF6) in EC:DEC (3:7 wt). Graphite/Li half cells using this electrolyte showed excellent rate capability up to 5C and good cycling stability (more than 98% capacity retention after 50 cycles at 1C). Additionally, the electrolyte was investigated in NCM/Li half cells. The cells were able to reach a capacity of 104 mAh g-1 at 5C and capacity retention of more than 97% after 50 cycles. These results show that an electrolyte with a considerably increased flash point with respect to common electrolyte systems comprising linear carbonates, could be realized without any negative effects on the electrochemical performance in Li-half cells.

  8. Liquid-liquid miscibility and volumetric properties of aqueous solutions of ionic liquids as a function of temperature

    International Nuclear Information System (INIS)

    The volumetric properties of seven {water + ionic liquid} binary mixtures have been studied as a function of temperature from (293 to 343) K. The phase behaviour of the systems was first investigated using a nephelometric method and excess molar volumes were calculated from densities measured using an Anton Paar densimeter and fitted using a Redlich-Kister type equation. Two ionic liquids fully miscible with water (1-butyl-3-methylimidazolium tetrafluoroborate ([C1C4Im][BF4]) and 1-ethyl-3-methylimidazolium ethylsulfate ([C1C2Im][EtSO4])) and five ionic liquids only partially miscible with water (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C1C2Im][NTf2]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C1C4Im][NTf2]), 1-butyl-3-methylimidazolium hexafluorophosphate ([C1C4Im][PF6]), 1-butyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C1C4Pyrro][NTf2]), and butyltrimethylammonium bis(trifluoromethylsulfonyl)imide ([N4111][NTf2])) were chosen. Small excess volumes (less than 0.5 cm3 . mol-1 at 298 K) are obtained compared with the molar volumes of the pure components (less than 0.3% of the molar volume of the pure ionic liquid). For all the considered systems, except for {[C1C2Im][EtSO4] + water}, positive excess molar volumes were calculated. Finally, an increase of the non-ideality character is observed for all the systems as temperature increases.

  9. Saturation properties of 1-alkyl-3-methylimidazolium based ionic liquids.

    Science.gov (United States)

    Rane, Kaustubh S; Errington, Jeffrey R

    2014-07-24

    We study the liquid-vapor saturation properties of room temperature ionic liquids (RTILs) belonging to the homologous series 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cnmim][NTf2]) using Monte Carlo simulation. We examine the effect of temperature and cation alkyl chain length n on the saturated densities, vapor pressures, and enthalpies of vaporization. These properties are explicitly calculated for temperatures spanning from 280 to 1000 K for RTILs with n = 2, 4, 6, 8, 10, and 12. We also explore how the identity of the anion influences saturation properties. Specifically, we compare results for [C(4)mim][NTf2] with those for 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim][BF4]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim][PF6]). Simulations are completed with a recently developed realistic united-atom force field. A combination of direct grand canonical and isothermal-isobaric temperature expanded ensemble simulations are used to construct phase diagrams. Our results are compared with experimental data and Gibbs ensemble simulation data. Overall, we find good agreement between our results and those measured experimentally. We find that the vapor pressures and enthalpies of vaporization show a strong dependence on the size of the alkyl chain at low temperatures, whereas no particular trend is observed at high temperatures. Finally, we also discuss the effect of temperature on liquid phase nanodomains observed in RTILs with large hydrophobic groups. We do not observe a drastic change in liquid phase structure upon variation of the temperature, which suggests there is not a sharp phase transition between a nanostructured and homogeneous liquid, as has been suggested in earlier studies. PMID:24986360

  10. Hydroxyl-functionalized 1-(2-hydroxyethyl)-3-methyl imidazolium ionic liquids: thermodynamic and structural properties using molecular dynamics simulations and ab initio calculations.

    Science.gov (United States)

    Fakhraee, Mostafa; Zandkarimi, Borna; Salari, Hadi; Gholami, Mohammad Reza

    2014-12-11

    The influences of hydroxyl functional group (-OH) on the thermodynamic and structural properties of ionic liquids (ILs) composed of 1-(2-Hydroxyethyl)-3-methyl imidazolium ([C2OHmim](+)) cation and the six different conventional anions, including [Cl](-), [NO3](-), [BF4](-), [PF6](-), [TfO](-), and [Tf2N](-) have been extensively investigated using classical molecular dynamics (MD) simulations combined with ab initio calculations over a wide range of temperature (298-550 K). The volumetric thermodynamic properties, enthalpy of vaporization, cohesive energy density, Hildebrand solubility parameter, and heat capacity at constant pressure were estimated at desired temperature. The simulated densities were in good agreement with the experimental data with a slight overestimation. The interionic interaction of selected ILs was also computed using both the MD simulations and ab initio calculations. It was found that the highest association of cation and anion is attributed to [C2OHmim][Cl] followed by [C2OHmim][NO3], and [C2OHmim][Tf2N] with the bulkiest anion has the weakest interionic interaction among chosen ILs. The similar trend of interactions energies was nearly observed from cohesive energy density results. Additional structural details were comprehensively yielded by calculating radial distribution functions (RDFs) and spatial distribution function (SDFs) at 358 K. The most stable configurations of isolated and dimer ion pairs of these ILs were in excellent consistency with RDFs and SDFs results. Significant changes in arrangement of anions around the [C2OHmim](+) cation in comparison with conventional imidazolium-based ILs can be inferred from the MD simulations and ab initio results. Also, microscopic structural properties disclosed that the most strong cation-cation interaction is ascribed to the hydroxyl-functionalized ILs composed of bulkier anions, whereas ILs incorporating [Cl](-) and [NO3](-) anions are mainly involved in cation-anion interactions. The

  11. Modeling stability and flexibility of α-Chymotrypsin in room temperature ionic liquids.

    Science.gov (United States)

    Latif, Muhammad A M; Tejo, Bimo A; Abedikargiban, Roghayeh; Abdul Rahman, Mohd B; Micaêlo, Nuno M

    2014-01-01

    We investigate the structure and dynamics of α-Chymotrypsin in five room temperature ionic liquids (RTILs) sharing a common cation, hydrated with different water percentages (w/w) (weight of water over protein). Results from molecular dynamics simulations are correlated with experimental evidences from studies on the activity of enzymes in RTILs. α-Chymotrypsin protein structure is closer to its native crystallographic structure in RTILs than in aqueous environment. We show that the structural properties of α-Chymotrypsin were affected by the water concentration assayed in a typical bell-shaped profile, which is also frequently reported for organic solvents. The protein structure was more native like at 10-20% of water (w/w) for all RTILs except for [BMIM][Cl]. We found that the fluctuations of the main chain in [BMIM][BF4] and [BMIM][TfO] were not significantly affected by the increasing amount of water. However, we were able to show that the flexible regions were the ones more hydrated, indicating that water is responsible for the flexibility of the protein. The solvation of the enzyme in water-immiscible RTILs, such as [BMIM][PF6] and [BMIM][Tf2N] lead to higher enzyme flexibility at increased water content. Enzyme solvation by [BMIM][Cl] resulted in ion penetration in the core enzyme structure, causing incremented flexibility and destabilization at low water percentages. All RTILs stripped water molecules from the protein surface, following a similar behavior also found in organic solvents. Anions formed structured arrangements around the protein, which allowed non-stripped water molecules to localize on the protein surface. PMID:23844874

  12. Ultrafast vibrational spectroscopy (2D-IR) of CO2 in ionic liquids: Carbon capture from carbon dioxide's point of view

    Science.gov (United States)

    Brinzer, Thomas; Berquist, Eric J.; Ren, Zhe; Dutta, Samrat; Johnson, Clinton A.; Krisher, Cullen S.; Lambrecht, Daniel S.; Garrett-Roe, Sean

    2015-06-01

    The CO2ν3 asymmetric stretching mode is established as a vibrational chromophore for ultrafast two-dimensional infrared (2D-IR) spectroscopic studies of local structure and dynamics in ionic liquids, which are of interest for carbon capture applications. CO2 is dissolved in a series of 1-butyl-3-methylimidazolium-based ionic liquids ([C4C1im][X], where [X]- is the anion from the series hexafluorophosphate (PF 6- ), tetrafluoroborate (BF 4- ), bis-(trifluoromethyl)sulfonylimide (Tf2N-), triflate (TfO-), trifluoroacetate (TFA-), dicyanamide (DCA-), and thiocyanate (SCN-)). In the ionic liquids studied, the ν3 center frequency is sensitive to the local solvation environment and reports on the timescales for local structural relaxation. Density functional theory calculations predict charge transfer from the anion to the CO2 and from CO2 to the cation. The charge transfer drives geometrical distortion of CO2, which in turn changes the ν3 frequency. The observed structural relaxation timescales vary by up to an order of magnitude between ionic liquids. Shoulders in the 2D-IR spectra arise from anharmonic coupling of the ν2 and ν3 normal modes of CO2. Thermal fluctuations in the ν2 population stochastically modulate the ν3 frequency and generate dynamic cross-peaks. These timescales are attributed to the breakup of ion cages that create a well-defined local environment for CO2. The results suggest that the picosecond dynamics of CO2 are gated by local diffusion of anions and cations.

  13. Ultrafast vibrational spectroscopy (2D-IR) of CO2 in ionic liquids: Carbon capture from carbon dioxide’s point of view

    International Nuclear Information System (INIS)

    The CO2ν3 asymmetric stretching mode is established as a vibrational chromophore for ultrafast two-dimensional infrared (2D-IR) spectroscopic studies of local structure and dynamics in ionic liquids, which are of interest for carbon capture applications. CO2 is dissolved in a series of 1-butyl-3-methylimidazolium-based ionic liquids ([C4C1im][X], where [X]− is the anion from the series hexafluorophosphate (PF6−), tetrafluoroborate (BF4−), bis-(trifluoromethyl)sulfonylimide (Tf2N−), triflate (TfO−), trifluoroacetate (TFA−), dicyanamide (DCA−), and thiocyanate (SCN−)). In the ionic liquids studied, the ν3 center frequency is sensitive to the local solvation environment and reports on the timescales for local structural relaxation. Density functional theory calculations predict charge transfer from the anion to the CO2 and from CO2 to the cation. The charge transfer drives geometrical distortion of CO2, which in turn changes the ν3 frequency. The observed structural relaxation timescales vary by up to an order of magnitude between ionic liquids. Shoulders in the 2D-IR spectra arise from anharmonic coupling of the ν2 and ν3 normal modes of CO2. Thermal fluctuations in the ν2 population stochastically modulate the ν3 frequency and generate dynamic cross-peaks. These timescales are attributed to the breakup of ion cages that create a well-defined local environment for CO2. The results suggest that the picosecond dynamics of CO2 are gated by local diffusion of anions and cations

  14. Use of starch and potato peel waste for perchlorate bioreduction in water.

    Science.gov (United States)

    Okeke, Benedict C; Frankenberger, William T

    2005-07-15

    The cost of carbon substrates for microbial reduction of perchlorate (ClO(4)(-)) is central to the success and competitiveness of a sustainable bioremediation strategy for ClO(4)(-). This study explored the potential application of starch in combination with an amylolytic bacterial consortia and potato peel waste for ClO(4)(-) bioreduction. We obtained a potent amylolytic bacterial consortium that consisted of a Citrobacter sp. S4, Streptomyces sp. S2, Flavobacterium sp. S6, Pseudoxanthomonas sp. S5, Streptomyces sp. S7, and an Aeromonas sp. S8 identified by 16S rDNA sequencing. ClO(4)(-) concentration substantially decreased in purified starch medium inoculated with the amylolytic bacterial consortium and Dechlorosoma sp. perclace. Potato peel waste supported ClO(4)(-) reduction by perclace with the rate of ClO(4)(-) reduction being dependent on the amount of potato peels. Over 90% ClO(4)(-) removal was achieved in 4 days in a single time point experiment with 2% (w/v) potato peels waste. ClO(4)(-) reduction in a non-sterile 0.5% potato peel media inoculated with perclace occurred with an initial concentration of 10.14+/-0.04 mg L(-1) to 2.87+/-0.4 mg L(-1) (71.7% reduction) within 5 days. ClO(4)(-) was not detected in the cultures in 6 days. In a non-sterile 0.5% potato media without perclace, ClO(4)(-) depletion occurred slowly from an initial value of 9.99+/-0.15 mg L(-1) to 6.33+/-0.43 mg L(-1) (36.63% reduction) in 5 days. Thereafter, ClO(4)(-) was rapidly degraded achieving 77.1% reduction in 7 days and not detected in 9 days. No susbstantial reduction of ClO(4)(-) was observed in the sterile potato peel media without perclace in 7 days. Redox potential of the potato peel cultures was favorable for ClO(4)(-) reduction, decreasing to as low as -294 mV in 24 h. Sugar levels remained very low in cultures effectively reducing ClO(4)(-) and was substantially higher in sterilized controls. Our results indicate that potato peel waste in combination with amylolytic microorganisms and Dechlorosoma sp. perclace can be economically used to achieve complete ClO(4)(-) removal from water. PMID:16084965

  15. 1,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled β-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexes.

    Science.gov (United States)

    Ansari, Mohd Asif; Mandal, Abhishek; Paretzki, Alexa; Beyer, Katharina; Fiedler, Jan; Kaim, Wolfgang; Lahiri, Goutam Kumar

    2016-06-01

    The dinuclear complexes {(μ-H2L)[Ru(bpy)2]2}(ClO4)2 ([3](ClO4)2), {(μ-H2L)[Ru(pap)2]2}(ClO4)2 ([4](ClO4)2), and the asymmetric [(bpy)2Ru(μ-H2L)Ru(pap)2](ClO4)2 ([5](ClO4)2) were synthesized via the mononuclear species [Ru(H3L)(bpy)2]ClO4 ([1]ClO4) and [Ru(H3L)(pap)2]ClO4 ([2]ClO4), where H4L is the centrosymmetric 1,5-diamino-9,10-anthraquinone, bpy is 2,2'-bipyridine, and pap is 2-phenylazopyridine. Electrochemistry of the structurally characterized [1]ClO4, [2]ClO4, [3](ClO4)2, [4](ClO4)2, and [5](ClO4)2 reveals multistep oxidation and reduction processes, which were analyzed by electron paramagnetic resonance (EPR) of paramagnetic intermediates and by UV-vis-NIR spectro-electrochemistry. With support by time-dependent density functional theory (DFT) calculations the redox processes could be assigned. Significant results include the dimetal/bridging ligand mixed spin distribution in 3(3+) versus largely bridge-centered spin in 4(3+)-a result of the presence of Ru(II)-stabilizig pap coligands. In addition to the metal/ligand alternative for electron transfer and spin location, the dinuclear systems allow for the observation of ligand/ligand and metal/metal site differentiation within the multistep redox series. DFT-supported EPR and NIR absorption spectroscopy of the latter case revealed class II mixed-valence behavior of the oxidized asymmetric system 5(3+) with about equal contributions from a radical bridge formulation. In comparison to the analogues with the deprotonated 1,4-diaminoanthraquinone isomer the centrosymmetric H2L(2-) bridge shows anodically shifted redox potentials and weaker electronic coupling between the chelate sites. PMID:27171539

  16. Effect of side-chain asymmetry on the intermolecular structure and order-disorder transition in alkyl-substituted polyfluorenes

    DEFF Research Database (Denmark)

    Knaapila, Matti; Stepanyan, R.; Torkkeli, M.;

    2016-01-01

    or below the average grafting distance). Calorimetry and x-ray scattering indicate the condition TODT(PF6)∼TODTbi(PF1−8) following the low grafting prediction. PF6 side chains coming from the alternating backbone layers appear as two separate layers with thickness H(PF6), whereas PF1-8 side chains...

  17. Treatment of Amiodarone-Induced Thyrotoxicosis Type 2 : A Randomized Clinical Trial

    NARCIS (Netherlands)

    Eskes, Silvia A.; Endert, Erik; Fliers, Eric; Geskus, Ronald B.; Dullaart, Robin P. F.; Links, Thera P.; Wiersinga, Wilmar M.

    2012-01-01

    Context: Amiodarone-induced thyrotoxicosis (AIT) type 2 is self-limiting in nature, but most physicians are reluctant to continue amiodarone. When prednisone fails to restore euthyroidism, possibly due to mixed cases of AIT type 1 and 2, perchlorate (ClO4) might be useful because ClO4 reduces the cy

  18. Molecular sieve supported ionic liquids as efficient adsorbent for CO2 capture

    OpenAIRE

    Yang Na; Wang Rui

    2015-01-01

    [NH3e-mim][BF4], [OHe-mim][BF4] and [HOEAm] were selected and supported onto molecular sieves NaY, USY, SAPO-34 and MCM-41, to prepare supported ionic liquids. It was found that [NH3e-mim][BF4]/NaY has excellent CO2 adsorption performance, with adsorption capacity of 0.108 mmolCO2/g. This paper investigates the optimal adsorption conditions and recyclability of [NH3e-mim][BF4]/NaY. The results show that [NH3e-mim][BF4]/NaY has good CO2 adsorption under the ...

  19. Determination of three physical properties of quinoline ionic liquids with hexafluorophosphate

    OpenAIRE

    Tang Dan; Wang Litao; Yao Shun; Chen Yanwen; Wang Daocai; Song Hang

    2016-01-01

    Densities of one acidic ionic liquid (IL) Quinolinum hexafluorophosphate ([HBpy][PF6]), and four neutral dicationic ionic liquids (ILs) based on quinoline and hexafluoro-phosphate and linked with poly(ethylene glycol) (PEG): ([PEG200-DIL][PF6]2, [PEG400-DIL][PF6]2, [PEG800-DIL][PF6]2 and [PEG1000-DIL][PF6]2) were determined. In addition, the solubilities of six ILs in six lower alcohols, water, acetonitrile and diethyl ether were measured at 288.15 K; and the hydroscopicity of above five ILs ...

  20. Isotopic tracing of perchlorate sources in groundwater from Pomona, California

    International Nuclear Information System (INIS)

    Highlights: • Isotopic analysis of groundwater perchlorate can provide source identification. • Citrus cultivation in Pomona, CA caused perchlorate contamination of groundwater. • Hydrologic modeling and mass balance support interpretation of perchlorate source. - Abstract: The groundwater of Pomona, California, is contaminated with perchlorate (ClO4-). This water is treated to reduce the ClO4- concentration to less than 6 μg L−1 for compliance with California Department of Public Health drinking water regulations. A study of the isotopic composition of oxygen and chlorine in ClO4- has been conducted to determine the source of the contamination. Isotopic compositions were measured for ClO4- samples extracted from 14 wells, yielding ranges of δ18O values from −10.8‰ to −8.0‰, Δ17O values from +4.6‰ to +7.5‰, and δ37Cl values from −12.8‰ to −8.9‰. Evaluation of mixing proportions using published isotopic data for three ClO4- end-members (synthetic, Atacama, and indigenous natural ClO4-) indicates that contamination is dominantly (85–89%) Atacama ClO4- derived from past use of imported Chilean nitrate fertilizer in citrus cultivation. This interpretation is consistent with (1) aerial photography archives showing extensive citrus fields surrounding Pomona in the early- to mid-20th century, (2) mass-balance estimates for ClO4-, and (3) numerical hydrologic models yielding travel-times for ClO4- from fields to wells that are in the range of 15 to >100 years. The hydrologic models predict that ClO4- contamination of Pomona groundwater will persist for decades into the future

  1. Perchlorate content of plant foliage reflects a wide range of species-dependent accumulation but not ozone-induced biosynthesis

    International Nuclear Information System (INIS)

    Perchlorate (ClO4−) interferes with uptake of iodide in humans. Emission inventories do not explain observed distributions. Ozone (O3) is implicated in the natural origin of ClO4−, and has increased since pre-industrial times. O3 produces ClO4−in vitro from Cl−, and plant tissues contain Cl− and redox reactions. We hypothesize that O3 exposure may induce plant synthesis of ClO4−. We exposed contrasting crop species to environmentally relevant O3 concentrations. In the absence of O3 exposure, species exhibited a large range of ClO4− accumulation but there was no relationship between leaf ClO4− and O3, whether expressed as exposure or cumulative flux (dose). Older, senescing leaves accumulated more ClO4− than younger leaves. O3 exposed vegetation is not a source of environmental ClO4−. There was evidence of enhanced ClO4− content in the soil surface at the highest O3 exposure, which could be a significant contributor to environmental ClO4−. -- Highlights: • Exposure to ozone in crop species does not induce accumulation nor biosynthesis of perchlorate. • Older leaves accumulate more perchlorate than younger leaves. • Soil surface may accumulate perchlorate following exposure to ozone. • Species differ greatly in accumulation of perchlorate from the rhizosphere, independent of ozone. • Ozone exposed vegetation is not a candidate source of environmental perchlorate. -- Exposure of crop species to ozone did not lead to biosynthesis or greater accumulation of foliar perchlorate. Older leaves accumulated more perchlorate than younger leaves

  2. Widespread presence of naturally occurring perchlorate in high plains of Texas and New Mexico

    Science.gov (United States)

    Rajagopalan, S.; Anderson, T.A.; Fahlquist, L.; Rainwater, K.A.; Ridley, M.; Jackson, W.A.

    2006-01-01

    Perchlorate (ClO4-) occurrence in groundwater has previously been linked to industrial releases and the historic use of Chilean nitrate fertilizers. However, recently a number of occurrences have been identified for which there is no obvious anthropogenic source. Groundwater from an area of 155 000 km2 in 56 counties in northwest Texas and eastern New Mexico is impacted by the presence of ClO4-. Concentrations were generally low (<4 ppb), although some areas are impacted by concentrations up to 200 ppb. ClO4- distribution is not related to well type (public water system, domestic, agricultural, or water-table monitoring) or aquifer (Ogallala, Edward Trinity High Plains, Edwards Trinity Plateau, Seymour, or Cenozoic). Results from vertically nested wells strongly indicate a surface source. The source of ClO4- appears to most likely be atmospheric deposition. Evidence supporting this hypothesis primarily relates to the presence of ClO 4- in tritium-free older water, the lack of relation between land use and concentration distribution, the inability of potential anthropogenic sources to account for the estimated mass of ClO4-, and the positive relationship between conserved anions (e.g., IO3-, Cl-, SO4-2) and ClO4-. The ClO4- distribution appears to be mainly related to evaporative concentration and unsaturated transport. This process has led to higher ClO4- and other ion concentrations in groundwater where the water table is relatively shallow, and in areas with lower saturated thickness. Irrigation may have accelerated this process in some areas by increasing the transport of accumulated salts and by increasing the number of evaporative cycles. Results from this study highlight the potential for ClO4- to impact groundwater in arid and semiarid areas through long-term atmospheric deposition. ?? 2006 American Chemical Society.

  3. Heteropolyhedral silver compounds containing the polydentate ligand N,N,O-E-[6-(hydroxyimino)ethyl]-1,3,7-trimethyllumazine. Preparation, spectral and XRD structural study and AIM calculations.

    Science.gov (United States)

    Jiménez-Pulido, Sonia B; Hueso-Ureña, Francisco; Fernández-Liencres, M Paz; Fernández-Gómez, Manuel; Moreno-Carretero, Miguel N

    2013-01-14

    The oxime derived from 6-acetyl-1,3,7-trimethyllumazine (1) ((E-6-(hydroxyimino)ethyl)-1,3,7-trimethylpteridine-2,4(1H,3H)-dione, DLMAceMox) has been prepared and its molecular and crystal structure determined from spectral and XRD data. The oxime ligand was reacted with silver nitrate, perchlorate, thiocyanate, trifluoromethylsulfonate and tetrafluoroborate to give complexes with formulas [Ag(2)(DLMAceMox)(2)(NO(3))(2)](n) (2), [Ag(2)(DLMAceMox)(2)(ClO(4))(2)](n) (3), [Ag(2)(DLMAceMox)(2)(SCN)(2)] (4), [Ag(2)(DLMAceMox)(2)(CF(3)SO(3))(2)(CH(3)CH(2)OH)]·CH(3)CH(2)OH (5) and [Ag(DLMAceMox)(2)]BF(4) (6). Single-crystal XRD studies show that the asymmetrical residual unit of complexes 2, 3 and 5 contains two quite different but connected silver centers (Ag1-Ag2, 2.9-3.2 Å). In addition to this, the Ag1 ion displays coordination with the N5 and O4 atoms from both lumazine moieties and a ligand (nitrato, perchlorato or ethanol) bridging to another disilver unit. The Ag2 ion is coordinated to the N61 oxime nitrogens, a monodentate and a (O,O)-bridging nitrato/perchlorato or two monodentate O-trifluoromethylsulfonato anions. The coordination polyhedra can be best described as a strongly distorted octahedron (around Ag1) and a square-based pyramid (around Ag2). The Ag-N and Ag-O bond lengths range between 2.22-2.41 and 2.40-2.67 Å, respectively. Although the structure of 4 cannot be resolved by XRD, it is likely to be similar to those described for 2, 3 and 5, containing Ag-Ag units with S-thiocyanato terminal ligands. Finally, the structure of the tetrafluoroborate compound 6 is mononuclear with a strongly distorted tetrahedral AgN(4) core (Ag-N, 2.27-2.43 Å). Always, the different Ag-N distances found clearly point to the more basic character of the oxime N61 nitrogen atom when compared with the pyrazine N5 one. A topological analysis of the electron density within the framework provided by the quantum theory of atoms in molecules (QTAIM) using DFT(M06L) levels of

  4. Synthesis, spectroscopic analysis and photolabilization of water-soluble ruthenium(III)-nitrosyl complexes.

    Science.gov (United States)

    Merkle, Anna C; McQuarters, Ashley B; Lehnert, Nicolai

    2012-07-14

    In this paper, the synthesis, structural and spectroscopic characterization of a series of new Ru(III)-nitrosyls of {RuNO}(6) type with the coligand TPA (tris(2-pyridylmethyl)amine) are presented. The complex [Ru(TPA)Cl(2)(NO)]ClO(4) (2) was prepared from the Ru(III) precursor [Ru(TPA)Cl(2)]ClO(4) (1) by simple reaction with NO gas. This led to the surprising displacement of one of the pyridine (py) arms of TPA by NO (instead of the substitution of a chloride anion by NO), as confirmed by X-ray crystallography. NO complexes where TPA serves as a tetradentate ligand were obtained by reacting the new Ru(II) precursor [Ru(TPA)(NO(2))(2)] (3) with a strong acid. This leads to the dehydration of nitrite to NO(+), and the formation of the {RuNO}(6) complex [Ru(TPA)(ONO)(NO)](PF(6))(2) (4), which was also structurally characterized. Derivatives of 4 where nitrite is replaced by urea (5) or water (6) were also obtained. The nitrosyl complexes obtained this way were then further investigated using IR and FT-Raman spectroscopy. Complex 2 with the two anionic chloride coligands shows the lowest N-O and highest Ru-NO stretching frequencies of 1903 and 619 cm(-1) of all the complexes investigated here. Complexes 5 and 6 where TPA serves as a tetradentate ligand show ν(N-O) at higher energy, 1930 and 1917 cm(-1), respectively, and ν(Ru-NO) at lower energy, 577 and 579 cm(-1), respectively, compared to 2. These vibrational energies, as well as the inverse correlation of ν(N-O) and ν(Ru-NO) observed along this series of complexes, again support the Ru(II)-NO(+) type electronic structure previously proposed for {RuNO}(6) complexes. Finally, we investigated the photolability of the Ru-NO bond upon irradiation with UV light to determine the quantum yields (φ) for NO photorelease in complexes 2, 4, 5, and additional water-soluble complexes [Ru(H(2)edta)(Cl)(NO)] (7) and [Ru(Hedta)(NO)] (8). Although {RuNO}(6) complexes are frequently proposed as NO delivery agents in vivo

  5. Developing New Electrolytes for Advanced Li-ion Batteries

    Science.gov (United States)

    McOwen, Dennis Wayne

    synthesized for this investigation: dilithium 1,2,5-thiadiazolidine-3,4-dione-1,1-dioxide (Li2TDD), lithium ethyl N-trifluoroacetylcarbamate (LiETAC), lithium hexafluoroisopropoxide (LiHFI), lithium pentafluorophenolate (LiPFPO), and lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI). Using crystalline solvate structure analysis and electrolyte solvation numbers, each of these lithium salts were compared to more well-characterized lithium salts, such as LiPF6 and LiBF4. From this study, links between anion structural characteristics and the anion...Li+ cation interactions (i.e., ionic association strength) were made. From the screening of the five lithium salts that were synthesized, LiTDI was determined to be a promising candidate for Li-ion battery electrolytes. Further characterization of carbonate- and mixed carbonate-LiTDI electrolytes (e.g., ionic conductivity) confirmed this to be the case. Coin cells containing LiTDI or LiPF6 electrolytes showed that cells with either electrolyte could deliver nearly identical power density at 25 °C. Additionally, thermogravimetric analysis (TGA) and NMR suggested that the LiTDI salt and carbonate-LiTDI electrolytes are thermally stable up to at least 60 °C. Further supporting this finding, coin cells cycled at 60 °C with LiPF6 lost significantly more capacity than those with LiTDI. Therefore, LiTDI is a prime candidate for the complete replacement of LiPF6 to significantly increase Li-ion battery tolerance to heat, improving the safety characteristics. In addition to searching for new lithium salts, the effect of lithium salt concentration on electrolyte physicochemical properties was investigated. This radically different approach to modifying electrolyte properties determined that amorphous, highly concentrated carbonate-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolytes have drastically different behavior than more dilute electrolytes. For example, the thermal stability and anodic stability vs. a Pt

  6. Performance analysis of absorption heat transformer cycles using ionic liquids based on imidazolium cation as absorbents with 2,2,2-trifluoroethanol as refrigerant

    International Nuclear Information System (INIS)

    Highlights: • TFE + [emim][BF4] (or [bmim][BF4]) absorption heat transformer cycles are studied. • Influence of various operating conditions on cycle’s performance is investigated. • Performance comparisons with H2O + LiBr and TFE + TEGDME cycles are done. • Enthalpy data for TFE + [emim][BF4] (or [bmim][BF4]) liquid mixtures are calculated. • TFE + [emim][BF4] (or [bmim][BF4]) cycles have higher gross temperature lift (GTL). - Abstract: A detailed thermodynamic performance analysis of a single-stage absorption heat transformer and double absorption heat transformer cycles using new working pairs composed of ionic liquids (1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF4]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4])) as absorbent and 2,2,2-trifluoroethanol (TFE) as refrigerant has been studied. Several performance indicators were used to evaluate and compare the performance of the cycles using the TFE + [emim][BF4] and TFE + [bmim][BF4] working pairs with the conventional H2O + LiBr and organic TFE + TEGDME working pairs. The obtained results show that the ionic liquid based working pairs are suitable candidates to replace the conventional H2O + LiBr working pairs in order to avoid the disadvantages associated with it mainly crystallization and corrosion and also they perform better (higher gross temperature lift) than TFE + TEGDME working pair at several operating conditions considered in this work

  7. Temporal and spatial variation of perchlorate in streambed sediments: results from in-situ dialysis samplers

    International Nuclear Information System (INIS)

    The fate of perchlorate (ClO4-) in streambed sediments is becoming a concern due to the increasing number of groundwater and surface water contamination sites in the United States. Dialysis samplers were deployed at three sites over a period of 1 year to determine the vertical distribution of ClO4-in sediment pore water. Results indicated that the spatial and temporal ClO4-penetration into sediments could be affected by numerous factors, such as temperature, microbial degradation, ClO4-surface water concentration, and sediment physico-geological properties. In general, maximum ClO4-penetration into sediments at the studied sites was 30 cm below the sediment-water surface. The vertical sequential depletion of electron acceptors in sediments suggested that microbial reduction was responsible for ClO4-depletion in stream sediments. Biodegradation of ClO4-occurred over a seasonally variable active depth zone of 1-10 cm. Results implied that there was a rapid natural attenuation potential of perchlorate in saturated near-surface sediments. -Perchlorate may be rapidly attenuated in saturated near-surface sediments

  8. Pb(II)-promoted amide cleavage: mechanistic comparison to a Zn(II) analogue.

    Science.gov (United States)

    Elton, Eric S; Zhang, Tingting; Prabhakar, Rajeev; Arif, Atta M; Berreau, Lisa M

    2013-10-01

    Two new Pb(II) complexes of the amide-appended nitrogen/sulfur epppa (N-((2-ethylthio)ethyl)-N-((6-pivaloylamido-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine) chelate ligand, [(epppa)Pb(NO3)2] (4-NO3) and [(epppa)Pb(ClO4)2] (4-ClO4), were prepared and characterized. In the solid state, 4-NO3 exhibits κ(5)-epppa chelate ligand coordination as well as the coordination of two bidentate nitrate ions. In acetonitrile, 4-NO3 is a 1:1 electrolyte with a coordinated NO3(-), whereas 4-ClO4 is a 1:2 electrolyte. Treatment of 4-ClO4 with 1 equiv Me4NOH·5H2O in CH3CN:CH3OH (3:5) results in amide methanolysis in a reaction that is akin to that previously reported for the Zn(II) analogue [(epppa)Zn](ClO4)2 (3-ClO4). (1)H NMR kinetic studies of the amide methanolysis reactions of 4-ClO4 and 3-ClO4 as a function of temperature revealed free energies of activation of 21.3 and 24.5 kcal/mol, respectively. The amide methanolysis reactions of 4-ClO4 and 3-ClO4 differ in terms of the effect of the concentration of methanol (saturation kinetics for 4-ClO4; second-order behavior for 3-ClO4), the observation of a small solvent kinetic isotope effect (SKIE) only for the reaction of the Zn(II)-containing 3-ClO4, and the properties of an initial intermediate isolated from each reaction upon treatment with Me4NOH·5H2O. These experimental results, combined with computational studies of the amide methanolysis reaction pathways of 4-ClO4 and 3-ClO4, indicate that the Zn(II)-containing 3-ClO4 initially undergoes amide deprotonation upon treatment with Me4NOH·5H2O. Subsequent amide protonation from coordinated methanol yields a structure containing a coordinated neutral amide and methoxide anion from which amide cleavage can then proceed. The rate-determining step in this pathway is either amide protonation or protonation of the leaving group. The Pb(II)-containing 4-ClO4 instead directly forms a neutral amide-containing, epppa-ligated Pb(II)-OH/Pb(II)-OCH3 equilibrium mixture upon treatment with Me4NOH·5H2O in methanol. The rate-determining step in the amide methanolysis pathway of 4-ClO4 is nucleophilic attack of the Pb(II)-OCH3 moiety on the coordinated amide. Overall, it is the larger size of the Pb(II) center and the availability of coordination positions that enable direct formation of a Pb(II)-OH/Pb(II)-OCH3 mixture versus the initial amide deprotonation identified in the reaction of the Zn(II)-containing 3-ClO4. PMID:24066688

  9. Close Columnar Packing of Triangulenium Ions in Langmuir Films

    DEFF Research Database (Denmark)

    Simonsen, Jens B.; Kjær, Kristian; Howes, Paul;

    2009-01-01

    (GIXD). Compounds 5a center dot PF6 and 5b center dot PF6 both self-assemble into 2D-crystalline Langmuir monolayers, in which the planar triangular shaped carbenium ions form columnar aggregates segregated from the PF6- ions. The column width is found to be close to the width of the triangulenium......Three new tris(dialkylamino)trioxatriangulenium (ATOTA(+)) salts rendered amphiphilic by attachment of two (5a center dot PF6 and 5b center dot PF6) or four (5c center dot PF6) n-decyl chains have been synthesized, and their Langmuir films have been studied by grazing incidence X-ray diffraction...

  10. The electrochemistry of arylated anthraquinones in room temperature ionic liquids

    OpenAIRE

    Gomis Berenguer, Alicia; Gómez Mingot, María; García Cruz, Leticia; Thiemann, Thies; Banks, Craig E.; Montiel Leguey, Vicente; Iniesta Valcárcel, Jesús

    2013-01-01

    Arylated anthraquinone derivatives of different sizes and different π-basicities have been prepared, and the electrochemical behaviour of these substances has been studied on screen printed graphite electrodes in the three room temperature ionic liquids (RTILs), 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM][PF6]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6MIM][PF6]) and 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]). Half redox potentials for the first and...

  11. The base-catalyzed H/D--exchange of anisole moiety of ruthenium complex in cooperation with demethylation by hydroxide anion in methanol-d4

    International Nuclear Information System (INIS)

    [Ru (η5-C5H5)(η6-arene A)]BF4 (arene A = nitrobenzene, m- or p-nitrotoluene, anisole, phenetole, m- or p-methylanisole) were quantitatively converted to pure [Ru(η5-C5H5)(η-arene B)]BF4 (arene B = phenoxido-2d, m- or p-monodeuterated methylphenoxido) in the presence of excess KOH in CD3OD, whereas [Ru(η5-C5H5)(η6-anisole)]BF4 was quantitatively obtained by treatment [Ru(η5-C5H5)(η6-nitrobenzene)]BF4 with 1 equivalent KOH or CH3OK. (author)

  12. Fluorescence quenching of coumarin 153 by hydroxyl-functionalized room temperature ionic liquids.

    Science.gov (United States)

    Li, Shuang; Yu, Anchi; Lu, Rong

    2016-08-01

    Steady-state absorption and fluorescence as well as time-resolved fluorescence of coumarin 151 (C151) and coumarin 153 (C153) were measured in hydroxyl-functionalized ionic liquids ([HOEmim][BF4] and [HOEmim][N(CN)2]) and in nonhydroxyl-functionalized ionic liquids ([Emim][BF4] and [Emim][N(CN)2]). Both the steady-state fluorescence and time-resolved fluorescence observations reveal that hydroxyl-functionalized ionic liquid quenches the fluorescence of C153 while the nonhydroxyl-functionalized ionic liquid does not. We also measured the time-resolved fluorescence anisotropy of C151 and C153 in both [HOEmim][BF4] and [Emim][BF4]. It is found that the ratio of the rotational relaxation lifetime of C153 in [HOEmim][BF4] with respect to that in [Emim][BF4] is about 15% larger than that of C151 in [HOEmim][BF4] with respect to that in [Emim][BF4], indicating extra interaction between C153 and [HOEmim][BF4] exists except the effect of the viscosity of ionic liquid. PMID:27153524

  13. Fluorescence quenching of coumarin 153 by hydroxyl-functionalized room temperature ionic liquids

    Science.gov (United States)

    Li, Shuang; Yu, Anchi; Lu, Rong

    2016-08-01

    Steady-state absorption and fluorescence as well as time-resolved fluorescence of coumarin 151 (C151) and coumarin 153 (C153) were measured in hydroxyl-functionalized ionic liquids ([HOEmim][BF4] and [HOEmim][N(CN)2]) and in nonhydroxyl-functionalized ionic liquids ([Emim][BF4] and [Emim][N(CN)2]). Both the steady-state fluorescence and time-resolved fluorescence observations reveal that hydroxyl-functionalized ionic liquid quenches the fluorescence of C153 while the nonhydroxyl-functionalized ionic liquid does not. We also measured the time-resolved fluorescence anisotropy of C151 and C153 in both [HOEmim][BF4] and [Emim][BF4]. It is found that the ratio of the rotational relaxation lifetime of C153 in [HOEmim][BF4] with respect to that in [Emim][BF4] is about 15% larger than that of C151 in [HOEmim][BF4] with respect to that in [Emim][BF4], indicating extra interaction between C153 and [HOEmim][BF4] exists except the effect of the viscosity of ionic liquid.

  14. Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate-Dimethylsulfoxide System

    Science.gov (United States)

    Gafurov, M. M.; Kirillov, S. A.; Gorobets, M. I.; Rabadanov, K. Sh.; Ataev, M. B.; Tretyakov, D. O.; Aydemirov, K. M.

    2015-01-01

    The phase diagram and electrical conductivity isotherms for the lithium tetrafluoroborate (LiBF4)-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF4-DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF4 - ions were found. The bonds of Li+ ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τω values for DMSO molecules in the Li+-ion solvate shell of the LiBF4-DMSO system were similar to those for associated solvent molecules.

  15. Theoretical insights into the properties of amino acid ionic liquids in aqueous solution.

    Science.gov (United States)

    Zhu, Xueying; Ai, Hongqi

    2016-07-01

    This report presents a systematic investigation of the interactions of water molecule(s) with a series of amino acid cations (Gly(+), Ala(+), Val(+), and Leu(+)), halogen anions (Cl(-), Br(-), BF4 (-), and PF6 (-)), and clusters (GlyCl) n (n = 1-5). The results reveal that H-bonds between amino acid ionic liquids (AAILs) and water molecules are crucial to the properties of aqueous solution of AAILs. The properties of AAIL in water solution depend on the alkyl chain of the amino acid cation, the size of the halogen anion, and the number of water molecules, which provides a certain theoretical basis for the design and application of new AAILs. A series of calculations for some different models showed that quadruple-GlyCl hydrate represents a basic unit for the Gly-water binary system, and can be employed as the simplest model for studying an AAIL-water cluster. On the basis of this model, the effects of water on the hygroscopicity, speed of solubility, viscosity, density, solution enthalpy, and polarity of the AAIL were also predicted. Most importantly, unlike traditional ILs, the novel GlyCl-type AAIL favors interaction of its cationic part, rather than its anionic part, with surrounding water molecules, thus amino acid cationic ILs expand the types of IL available, increasing the choice of ILs for different purposes. We hope that the application of this AAIL in many fields will lead to optimization of this class of compound and be of benefit to the environment. Graphical Abstract Quadruple-GlyCl hydrate represents the basic unit for a GlyCl-water binary system, which can be employed as the simplest model for studying an amino acid ionic liquid (AAIL)-water cluster. The effects of available water on some properties of AAIL are predicted. GlyCl-type AAIL is a novel IL, which prefers its cationic part over its anionic part for interaction with surrounding water molecules. The properties of AAIL in water solution can be adjusted by varying the ion used and the

  16. Ionic liquids for nano- and microstructures preparation. Part 2: Application in synthesis.

    Science.gov (United States)

    Łuczak, Justyna; Paszkiewicz, Marta; Krukowska, Anna; Malankowska, Anna; Zaleska-Medynska, Adriana

    2016-01-01

    Ionic liquids (ILs) are widely applied to prepare metal nanoparticles and 3D semiconductor microparticles. Generally, they serve as a structuring agent or reaction medium (solvent), however it was also demonstrated that ILs can play a role of a co-solvent, metal precursor, reducing as well as surface modifying agent. The crucial role and possible types of interactions between ILs and growing particles have been presented in the Part 1 of this review paper. Part 2 of the paper gives a comprehensive overview of recent experimental studies dealing with application of ionic liquids for preparation of metal and semiconductor based nano- and microparticles. A wide spectrum of preparation routes using ionic liquids is presented, including precipitation, sol-gel technique, hydrothermal method, nanocasting and ray-mediated methods (microwave, ultrasound, UV-radiation and γ-radiation). It was found that ionic liquids formed of a 1-butyl-3-methylimidazolium [BMIM] combined with tetrafluoroborate [BF4], hexafluorophosphate [PF6], and bis(trifluoromethanesulfonyl)imide [Tf2N] are the most often used ILs in the synthesis of nano- and microparticles, due to their low melting temperature, low viscosity and good transportation properties. Nevertheless, examples of other IL classes with intrinsic nanoparticles stabilizing abilities such as phosphonium and ammonium derivatives are also presented. Experimental data revealed that structure of ILs (both anion and cation type) affects the size and shape of formed metal particles, and in some cases may even determine possibility of particles formation. The nature of the metal precursor determines its affinity to polar or nonpolar domains of ionic liquid, and therefore, the size of the nanoparticles depends on the size of these regions. Ability of ionic liquids to form varied extended interactions with particle precursor as well as other compounds presented in the reaction media (water, organic solvents etc.) provides nano- and

  17. Local Structure in Terms of Nearest-Neighbor Approach in 1-Butyl-3-methylimidazolium-Based Ionic Liquids: MD Simulations.

    Science.gov (United States)

    Marekha, Bogdan A; Koverga, Volodymyr A; Chesneau, Erwan; Kalugin, Oleg N; Takamuku, Toshiyuki; Jedlovszky, Pál; Idrissi, Abdenacer

    2016-06-01

    Description of the local microscopic structure in ionic liquids (ILs) is a prerequisite to obtain a comprehensive understanding of the influence of the nature of ions on the properties of ILs. The local structure is mainly determined by the spatial arrangement of the nearest neighboring ions. Therefore, the main interaction patterns in ILs, such as cation-anion H-bond-like motifs, cation-cation alkyl tail aggregation, and ring stacking, were considered within the framework of the nearest-neighbor approach with respect to each particular interaction site. We employed classical molecular dynamics (MD) simulations to study in detail the spatial, radial, and orientational relative distribution of ions in a set of imidazolium-based ILs, in which the 1-butyl-3-methylimidazolium (C4mim(+)) cation is coupled with the acetate (OAc(-)), chloride (Cl(-)), tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)), trifluoromethanesulfonate (TfO(-)), or bis(trifluoromethanesulfonyl)amide (TFSA(-)) anion. It was established that several structural properties are strongly anion-specific, while some can be treated as universally applicable to ILs, regardless of the nature of the anion. Namely, strongly basic anions, such as OAc(-) and Cl(-), prefer to be located in the imidazolium ring plane next to the C-H(2/4-5) sites. By contrast, the other four bulky and weakly coordinating anions tend to occupy positions above/below the plane. Similarly, the H-bond-like interactions involving the H(2) site are found to be particularly enhanced in comparison with the ones at H(4-5) in the case of asymmetric and/or more basic anions (C4mimOAc, C4mimCl, C4mimTfO, and C4mimTFSA), in accordance with recent spectroscopic and theoretical findings. Other IL-specific details related to the multiple H-bond-like binding and cation stacking issues are also discussed in this paper. The secondary H-bonding of anions with the alkyl hydrogen atoms of cations as well as the cation-cation alkyl chain

  18. Derivation of structure-activity relationships from the anticancer properties of ruthenium(II) arene complexes with 2-aryldiazole ligands.

    Science.gov (United States)

    Martínez-Alonso, Marta; Busto, Natalia; Jalón, Félix A; Manzano, Blanca R; Leal, José M; Rodríguez, Ana M; García, Begoña; Espino, Gustavo

    2014-10-20

    The ligands 2-pyridin-2-yl-1H-benzimidazole (HL(1)), 1-methyl-2-pyridin-2-ylbenzimidazole (HL(2)), and 2-(1H-imidazol-2-yl)pyridine (HL(3)) and the proligand 2-phenyl-1H-benzimidazole (HL(4)) have been used to prepare five different types of new ruthenium(II) arene compounds: (i) monocationic complexes with the general formula [(η(6)-arene)RuCl(κ(2)-N,N-HL)]Y [HL = HL(1), HL(2), or HL(3); Y = Cl or BF4; arene = 2-phenoxyethanol (phoxet), benzene (bz), or p-cymene (p-cym)]; (ii) dicationic aqua complexes of the formula [(η(6)-arene)Ru(OH2)(κ(2)-N,N-HL(1))](Y)2 (Y = Cl or TfO; arene = phoxet, bz, or p-cym); (iii) the nucleobase derivative [(η(6)-arene)Ru(9-MeG)(κ(2)-N,N-HL(1))](PF6)2 (9-MeG = 9-methylguanine); (iv) neutral complexes consistent with the formulation [(η(6)-arene)RuCl(κ(2)-N,N-L(1))] (arene = bz or p-cym); (v) the neutral cyclometalated complex [(η(6)-p-cym)RuCl(κ(2)-N,C-L(4))]. The cytototoxic activity of the new ruthenium(II) arene compounds has been evaluated in several cell lines (MCR-5, MCF-7, A2780, and A2780cis) in order to establish structure-activity relationships. Three of the compounds with the general formula [(η(6)-arene)RuCl(κ(2)-N,N-HL(1))]Cl differing in the arene moiety have been studied in depth in terms of thermodynamic dissociation constants, aquation kinetic constants, and DNA binding measurements. The biologically most active compound is the p-cym derivative, which strongly destabilizes the DNA double helix, whereas those with bz and phoxet have only a small effect on the stability of the DNA double helix. Moreover, the inhibitory activity of several compounds toward CDK1 has also been evaluated. The DNA binding ability of some of the studied compounds and their CDK1 inhibitory effect suggest a multitarget mechanism for their biological activity. PMID:25302401

  19. Global patterns and environmental controls of perchlorate and nitrate co-occurrence in arid and semi-arid environments

    Science.gov (United States)

    Jackson, W. Andrew; Böhlke, J. K.; Andraski, Brian J.; Fahlquist, Lynne; Bexfield, Laura; Eckardt, Frank D.; Gates, John B.; Davila, Alfonso F.; McKay, Christopher P.; Rao, Balaji; Sevanthi, Ritesh; Rajagopalan, Srinath; Estrada, Nubia; Sturchio, Neil; Hatzinger, Paul B.; Anderson, Todd A.; Orris, Greta; Betancourt, Julio; Stonestrom, David; Latorre, Claudio; Li, Yanhe; Harvey, Gregory J.

    2015-09-01

    Natural perchlorate (ClO4-) is of increasing interest due to its wide-spread occurrence on Earth and Mars, yet little information exists on the relative abundance of ClO4- compared to other major anions, its stability, or long-term variations in production that may impact the observed distributions. Our objectives were to evaluate the occurrence and fate of ClO4- in groundwater and soils/caliche in arid and semi-arid environments (southwestern United States, southern Africa, United Arab Emirates, China, Antarctica, and Chile) and the relationship of ClO4- to the more well-studied atmospherically deposited anions NO3- and Cl- as a means to understand the prevalent processes that affect the accumulation of these species over various time scales. ClO4- is globally distributed in soil and groundwater in arid and semi-arid regions on Earth at concentrations ranging from 10-1 to 106 μg/kg. Generally, the ClO4- concentration in these regions increases with aridity index, but also depends on the duration of arid conditions. In many arid and semi-arid areas, NO3- and ClO4- co-occur at molar ratios (NO3-/ClO4-) that vary between ∼104 and 105. We hypothesize that atmospheric deposition ratios are largely preserved in hyper-arid areas that support little or no biological activity (e.g. plants or bacteria), but can be altered in areas with more active biological processes including N2 fixation, N mineralization, nitrification, denitrification, and microbial ClO4- reduction, as indicated in part by NO3- isotope data. In contrast, much larger ranges of Cl-/ClO4- and Cl-/NO3- ratios indicate Cl- varies independently from both ClO4- and NO3-. The general lack of correlation between Cl- and ClO4- or NO3- implies that Cl- is not a good indicator of co-deposition and should be used with care when interpreting oxyanion cycling in arid systems. The Atacama Desert appears to be unique compared to all other terrestrial locations having a NO3-/ClO4- molar ratio ∼103. The relative enrichment in ClO4- compared to Cl- or NO3- and unique isotopic composition of Atacama ClO4- may reflect either additional in-situ production mechanism(s) or higher relative atmospheric production rates in that specific region or in the geological past. Elevated concentrations of ClO4- reported on the surface of Mars, and its enrichment with respect to Cl- and NO3-, could reveal important clues regarding the climatic, hydrologic, and potentially biologic evolution of that planet. Given the highly conserved ratio of NO3-/ClO4- in non-biologically active areas on Earth, it may be possible to use alterations of this ratio as a biomarker on Mars and for interpreting major anion cycles and processes on both Mars and Earth, particularly with respect to the less-conserved NO3- pool terrestrially.

  20. ANALYSIS OF HYDROPONIC FERTILIZER MATRIXES FOR PERCHLORATE: COMPARISON OF ANALYTICAL TECHNIQUES

    Science.gov (United States)

    Seven retail hydroponic nitrate fertilizer products, two liquid and five solid, were comparatively analyzed for the perchlorate anion (ClO4-) by ion chromatography (IC) with suppressed conductivity detection, complexation electrospray ionization mass spectrometry (cESI-MS), norma...

  1. Soil, plant, and terrain effects on natural perchlorate distribution in a desert landscape

    Science.gov (United States)

    Andraski, Brian J.; Jackson, W.A.; Welborn, Toby L.; Böhlke, John Karl; Sevanthi, Ritesh; Stonestrom, David A.

    2014-01-01

    Perchlorate (ClO4−) is a contaminant that occurs naturally throughout the world, but little is known about its distribution and interactions in terrestrial ecosystems. The objectives of this Amargosa Desert, Nevada study were to determine (i) the local-scale distribution of shallow-soil (0–30 cm) ClO4− with respect to shrub proximity (far and near) in three geomorphic settings (shoulder slope, footslope, and valley floor); (ii) the importance of soil, plant, and terrain variables on the hillslope-distribution of shallow-soil and creosote bush [Larrea tridentata (Sessé & Moc. ex DC.) Coville] ClO4−; and (iii) atmospheric (wet plus dry, including dust) deposition of ClO4− in relation to soil and plant reservoirs and cycling. Soil ClO4− ranged from 0.3 to 5.0 μg kg−1. Within settings, valley floor ClO4− was 17× less near shrubs due in part to enhanced leaching, whereas shoulder and footslope values were ∼2× greater near shrubs. Hillslope regression models (soil, R2 = 0.42; leaf, R2 = 0.74) identified topographic and soil effects on ClO4− deposition, transport, and cycling. Selective plant uptake, bioaccumulation, and soil enrichment were evidenced by leaf ClO4− concentrations and Cl−/ClO4− molar ratios that were ∼8000× greater and 40× less, respectively, than soil values. Atmospheric deposition ClO4− flux was 343 mg ha−1 yr−1, ∼10× that for published southwestern wet-deposition fluxes. Creosote bush canopy ClO4− (1310 mg ha−1) was identified as a previously unrecognized but important and active reservoir. Nitrate δ18O analyses of atmospheric deposition and soil supported the leaf-cycled–ClO4− input hypothesis. This study provides basic data on ClO4− distribution and cycling that are pertinent to the assessment of environmental impacts in desert ecosystems and broadly transferable to anthropogenically contaminated systems.

  2. Perchlorate in pleistocene and holocene groundwater in North-Central New Mexico

    Science.gov (United States)

    Plummer, L.N.; Böhlke, J.K.; Doughten, M.W.

    2006-01-01

    Groundwater from remote parts of the Middle Rio Grande Basin in north-central New Mexico has perchlorate (ClO4-) concentrations of 0.12-1.8 ??g/L Because the water samples are mostly preanthropogenic in age (0-28 000 years) and there are no industrial sources in the study area, a natural source of the ClO4- is likely. Most of the samples have Br-, Cl-, and SO42- concentrations that are similar to those of modern bulk atmospheric deposition with evapotranspiration (ET) factors of about 7-40. Most of the ET values for Pleistocene recharge were nearly twice that for Holocene recharge. The NO3-/Cl- and ClO4-/Cl- ratios are more variable than those of Br -/Cl- or SO42-/Cl-. Samples thought to have recharged under the most arid conditions in the Holocene have relatively high NO3-/Cl- ratios and low ??15N values (+1 per mil (???)) similar to those of modern bulk atmospheric N deposition. The ??18O values of the NO 3- (-4 to 0 ???) indicate that atmospheric N0 3- was not transmitted directly to the groundwater but may have been cycled in the soils before infiltrating. Samples with nearly atmospheric NO3-/Cl- ratios have relatively high ClO4- concentrations (1.0-1.8 ??g/L) with a nearly constant ClO4-/Cl- mole ratio of (1.4 ?? 0.1) ?? 10-4, which would be consistent with an average ClO 4- concentration of 0.093 ?? 0.005 ??g/L in bulk atmospheric deposition during the late Holocene in north-central NM. Samples thought to have recharged underwetter conditions have higher ??15N values (+3 to +8 ???), lower N03-/Cl- ratios, and lower ClO4-/Cl- ratios than the ones most likely to preserve an atmospheric signal. Processes in the soils that may have depleted atmospherically derived NO3- also may have depleted ClO4- to varying degrees prior to recharge. If these interpretations are correct, then ClO4- concentrations of atmospheric origin as high as 4 ??g/L are possible in preanthropogenic groundwater in parts of the Southwest where ET approaches a factor of 40. Higher ClO4- concentrations in uncontaminated groundwater could occur in recharge beneath arid areas where ET is greater than 40, where long-term accumulations of atmospheric salts are leached suddenly from dry soils, or where other (nonatmospheric) natural sources of ClO/4- exist.

  3. Manganese (III) cyclam complexes with aqua, iodo, nitrito, perchlorato and acetic acid/acetato axial ligands

    DEFF Research Database (Denmark)

    Mossin, Susanne; Sørensen, Henning Osholm; Weihe, Høgni;

    2005-01-01

    The syntheses, structures and magnetic properties of five new manganese (III) cyclam complexes, trans-[Mn(cyclam)(OH2)(2)]-(CF3SO3)(3)center dot-H2O, trans-[Mn(cyclam)I-2]I, trans-[Mn(cyclam)(ONO)(2)]ClO4, trans-[Mn(cyclam)(OClO3)(2)]ClO4 and trans-[Mn(cyclam) (CH3COO)(CH3COOH)](ClO4)(2), are rep...

  4. Analysis of Redox Series of Unsymmetrical 1,4-Diamido-9,10-anthraquinone-Bridged Diruthenium Compounds.

    Science.gov (United States)

    Mandal, Abhishek; Hoque, Md Asmaul; Grupp, Anita; Paretzki, Alexa; Kaim, Wolfgang; Lahiri, Goutam Kumar

    2016-03-01

    The unsymmetrical diruthenium complexes [(bpy)2Ru(II)(μ-H2L(2-))Ru(III)(acac)2]ClO4 ([3]ClO4), [(pap)2RuII(μ-H2L(2-))Ru(III)(acac)2]ClO4 ([4]ClO4), and [(bpy)2Ru(II)(μ-H2L(2-))Ru(II)(pap)2](ClO4)2 ([5](ClO4)2) have been obtained by way of the mononuclear precursors [(bpy)2Ru(II)(H3L(-))]ClO4 ([1]ClO4) and [(pap)2Ru(II)(H3L(-))]ClO4 ([2]ClO4) (where bpy = 2,2′-bipyridine, pap = 2-phenylazopyridine, acac(-) = 2,4-pentanedionate, and H4L = 1,4-diamino-9,10-anthraquinone). Structural characterization by single-crystal X-ray diffraction and magnetic resonance (nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR)) were used to establish the oxidation state situation in each of the isolated materials. Cyclic voltammetry, EPR, and ultraviolet-visible-near-infrared (UV-vis-NIR) spectroelectrochemistry were used to analyze the multielectron transfer series of the potentially class I mixed-valent dinuclear compounds, considering the redox activities of differently coordinated metals, of the noninnocent bridge and of the terminal ligands. Comparison with symmetrical analogues [L2′Ru(μ-H2L)RuL2′](n) (where L′ = bpy, pap, or acac(-)) shows that the redox processes in the unsymmetrical dinuclear compounds are not averaged, with respect to the corresponding symmetrical systems, because of intramolecular charge rearrangements involving the metals, the noninnocent bridge, and the ancillary ligands. PMID:26887785

  5. Blends of lithium bis(oxalato)borate and lithium tetrafluoroborate: Useful substitutes for lithium difluoro(oxalato)borate in electrolytes for lithium metal based secondary batteries?

    International Nuclear Information System (INIS)

    Highlights: • Stability studies at salts with the difluoro(oxalato)borate anion show that ligand exchange occurs under thermal stress at 60 °C. • NMR measurements at solutions of LiBOB/LiBF4 blend electrolytes show that ligand exchange occurs in solutions at room temperature as well. • Formation of traces of LiDFOB in LiBOB/LiBF4 blend electrolytes is responsible for the favorable SEI and excellent lithium cycling. • SEI compositions of blend electrolytes became more similar to the SEI composition of the LiDFOB-based electrolyte with increasing LiBF4 content. • LiBOB/LiBF4 blend electrolytes show a superior lithium cycling performance compared to single salts nearly reaching the performance of LiDFOB based electrolytes. -- Abstract: This work was inspired by the observation that some borates exchange their ligands that are attached to boron. Therefore, we investigated the effect of blends of two salts, lithium bis(oxalato)borate (LiBOB), lithium tetrafluoroborate (LiBF4) on lithium cycling on copper with solutions based on ethylene carbonate (EC) and diethyl carbonate (DEC) (3:7, by wt.). Coulombic efficiencies of dissolution rate (D-rate) tests demonstrated an enhanced performance of LiBOB/LiBF4 blend electrolytes compared to the LiBOB-based and LiBF4-based electrolytes, increasing with increasing LiBF4 content. The coulombic efficiencies of the LiBOB/LiBF4 blend electrolyte with highest LiBF4 content reached almost the coulombic efficiencies of the lithium difluoro(oxalato)borate (LiDFOB) based electrolyte at high current densities in D-rate tests. Voltage drop values, conductivity measurements, and AC impedance measurements show the good performance of the LiBOB/LiBF4 blend electrolytes. The composition of the solid electrolyte interphase (SEI) of the LiBOB/LiBF4 blend electrolytes studied by X-ray photoelectron spectroscopy (XPS) becomes more similar to the composition of the SEI of the LiDFOB-based electrolyte with increasing LiBF4 content. Nuclear

  6. Evidence of water-in-ionic liquid microemulsion formation by nonionic surfactant Brij-35.

    Science.gov (United States)

    Rai, Rewa; Pandey, Siddharth

    2014-09-01

    Brij-35, a common and popular nonionic surfactant, is shown to form water-in-ionic liquid (w/IL) microemulsions with IL 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) as the bulk phase. The presence of w/[bmim][PF6] microemulsions is hinted by the significantly increased solubility of water in Brij-35 solution of [bmim][PF6]. The formation of w/[bmim][PF6] microemulsions by Brij-35 is confirmed using dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) measurements. Brij-35 forms reverse micelle-type aggregates within [bmim][PF6] in the absence of added-water. These reverse micelles become w/[bmim][PF6] microemulsions as the water is added to the system. As the water loading (w0) is increased, the average diameter of the aggregates increases. Fourier transform infrared (FTIR) absorbance data reveal the presence of both "bound" and "free" water within the system. The "bound" water is associated with the water pools of the w/[bmim][PF6] microemulsions. Excited-state proton transfer (ESPT) involving probe pyranine shows deprotonation of pyranine within the water pools of the w/[bmim][PF6] microemulsions. PMID:25121578

  7. Raman and ab initio studies of simple and binary 1-alkyl-3-methylimidazolium ionic liquids

    DEFF Research Database (Denmark)

    Berg, R.W.; Deetlefs, M.; Seddon, K.R.;

    2005-01-01

    Raman spectra of the ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim][PF6]), 1-hexyl-3-methylimidazolium chloride ([C(6)mim]Cl), and 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)mim][PF6]), and binary mixtures thereof, have been assigned using ab initio MP2...

  8. 二茂铁四氟硼酸盐用作潜热阳离子引发剂对环氧树脂的热固化引发环氧化合物阳离子热聚合%Novel Ferricenium Tetrafluoroborate Salt as Latent Thermal Cationic Initiator for Curing of Epoxy Resins

    Institute of Scientific and Technical Information of China (English)

    王涛; 王志华; 刘金萍

    2004-01-01

    A novel latent thermal initiator, ferricenium tetrafiuoroborate salt (FcBF4), for cationic polymerization of epoxides is reported. The activities of FcBF4 for different epoxides, including bisphenol-A-type epoxy oligomer E44, cycloaliphatic epoxy ERL4221, and glycidylether epoxy GGE, were evaluated by differential scanning calorimetry (DSC). The results showed a moderate thermal initiation activity for E44 and GGE at 78℃ and 108℃respectively. When adding GGE to E44, the reaction was enhanced. The temperature of thermal degradation of the cured specimens for the system of E44/FcBF4, E44+10%GGE/FcBF4 and E44+10%ERL4221/FcBF4 is higher than 350℃.

  9. Novel Ferricenium Tetrafluoroborate Salt as Latent Thermal Cationic Initiator for Curing of Epoxy Resins

    Institute of Scientific and Technical Information of China (English)

    王涛; 王志华; 刘金萍

    2004-01-01

    A novel latent thermal initiator, ferricenium tetrafluoroborate salt (FcBF4), for cationic polymerization of epoxides is reported. The activities of FcBF4 for different epoxides, including bisphenol-A-type epoxy oligomer E44, cycloaliphatic epoxy ERL4221, and glycidylether epoxy GGE, were evaluated by differential scanning calorimetry (DSC). The results showed a moderate thermal initiation activity for E44 and GGE at 78℃ and 108℃ respectively. When adding GGE to E44, the reaction was enhanced. The temperature of thermal degradation of the cured specimens for the system of E44/FcBF4, E44+10%GGE/FcBF4 and E44+10%ERL4221/FcBF4 is higher than 350℃.

  10. Syntheses, characterizations and structures of cadmium(II) and zinc(II) pseudohalide complexes containing pyridylpyrazole ligand

    International Nuclear Information System (INIS)

    The details of syntheses, characterizations and structures of cadmium(II) and zinc(II) pseudohalide complexes of the types (M(L)(NCS)2), (M(L)(N3)PF6, (Zn(L)(NCO)PF6 and (Cd(L)(NCO)2)(PF6)2 (1-6) (M = CdII and ZnII; L = N,N-bis(3,5-dimethylpyrazol-1-ylmethyl)aminomethylpyridine) are described. All the complexes are characterized using their spectroscopic and other physicochemical results. Crystal structures of (Cd(L)(NCO))2(PF6)2 (3) and (Zn(L)(N3))PF6 (5) have been solved by single crystal X-ray diffraction measurements. Each metal center in binuclear compound 3 has double NCO- bridged distorted octahedral structure whereas in mononuclear compound 5 adopts a distorted trigonal bipyramidal geometry. (author)

  11. Electron donors and co-contaminants affect microbial community composition and activity in perchlorate degradation.

    Science.gov (United States)

    Guan, Xiangyu; Xie, Yuxuan; Wang, Jinfeng; Wang, Jing; Liu, Fei

    2015-04-01

    Although microbial reduction of perchlorate (ClO4(-)) is a promising and effective method, our knowledge on the changes in microbial communities during ClO4(-) degradation is limited, especially when different electron donors are supplied and/or other contaminants are present. Here, we examined the effects of acetate and hydrogen as electron donors and nitrate and ammonium as co-contaminants on ClO4(-) degradation by anaerobic microcosms using six treatments. The process of degradation was divided into the lag stage (SI) and the accelerated stage (SII). Quantitative PCR was used to quantify four genes: pcrA (encoding perchlorate reductase), cld (encoding chlorite dismutase), nirS (encoding copper and cytochrome cd1 nitrite reductase), and 16S rRNA. While the degradation of ClO4(-) with acetate, nitrate, and ammonia system (PNA) was the fastest with the highest abundance of the four genes, it was the slowest in the autotrophic system (HYP). The pcrA gene accumulated in SI and played a key role in initiating the accelerated degradation of ClO4(-) when its abundance reached a peak. Degradation in SII was primarily maintained by the cld gene. Acetate inhibited the growth of perchlorate-reducing bacteria (PRB), but its effect was weakened by nitrate (NO3(-)), which promoted the growth of PRB in SI, and therefore, accelerated the ClO4(-) degradation rate. In addition, ammonia (NH4(+)), as nitrogen sources, accelerated the growth of PRB. The bacterial communities' structure and diversity were significantly affected by electron donors and co-contaminants. Under heterotrophic conditions, both ammonia and nitrate promoted Azospira as the most dominant genera, a fact that might significantly influence the rate of ClO4(-) natural attenuation by degradation. PMID:25382499

  12. Formation of gold decorated porphyrin nanoparticles and evaluation of their photothermal and photodynamic activity.

    Science.gov (United States)

    Chen, Ruey-Juen; Chen, Po-Chung; Prasannan, Adhimoorthy; Vinayagam, Jayaraman; Huang, Chun-Chiang; Chou, Peng-Yi; Weng, Cheng-Chih; Tsai, Hsieh Chih; Lin, Shuian-Yin

    2016-06-01

    A core-shell gold (Au) nanoparticle with improved photosensitization have been successfully fabricated using Au nanoparticles and 5,10,15,20 tetrakis pentafluorophenyl)-21H,23H-porphine (PF6) dye, forming a dyad through molecular self-assembly. Au nanoparticles were decorated on the shell and PF6 was placed in the core of the nanoparticles. Highly stable Au nanoparticles were achieved using PF6 with poly(N-vinylcaprolactam-co-N-vinylimidazole)-g-poly(d,l-lactide) graft copolymer hybridization. This was compared with hybridization using cetyltrimethylammonium bromide and polyethylene glycol-b-poly(d,l-lactide) for shell formation with PF6-Au. The resulting PF6-poly(N-vinylcaprolactam-co-N-vinylimidazole)-g-poly(d,l-lactide)-Au core-shell nanoparticle were utilized for photothermal and photodynamic activities. The spectroscopic analysis and zeta potential values of micelles revealed the presence of a thin Au layer coated on the PF6 nanoparticle surface, which generally enhanced the thermal stability of the gold nanoparticles and the photothermal effect of the shell. The core-shell PF6-Au nanoparticles were avidly taken up by cells and demonstrated cellular phototoxicity upon irradiation with 300W halogen lamps. The structural arrangement of PF6 dyes in the core-shell particles assures the effectiveness of singlet oxygen production. The study verifies that PF6 particles when companied with Au nanoparticles as PF6-Au have possible combinational applications in photodynamic and photothermal therapies for cancer cells because of their high production of singlet oxygen and heat. PMID:27040265

  13. A Colorimetric Bioassay for Perchlorate

    Science.gov (United States)

    Heinnickel, M. L.; Smith, S.; Coates, J. D.

    2007-12-01

    Recognition of perchlorate (ClO4-) as a widespread contaminant across the United States and its potential adverse affects towards human health has motivated the EPA to place ClO4- on its contaminant candidate list for drinking water supplies. While a federal MCL has not yet been set, a recommended public health goal of 1 ppb (μg.L-1) was established by the US EPA in 2002. To date, methods of detection require use of sensitive ion chromatographic equipment that are expensive, time consuming, and require highly trained personnel for use. Our studies are focused on the development of a highly sensitive, simple, and robust colorimetric bioassay based on the primary enzyme involved in microbial ClO4- reduction, the perchlorate reductase (Pcr). A previously published assay used reduced methyl viologen (MV, the dye is reduced with sodium hydrosulfite) as an electron donor to demonstrate Pcr activity. The assay directly correlates the amount of MV oxidized with the amount of ClO4- reduced by assuming a transfer of four electrons. To test this assumption, we compared actual concentrations of MV oxidized to ClO4- reduced in this assay. ClO4- concentrations were determined using a Dionex ICS-500 ion chromatography system, while MV concentrations were determined using a standard curve generated at 578 nm. Comparisons between the two revealed that twelve molecules of MV were oxidized for each molecule of ClO4- reduced. The oxidation of these additional eight MV molecules is explained by the interaction of the dye with chlorite (the product of the Pcr reaction) and other contaminants that could be present in the enzyme prep. This unsettling result indicated this assay would be problematic for the detection of ClO4- in soil, which has many chemicals that could react with MV. To improve upon this assay, we have tried to reduce ClO4- using less reactive dyes and reductants. The reductants ascorbic acid, NADH, and dithiothreitol drive Pcr catalyzed ClO4- reduction, however, they are not effective unless an accompanying dye is used as a shuttle. N-methylphenazinium methosulfate (PMS) was selected as the most suitable dye because of its interaction with NADH, an oxygen stable reductant. In addition, the positive redox potential of PMS (E°' = +80 mV), makes it significantly less reactive than MV (E°' = -450 mV). A comparison of actual concentrations of ClO4- reduced vs. NADH oxidized show exactly four molecules of NADH oxidized for each molecule of ClO4- that is reduced (8 electrons). These studies have resulted in the successful development of a method that can accurately determine ClO4- concentrations with a small error using the enzyme Pcr and indicate the great potential for the ultimate development of a simple, robust, and highly sensitive colorimetric bioassay for perchlorate that can be widely used to screen laboratory and environmental samples .

  14. Study of microbial perchlorate reduction: Considering of multiple pH, electron acceptors and donors

    International Nuclear Information System (INIS)

    Graphical abstract: Schemes of perchlorate reduction in ClO4−/ClO3−–NO3− e−acceptor systems. - Highlights: • We created a multiple electron acceptor/donor system for ClO4− reduction. • Nitrate reduction was inhibited when using perchlorate-grown Azospira sp. KJ. • Reduction proceeded as an order of ClO3−, ClO4−and NO3−. • Oxidation of acetate was inhibited by succinate in acetate–succinate series. - Abstract: Bioremediation of perchlorate-cotaminated water by a heterotrophic perchlorate reducing bacterium creates a multiple electron acceptor-donor system. We experimentally determined the perchlorate reduction by Azospira sp. KJ at multiple pH, electron acceptors and donors systems; this was the aim of this study. Perchlorate reduction was drastically inhibited at the pH 6.0, and the maximum reduction of perchlorate by Azospira sp. KJ was observed at pH value of 8.0. Perchlorate reduction was retarded in ClO4−–ClO3−, ClO4−–ClO3−–NO3−,and ClO4−–NO3− acceptor systems, while being completely inhibited by the additional O2 in the ClO4−–O2 acceptor system. The reduction proceeded as an order of ClO3−, ClO4−, and NO3− in the ClO4−–ClO3−–NO3− system. KS,vmax, and qmax obtained at different e− acceptor and donor conditions are calculated as 140.5–190.6 mg/L, 8.7–13.2 mg-perchlorate/L-h, and 0.094–0.16 mg-perchlorate/mg-DW-h, respectively

  15. Ion Chromatographic Determination of low level Perchlorate in Natural Waters

    International Nuclear Information System (INIS)

    Perchlorate (ClO4-) is a persistent contaminant of drinking-, surface-, and ground-water, and of soils. Possible contributions of ClO4- contamination are the military, the space program, and supporting industries and fertilizers. Perchlorate has long been known to have a negative effect on the thyroid gland. It has been added to the United States Environmental Protection Agency's (EPA) Contaminant candidate List (CCL) in 1998, so that ClO4 can be regulated at a concentration safe to humans. This paper describes the determination of trace level ClO4- in various matrices utilizing ion chromatographic method. The method utilizes a Dionex IonPac AS11 column with suppressed conductivity detection, 1500ul sample loop, and a 100 mN NaOH eluent at a flow rate of 1.0ml/min. These parameters allow a method detection limit (MDL) of 0.277ug/1 and a short retention time of 8 minutes. A quality control, proficiency testing samples from the EPA and a number of environmental samples from New York State (ground water) and California (ground and surface waters) were analyzed by this technique. Concentrations measured were in the range of 1.9-217 ug/1. No evidence of ClO4- was found in various commonly used fertilizers. (author)

  16. Widespread occurrence of (per)chlorate in the Solar System

    Science.gov (United States)

    Jackson, W. Andrew; Davila, Alfonso F.; Sears, Derek W. G.; Coates, John D.; McKay, Christopher P.; Brundrett, Maeghan; Estrada, Nubia; Böhlke, J. K.

    2015-11-01

    Perchlorate (ClO4-) and chlorate (ClO3-) are ubiquitous on Earth and ClO4- has also been found on Mars. These species can play important roles in geochemical processes such as oxidation of organic matter and as biological electron acceptors, and are also indicators of important photochemical reactions involving oxyanions; on Mars they could be relevant for human habitability both in terms of in situ resource utilization and potential human health effects. For the first time, we extracted, detected and quantified ClO4- and ClO3- in extraterrestrial, non-planetary samples: regolith and rock samples from the Moon, and two chondrite meteorites (Murchison and Fayetteville). Lunar samples were collected by astronauts during the Apollo program, and meteorite samples were recovered immediately after their fall. This fact, together with the heterogeneous distribution of ClO4- and ClO3- within some of the samples, and their relative abundance with respect to other soluble species (e.g., NO3-) are consistent with an extraterrestrial origin of the oxychlorine species. Our results, combined with the previously reported widespread occurrence on Earth and Mars, indicate that ClO4- and ClO3- could be present throughout the Solar System.

  17. The effect of ionic liquid hydrophobicity and solvent miscibility on pluronic amphiphile self-assembly.

    Science.gov (United States)

    Sharma, Suraj Chandra; Atkin, Rob; Warr, Gregory G

    2013-11-21

    The phase behavior of the triblock copolymer, (EO)20(PO)70(EO)20 (P123), in the water-immiscible (hydrophobic) ionic liquids (ILs), 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6), and tris(pentafluoroethyl)trifluorophosphate (bmimFAP), has been investigated, and its amphiphilic self-assembly examined using small-angle X-ray scattering. The results obtained are contrasted with those for P123 in water. Direct and water-swellable micellar, hexagonal, and lamellar phases of P123 are found in bmimPF6, which behaves like a polar solvent despite being water immiscible, but bmimFAP behaves as a truly hydrophobic solvent, forming only a lamellar phase over a narrow composition range. The miscibility of bmimPF6 and water is increased by P123 addition, and at sufficiently high P123 concentrations, a single lamellar phase forms in which bmimPF6 and water are miscible in all proportions. In contrast, the preferential solubilization of bmimPF6 by PEO chains and bmimFAP by PPO chains causes the nanosegregation of these miscible ILs in concentrated P123 solutions. This leads to the formation of a P123/bmimPF6/bmimFAP microemulsion where bmimPF6 is the polar solvent and bmimFAP is the non-polar solvent. PMID:24138343

  18. Chemical Swarming: Depending on Concentration, an Amphiphilic Ruthenium Polypyridyl Complex Induces Cell Death via Two Different Mechanisms.

    Science.gov (United States)

    Siewert, Bianka; van Rixel, Vincent H S; van Rooden, Eva J; Hopkins, Samantha L; Moester, Miriam J B; Ariese, Freek; Siegler, Maxime A; Bonnet, Sylvestre

    2016-07-25

    The crystal structure and in vitro cytotoxicity of the amphiphilic ruthenium complex [3](PF6 )2 are reported. Complex [3](PF6 )2 contains a Ru-S bond that is stable in the dark in cell-growing medium, but is photosensitive. Upon blue-light irradiation, complex [3](PF6 )2 releases the cholesterol-thioether ligand 2 and an aqua ruthenium complex [1](PF6 )2 . Although ligand 2 and complex [1](PF6 )2 are by themselves not cytotoxic, complex [3](PF6 )2 was unexpectedly found to be as cytotoxic as cisplatin in the dark, that is, with micromolar effective concentrations (EC50 ), against six human cancer cell lines (A375, A431, A549, MCF-7, MDA-MB-231, and U87MG). Blue-light irradiation (λ=450 nm, 6.3 J cm(-2) ) had little influence on the cytotoxicity of [3](PF6 )2 after 6 h of incubation time, but it increased the cytotoxicity of the complex by a factor 2 after longer (24 h) incubation. Exploring the unexpected biological activity of [3](PF6 )2 in the dark elucidated an as-yet unknown bifaceted mode of action that depended on concentration, and thus, on the aggregation state of the compound. At low concentration, it acts as a monomer, inserts into the membrane, and can deliver [1](2+) inside the cell upon blue-light activation. At higher concentrations (>3-5 μm), complex [3](PF6 )2 forms supramolecular aggregates that induce non-apoptotic cell death by permeabilizing cell membranes and extracting lipids and membrane proteins. PMID:27373895

  19. Thermal stability of alkyl carbonate mixed-solvent electrolytes for lithium ion cells

    Science.gov (United States)

    Kawamura, Tetsuya; Kimura, Arihisa; Egashira, Minato; Okada, Shigeto; Yamaki, Jun-Ichi

    The thermal stability of some mixed-solvent electrolytes used in lithium cells was measured by differential scanning calorimetry (DSC) using airtight containers. The electrolytes used were ethylene carbonate ( EC)+ diethyl carbonate ( DEC) , EC+ dimethyl carbonate ( DMC) , propylene carbonate (PC)+DEC, and PC+DMC in which was dissolved 1 M LiPF 6 or 1 M LiClO 4. The influence of water addition and lithium metal addition on the thermal behavior of these electrolytes was also investigated. The exothermic peak of LiPF 6 electrolytes containing DEC was found at 255 °C, and the peak temperature of the electrolytes containing DEC was 15-20 °C lower than that of LiPF 6 electrolytes containing DMC. This effect was also observed in the electrolytes including LiClO 4. DMC was found to be more reactive than DEC. The thermal behavior of various kinds of LiPF 6 electrolytes with lithium metal was measured by DSC. The exothermic reaction of 1 M LiPF 6/EC+DEC, 1 M LiPF 6/EC+DMC, and 1 M LiPF 6/PC+DMC with lithium metal began at the melting point of lithium metal because of the break down of the solid electrolyte interface (SEI). The temperature was approximately 180 °C, whereas the self-heating of 1 M LiPF 6/PC+DEC occurred before the melting point of lithium metal. The temperature at which the self-exothermal reaction began was 140 °C. Therefore, the lithium metal in this electrolyte was found to be thermally unstable. When water was added to the above electrolytes with lithium metal, the exothermic reaction began at less than 130 °C, probably due to a collapse of SEI in response to the HF that was a product of the reaction between LiPF 6 and the added water.

  20. Synthesis and spectroscopic studies of silver and rhodium mono- and polynuclear complexes with multidentate phosphines (Ph2P)2CHR (R = H, Me, PPh2)

    NARCIS (Netherlands)

    Koten, G. van; Ploeg, A.F.M.J. van der

    1981-01-01

    Trinuclear [{(Ph{2}P){3}CH}Ag{3}(O{2}CR'){3}], dinuclear [{(Ph{2}P){2}CHR}Ag{2}(O{2}CR'){2}], [{(Ph{2}P){2}CHR}{2}Ag{2}](BF{4}){2} and (Rh{2}(Cl)(CO){2}{(Ph{2}P){2}CHMe}{2}][RhCl{2}(CO){2}], and mononuclear (Rh{(Ph{2}P){2}CHR}{2}](BF{4}), (Rh{(Ph{2}P){2}CHR}{2}HCl](BF{4}), d [Rh{(Ph{2}P){2}CHR}{2}Cl

  1. CALCULATION OF CONDUCTANCE FOR ORGANIC SOLUTIONS OF LITHIUM SALT USING MEAN SPHERICAL APPROXIMATION THEORY%应用平均球近似理论计算锂盐有机溶液电导率

    Institute of Scientific and Technical Information of China (English)

    韩景立

    2004-01-01

    The molar conductance of electrolytes LiPF6-PC (propylene carbonate), LiPF6·2DG (diglyme)-PC and LiPF6·PMDETA (pentamethy[diethylenetriamine)-PC were calculated by using mean spherical approximation(MSA). The range of concentration was from 0.001 mol·L-1 to 1 mol·L-1. The dissociation equilibrium of salts is taken into account. The mean relative deviations were 5.6%, 4.2% and 4.7%,respectively.

  2. A New Bioinspired Perchlorate Reduction Catalyst with Significantly Enhanced Stability via Rational Tuning of Rhenium Coordination Chemistry and Heterogeneous Reaction Pathway.

    Science.gov (United States)

    Liu, Jinyong; Han, Mengwei; Wu, Dimao; Chen, Xi; Choe, Jong Kwon; Werth, Charles J; Strathmann, Timothy J

    2016-06-01

    Rapid reduction of aqueous ClO4(-) to Cl(-) by H2 has been realized by a heterogeneous Re(hoz)2-Pd/C catalyst integrating Re(O)(hoz)2Cl complex (hoz = oxazolinyl-phenolato bidentate ligand) and Pd nanoparticles on carbon support, but ClOx(-) intermediates formed during reactions with concentrated ClO4(-) promote irreversible Re complex decomposition and catalyst deactivation. The original catalyst design mimics the microbial ClO4(-) reductase, which integrates Mo(MGD)2 complex (MGD = molybdopterin guanine dinucleotide) for oxygen atom transfer (OAT). Perchlorate-reducing microorganisms employ a separate enzyme, chlorite dismutase, to prevent accumulation of the destructive ClO2(-) intermediate. The structural intricacy of MGD ligand and the two-enzyme mechanism for microbial ClO4(-) reduction inspired us to improve catalyst stability by rationally tuning Re ligand structure and adding a ClOx(-) scavenger. Two new Re complexes, Re(O)(htz)2Cl and Re(O)(hoz)(htz)Cl (htz = thiazolinyl-phenolato bidentate ligand), significantly mitigate Re complex decomposition by slightly lowering the OAT activity when immobilized in Pd/C. Further stability enhancement is then obtained by switching the nanoparticles from Pd to Rh, which exhibits high reactivity with ClOx(-) intermediates and thus prevents their deactivating reaction with the Re complex. Compared to Re(hoz)2-Pd/C, the new Re(hoz)(htz)-Rh/C catalyst exhibits similar ClO4(-) reduction activity but superior stability, evidenced by a decrease of Re leaching from 37% to 0.25% and stability of surface Re speciation following the treatment of a concentrated "challenge" solution containing 1000 ppm of ClO4(-). This work demonstrates the pivotal roles of coordination chemistry control and tuning of individual catalyst components for achieving both high activity and stability in environmental catalyst applications. PMID:27182602

  3. Studies on 4-[N-(furfural) amino] antipyrine complexes of thorium (IV) and dioxouranium (VI)

    International Nuclear Information System (INIS)

    Thorium (IV) and dioxouranium (VI) complexes of Schiff base 4-[N-(furfural) amino] antipyrine (FFAP) derived from furfural and 4-aminoantipyrine having general composition ThX4.nL (X = Cl-, Br-, NCS-or NO3-, n = 2; x = I- or ClO4-n = 3, L = FFAP) and UO2X2.nL (X Br-, I-, NCS-,NO3- or CH3COO-, n = 2; X = ClO4-n = 3, L = FFAP) have been synthesized and characterized by molecular weight, conductivity, IR spectral and thermoanalytical studies. (author)

  4. Influence of the ammonium salt anion on the synergistic solvent extraction of lanthanides with mixtures of thenoyltrifluoroacetone and tridecylamine

    International Nuclear Information System (INIS)

    The synergistic solvent extraction of Pr, Gd and Yb with mixtures of thenoyltrifluoroacetone (HTTA) and primary ammonium salt (tridecylammonium chloride or perchlorate, TDAH(Cl, ClO4)) in C6H6 has been studied. The composition of the extracted species have been determined as Ln(TTA)3TDAHA(A- = Cl- or ClO4-). The values of the equilibrium constant KT,S have been calculated. The influence of the ammonium salt anion on the extraction process has been discussed. The separation factors of the pairs Gd/Pr and Yb/Gd have been determined

  5. Synthesis and spectrochemistry of metal complexes with 2,4-dimethyl-9-hydroxypyrido[1,2-a] pyrimidinium perchlorate

    International Nuclear Information System (INIS)

    Complexes of cadmium and certain other metals with 2,4-dimethyl-9-hydroxy-pyrido [1,2-a] pyrimidinium ([PION-9]ClO4) have been synthesized. The properties of the compounds are studied by spectroscopic (IR spectroscopy, electron absorption spectroscopy) methods. It is shown that [PION-9]ClO4 is included in the composition of the complex in deprotonation from and the bond with metal is realized via oxygen atom of hydroxylic group and nitrogen (1) atom. The metal-ligand ratio is 1:2

  6. Lanthanide perchlorate complexes of quinoline-1-oxide and isoquinoline-2-oxide

    OpenAIRE

    Kalyanasundaram, R; Navaneetham, NS; Soundararajan, S.

    1985-01-01

    Complexes of lanthanide perchlorates with quinoline-1-oxide and isoquinoline-2-oxide have been isolated for the first time characterised by analysis, conductance and IR, NMR and electronic spectoral studies. The complexes of quinoline-1-oxide have the composition $Ln(QNO)_8$$(ClO_4)_3$ where Ln = La, Pr or Nd and $Ln(QNO)_7$ where Ln = Gd, Dy, Ho, Er, Yb. The isoquinoline-2-oxide complexes analyse for the formula $Ln(IsoQNO)_7(ClO_4)_3$ where Ln = La-Yb.

  7. Manganese (III) cyclam complexes with aqua, iodo, nitrito, perchlorato and acetic acid/acetato axial ligands

    DEFF Research Database (Denmark)

    Mossin, Susanne; Sørensen, Henning Osholm; Weihe, Høgni; Glerup, Jørgen; Søtofte, Inger

    2005-01-01

    The syntheses, structures and magnetic properties of five new manganese (III) cyclam complexes, trans-[Mn(cyclam)(OH2)(2)]-(CF3SO3)(3)center dot-H2O, trans-[Mn(cyclam)I-2]I, trans-[Mn(cyclam)(ONO)(2)]ClO4, trans-[Mn(cyclam)(OClO3)(2)]ClO4 and trans-[Mn(cyclam) (CH3COO)(CH3COOH)](ClO4)(2), are rep...... pseudo-chain structure. The tilt of the axial ligands with respect to the equatorial plane containing the manganese and the cyclam nitrogen atoms is discussed....

  8. An investigation for a method for measuring microbial degradation for oxochlorates in waste water sludge

    OpenAIRE

    Najem, Hoger

    2015-01-01

    The oxochlorates, such as ClO4-, ClO3- and ClO2- are toxic compounds and therefore they must be removed from effluents. In general they are synthetic compounds from industries and naturally also presents in Chilean caliche. Salts of these compounds are used in many purposes for examples, NH4 ClO4 uses as a solid propellant in rocket, explosive and fireworks. It is difficult to removing this salt from environmental pollutions because it is soluble in water. Today, bioremediation process which ...

  9. Perchlorate production by ozone oxidation of chloride in aqueous and dry systems

    International Nuclear Information System (INIS)

    Overwhelming evidence now exists that perchlorate is produced through natural processes and can be ubiquitously found at environmentally relevant concentrations in arid and semi-arid locations. A number of potential production mechanisms have been hypothesized and ClO4- production by ozone oxidation of surface bound Cl- was demonstrated. However, no information concerning the impact of concentration, final reaction products distribution, impact of reaction phase, or oxidation of important oxychlorine intermediates has been reported. Using IC-MS-MS analysis and replicate oxidation experiments, we show that exposing aqueous solutions or Cl- coated sand or glass surfaces to O3 (0.96%) generated ClO4- with molar yields of 0.007 and 0.01% for aqueous Cl- solutions and 0.025 and 0.42% for Cl- coated sand and glass, respectively. Aqueous solutions of Cl- produced less ClO4- than Cl- coated sand or glass as well as a higher ratio of ClO3- to ClO4-. Reduction of the initial Cl- mass resulted in substantially higher molar yields of ClO4- and ClO3-. In addition, alkaline absorbers that captured gaseous products contained substantial quantities of Cl-, ClO3-, and ClO4-. Solutions of possible oxychlorine intermediates (OCl- and ClO3-) exposed to O3 produced only scant amounts of ClO4- while a ClO2- solution exposed to O3 produced substantial molar yields of ClO4- (4% molar yield). Scanning electron microscopy coupled with energy energy-dispersive X-ray analysis demonstrated a significant loss of Cl- and an increase in oxygen on the Cl- coated silica sand exposed to O3. While the experimental conditions are not reflective of natural conditions this work clearly demonstrates the relative potential of Cl- precursors in perchlorate production and the likely importance of dry aerosol oxidation over solution phase reactions. It also suggests that ClO2- may be a key intermediate while ClO3- and OCl- are unlikely to play a significant role

  10. Photocatalytic Water Oxidation Using Manganese Compounds Immobilized in Nafion Polymer Membranes

    OpenAIRE

    Young, Karin J.; GAO Yunlong; Brudvig, Gary W.

    2011-01-01

    Robust water oxidation catalysts using earth abundant metals are required as part of an overall scheme to convert sunlight into fuels. Here, we report the immobilization of [Mn4IVO5(terpy)4(H2O)2](ClO4)6 (terpy = 2,2′;6′,2″-terpyridine), [Mn4O6(tacn)4](ClO4)4 (tacn = 1,4,7-triazacyclononane), and manganese dioxide nanoparticles in Nafion on fluorine-doped tin oxide conducting glass electrodes. The electrodes are illuminated with white light in the presence of an applied potential and the resu...

  11. Characterization of the Initial Intermediate Formed during Photoinduced Oxygenation of the Ruthenium(II) Bis(bipyridyl)flavonolate Complex.

    Science.gov (United States)

    Han, Xiaozhen; Klausmeyer, Kevin K; Farmer, Patrick J

    2016-08-01

    A ruthenium(II) flavonolate complex, [Ru(II)(bpy)2fla][BF4], was synthesized to model the reactivity of the flavonol dioxygenases. The treatment of dry CH3CN solutions of [Ru(II)(bpy)2fla][BF4] with dioxygen under light leads to the oxidative O-heterocyclic ring opening of the coordinated substrate flavonolate, resulting in the formation of [Ru(II)(bpy)2(carboxylate)][BF4] (carboxylate = O-benzoylsalicylate or benzoate) species, as determined by electrospray ionization mass spectrometry. Moderation of the excitation and temperature allowed isolation and characterization of an intermediate, [Ru(II)(bpy)2bpg][BF4] (bpg = 2-benzoyloxyphenylglyoxylate), generated by the 1,2-addition of dioxygen to the central flavonolate ring. PMID:27437831

  12. Ambient Ionic Liquids Used in the Reduction ofAldehydes and Ketones

    Institute of Scientific and Technical Information of China (English)

    Dan Qian XU; Shu Ping LUO; Bao You LIU; Zhen Yuan XU; Yin Chu SHEN

    2004-01-01

    The sodium borohydride reduction of aldehydes and ketones to corresponding alcohols has been accomplished via the use of ionic liquids. The alcohols are easily obtained with excellent yields and the ionic liquid BMImBF4 could be reused.

  13. Microregion detection of ionic liquid microemulsions.

    Science.gov (United States)

    Gao, Yanan; Wang, Suqing; Zheng, Liqiang; Han, Shuaibing; Zhang, Xuan; Lu, Deming; Yu, Li; Ji, Yongqiang; Zhang, Gaoyong

    2006-09-15

    Nonaqueous ionic liquid (IL) microemulsion consisting of IL, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), surfactant TX-100, and toluene was prepared and the phase behavior of the ternary system was investigated. Electrical conductivity measurement was used for investigating the microregions of the nonaqueous IL microemulsions. On the basis of the percolation theory, the bmimBF(4)-in-toluene (IL/O), bicontinuous, and toluene-in-bmimBF(4) (O/IL) microregions of the microemulsions were successfully identified using insulative toluene as the titration phase. However, this method was invalid when conductive bmimBF(4) acted as the titration phase. The microregions obtained by conductivity measurements were further proved by electrochemical cyclic voltammetry experiments. The results indicated that the conductivity method was feasible for identifying microstructures of the nonaqueous IL microemulsions. PMID:16765365

  14. Unusually long-lived light-induced metastable state in a thermochromic copper(II) complex.

    Science.gov (United States)

    Takahashi, Kazuyuki; Nakajima, Rie; Gu, Zhong-ze; Yoshiki, Hajime; Fujishima, Akira; Sato, Osamu

    2002-08-01

    We report the first observation of a color change from red to purple for a thermochromic complex, [Cu(dieten)2](BF4)2 (dieten = N,N-diethylethylenediamine), which is induced by illuminating with UV light. PMID:12170790

  15. Nano-electromanipulation of Spin Crossover Nanorods: Towards Switchable Nanoelectronic Devices

    OpenAIRE

    Rotaru, Aurelian; Dugay, Julien; Tan, Reasmey P.; Gural'skiy, Il'ya A.; Salmon, Lionel; Demont, Philippe; Carrey, Julian; Molnar, Gabor; Respaud, Marc; Bousseksou, Azzedine

    2013-01-01

    The nanoscale manipulation and charge transport properties of the [Fe(Htrz)2(trz)](BF4) spin-crossover compound is demonstrated. Such 1D spin-crossover nanostructures are attractive building blocks for nanoelectronic switching and memory devices.

  16. Chemistry of dihydrogen complexes containing only phosphorus co-ligands

    Indian Academy of Sciences (India)

    Balaji R Jagirdar; Nisha Mathew

    2002-08-01

    A series of new dicationic dihydrogen complexes of ruthenium of the type cis-[(dppm)2Ru(2-H2)(L)][BF4]2 (dppm = Ph2PCH2PPh2; L = phosphite) have been prepared by protonating the precursor hydride complexes cis-[(dppm)2Ru(H)(L)][BF4] using HBF4$\\cdot$Et2O. The precursor hydride complexes have been obtained from trans-[(dppm)2Ru(H)(L)][BF4] (L = phosphite) via a rare acidcatalysed isomerization reaction in six coordinate species. The trans-[(dppm)2Ru(H)(L)][BF4] complexes (L = phosphine) upon protonation gave the isomerized derivatives, however, further addition of acid resulted in a five-coordinate species, [(dppm)2RuCl]+ presumably via an intermediate phosphine dihydrogen complex. The electronic as well as the steric properties of the co-ligands seem to strongly influence the structure-reactivity behaviour of this series of complexes.

  17. Volumetric properties, viscosities and refractive indices of binary liquid mixtures of tetrafluoroborate-based ionic liquids with methanol at several temperatures

    International Nuclear Information System (INIS)

    Highlights: • Mixtures of [bmim][BF4] or [emim][BF4] with methanol were studied. • Density, speed of sound, viscosity and refractive index were determined. • Excess volumes, isentropic compressibilities, properties deviations were calculated. • Properties excess and deviations were correlated with temperature and composition. - Abstract: Densities, speeds of sound, viscosities and refractive indices of two binary systems 1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4] + methanol and 1-ethyl-3-methylimidazolium tetrafluoroborate [emim][BF4] + methanol, as well as of all pure components, have been measured covering the whole range of compositions at T = (278.15 to 318.15) K and p = 101 kPa. From this data, excess molar volumes, excess isentropic compressibilities, viscosity deviations and refractive index deviations were calculated and fitted to extended versions of the Redlich–Kister equation. Estimated coefficients of these equations taking into account the dependence on composition and temperature simultaneously were also presented

  18. One-Way Diffusion of Ionic Liquids in a Mixing Process with Water

    Science.gov (United States)

    Oikawa, Noriko; Tahara, Daiki; Kurita, Rei

    2016-09-01

    In contrast to the usual diffusive mixing process between two miscible liquids, the ionic liquid [Cnmim][PF6] forms a droplet in water while mixing. The droplet retains a sharp interface with surface tension, gradually decreasing in size until completely mixed with water. This peculiar behavior in the mixing process accompanies one-way diffusion, in which ions diffuse in one direction only from the bulk IL droplet into the bulk continuum of water. The activation energy of the one-way diffusion at the [Cnmim][PF6]/water interface increases with increasing length of the hydrophobic alkyl chains attached to the cation molecules of [Cnmim][PF6]. It is considered that the hydrophobic nanoscale structure observed in [C4mim][PF6] plays an important role in the generation of the droplet and the mixing dynamics.

  19. Effect of side-chain asymmetry on the intermolecular structure and order-disorder transition in alkyl-substituted polyfluorenes

    Science.gov (United States)

    Knaapila, M.; Stepanyan, R.; Torkkeli, M.; Haase, D.; Fröhlich, N.; Helfer, A.; Forster, M.; Scherf, U.

    2016-04-01

    We study relations among the side-chain asymmetry, structure, and order-disorder transition (ODT) in hairy-rod-type poly(9,9-dihexylfluorene) (PF6) with two identical side chains and atactic poly(9-octyl-9-methyl-fluorene) (PF1-8) with two different side chains per repeat. PF6 and PF1-8 organize into alternating side-chain and backbone layers that transform into an isotropic phase at TODT(PF 6 ) and TbiODT(PF 1 -8 ) . We interpret polymers in terms of monodisperse and bidisperse brushes and predict scenarios TODTstructurally possible but not certain for PF6 and confirmed for PF1-8.

  20. A 2D [Fe-II-bistetrazole] coordination polymer exhibiting spin-crossover properties

    NARCIS (Netherlands)

    Quesada, Manuel; Prins, Ferry; Roubeau, Olivier; Gamez, Patrick; Teat, Simon J.; van Koningsbruggen, Petra J.; Haasnoot, Jaap G.; Reedijk, Jan

    2007-01-01

    The reaction of 1,3-bis(tetrazol-1-yl)-2-propanol (btzpol) with Fe(BF4)(2) center dot 6H(2)O in acetonitrile yields the remarkable 2D coordination polymer [Fe-II(btzpol)(1.8)(btzpol-OBF3)(1.2)](BF4)(0.8) center dot (H2O)(0.8)(CH3CN) (1). This compound has been structurally characterized using an X-r

  1. Electrochromic devices incorporating biohybrid electrolytes doped with a lithium salt, an ionic liquid or a mixture of both

    International Nuclear Information System (INIS)

    Highlights: • Poly(ϵ-caprolactone)/siloxane biohybrid electrolytes were prepared by sol-gel chemistry. • The electrolytes were doped with LiCF3SO3, an IL or the mixture of both. • The IL used was 1-ethyl-3-methyl imidazolium tetrafluoroborate ([Emim]BF4). • Prototype electrochromic devices incorporating the three electrolytes were tested. - Abstract: The sol-gel method was employed in the synthesis of di-urethane cross-linked poly(ϵ-caprolactone) (PCL(530))/siloxane biohybrid ormolytes incorporating either a mixture of lithium triflate (LiCF3SO3) and the ionic liquid (IL) 1-ethyl-3-methyl imidazolium tetrafluoroborate ([Emim]BF4), or solely with [Emim]BF4 or LiCF3SO3. The ormolyte doped with [Emim]BF4 is thermally more stable and exhibits higher ionic conductivity (4 × 10−4 and 2 × 10−3 S cm−1 at 36 and 98 °C, respectively) than those containing the LiCF3SO3/[Emim]BF4 mixture or just LiCF3SO3. The three ormolytes were employed in the production of glass/ITO/ormolyte/WO3/ITO/glass electrochromic devices (ECDs) designated as ECD@Y with Y = Li-[Emim]BF4, [Emim]BF4 and Li. The three ECDs displayed fast switching speed (ca. 30 s). ECD@Li-[Emim]BF4 exhibited an electrochromic contrast of 18.4% and an optical density change of 0.11 in the visible region, the coloration efficiency attained at 555 nm was 152 and 80.2 cm2C−1 in the “on” and “off” states, respectively, and the open circuit memory was 48 hours. In the “on” state the CIE 1931 color space coordinates were x = 0.29 and y = 0.30, corresponding to blue color

  2. IMPEDANCE CHARACTERISTICS OF POLYFURAN FILMS

    Institute of Scientific and Technical Information of China (English)

    Liang Li; Xiao-bo Wan; Gi Xue

    2002-01-01

    Electrochemical impedance spectroscopy (EIS) was first used for the characterization of polyfuran (PFu) films that had been formed electrochemically on an Au electrode. The polyfuran was measured in high oxidation state, intermediate oxidation state and reduction state, respectively. As the oxidation level is increased, the ionic conductivity of PFu/BF4-increases. And impedance studies on PFu show that the anion BF4- appears to be mobile with a high diffusion coefficient of approximately 10-8 cm2 @ s-1.

  3. Mechanism of dissolution of a lithium salt in an electrolytic solvent in a lithium ion secondary battery: a direct ab initio molecular dynamics (AIMD) study.

    Science.gov (United States)

    Tachikawa, Hiroto

    2014-06-01

    The mechanism of dissolution of the Li(+) ion in an electrolytic solvent is investigated by the direct ab initio molecular dynamics (AIMD) method. Lithium fluoroborate (Li(+)BF4(-)) and ethylene carbonate (EC) are examined as the origin of the Li(+) ion and the solvent molecule, respectively. This salt is widely utilized as the electrolyte in the lithium ion secondary battery. The binding of EC to the Li(+) moiety of the Li(+)BF4(-) salt is exothermic, and the binding energies at the CAM-B3LYP/6-311++G(d,p) level for n=1, 2, 3, and 4, where n is the number of EC molecules binding to the Li(+) ion, (EC)n(Li(+)BF4(-)), are calculated to be 91.5, 89.8, 87.2, and 84.0 kcal mol(-1) (per EC molecule), respectively. The intermolecular distances between Li(+) and the F atom of BF4(-) are elongated: 1.773 Å (n=0), 1.820 Å (n=1), 1.974 Å (n=2), 1.942 Å (n=3), and 4.156 Å (n=4). The atomic bond populations between Li(+) and the F atom for n=0, 1, 2, 3, and 4 are 0.202, 0.186, 0.150, 0.038, and 0.0, respectively. These results indicate that the interaction of Li(+) with BF4(-) becomes weaker as the number of EC molecules is increased. The direct AIMD calculation for n=4 shows that EC reacts spontaneously with (EC)3(Li(+)BF4(-)) and the Li(+) ion is stripped from the salt. The following substitution reaction takes place: EC+(EC)3(Li(+)BF4(-))→(EC)4Li(+)-(BF4(-)). The reaction mechanism is discussed on the basis of the theoretical results. PMID:24616076

  4. Temperature dependence of intra-stack defect spin-conduction-electron spin interaction in fluoranthene and perylene radical cation salts

    International Nuclear Information System (INIS)

    The electron spin resonance line-width anisotropy and intensity are analysed for the quasi-one-dimensional organic conductors (fluoranthene)2PF6 and (perylene)2PF6·2/3 tetrahydrofurane in the metallic phase above the Peierls transition temperature. Based on the bottleneck model of relaxation, the temperature dependence of the intra-stack exchange constant between conduction-electron spins and localized defect spins is derived and discussed

  5. Comparing Triflate and Hexafluorophosphate Anions of Ionic Liquids in Polymer Electrolytes for Supercapacitor Applications

    OpenAIRE

    Chiam-Wen Liew; Ramesh, S

    2014-01-01

    Two different ionic liquid-based biopolymer electrolyte systems were prepared using a solution casting technique. Corn starch and lithium hexafluorophosphate (LiPF6) were employed as polymer and salt, respectively. Additionally, two different counteranions of ionic liquids, viz. 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (also known as 1-butyl-3-methylimidazolium triflate) (BmImTf) were used and studied in this present...

  6. Molecular sieve supported ionic liquids as efficient adsorbent for CO2 capture

    Directory of Open Access Journals (Sweden)

    Yang Na

    2015-01-01

    Full Text Available [NH3e-mim][BF4], [OHe-mim][BF4] and [HOEAm] were selected and supported onto molecular sieves NaY, USY, SAPO-34 and MCM-41, to prepare supported ionic liquids. It was found that [NH3e-mim][BF4]/NaY has excellent CO2 adsorption performance, with adsorption capacity of 0.108 mmolCO2/g. This paper investigates the optimal adsorption conditions and recyclability of [NH3e-mim][BF4]/NaY. The results show that [NH3e-mim][BF4]/NaY has good CO2 adsorption under the condition of 20°C and 20% ILs loading amount. By vacuum heating, CO2 adsorption capacity reaches 0.451mmolCO2/g at fifth runs and reduces to 0.29mmolCO2/g at tenth runs. The structure and characterization of the [NH3e-mim][BF4]/NaY was examined by FT-IR, XRD, SEM and TG-DSC. TG-DSC also shows that it has good thermostability below 50°C.

  7. Novel nanohybrids of cobalt(III) Schiff base complexes and clay: Synthesis and structural determinations

    Science.gov (United States)

    Kianfar, Ali Hossein; Mahmood, Wan Ahmad Kamil; Dinari, Mohammad; Azarian, Mohammad Hossein; Khafri, Fatemeh Zare

    2014-06-01

    The [Co(Me2Salen)(PBu3)(OH2)]BF4 and [Co(Me2Salen)(PPh3)(Solv)]BF4, complexes were synthesized and characterized by FT-IR, UV-Vis, 1H NMR spectroscopy and elemental analysis techniques. The coordination geometry of [Co(Me2Salen)(PPh3)(H2O)]BF4 was determined by X-ray crystallography. It has been found that the complex is containing [Co(Me2Salen)(PPh3)(H2O)]BF4 and [Co(Me2Salen)(PPh3)(EtOH)]BF4 hexacoordinate species in the solid state. Cobalt atom exhibits a distorted octahedral geometry and the Me2Salen ligand has the N2O2 coordinated environment in the equatorial plane. The [Co(Me2Salen)(PPh3)(H2O)]BF4 complex shows a dimeric structure via hydrogen bonding between the phenolate oxygen and hydrogens of coordinated H2O molecule. These complexes were incorporated into Montmorillonite-K10 nanoclay. The modified clays were identified by FT-IR, XRD, EDX, TGA/DTA, SEM and TEM techniques. According to the XRD results of the new nanohybrid materials, the Schiff base complexes are intercalated in the interlayer spaces of the clay. SEM and TEM micrographs show that the resulting hybrid nanomaterials have layer structures. Also, TGA/DTG results show that the intercalation reaction was taken place successfully.

  8. Nanodroplet cluster formation in ionic liquid microemulsions.

    Science.gov (United States)

    Gao, Yanan; Voigt, Andreas; Hilfert, Liane; Sundmacher, Kai

    2008-08-01

    A common ionic liquid (IL), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), is used as polar solvent to induce the formation of a reverse bmimBF(4)-in-toluene IL microemulsion with the aid of the nonionic surfactant Triton X-100. The swelling process of the microemulsion droplets by increasing bmimBF(4) content is detected by dynamic light scattering (DLS), conductivity, UV/Vis spectroscopy, and freeze-fracture transmission electron microscopy (FF-TEM). The results show that the microemulsion droplets initially formed are enlarged by the addition of bmimBF(4). However, successive addition of bmimBF(4) lead to the appearance of large-sized microemulsion droplet clusters (200-400 nm). NMR spectroscopic analysis reveal that the special structures and properties of bmimBF(4) and Triton X-100 together with the polar nature of toluene contribute to the formation of such self-assemblies. These unique self-assembled structures of IL-based microemulsion droplet clusters may have some unusual and unique properties with a number of interesting possibilities for potential applications. PMID:18576451

  9. Preparation of extremely smooth and boron-fluorine co-doped TiO2 nanotube arrays with enhanced photoelectrochemical and photocatalytic performance

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Highly ordered TNTs are prepared by first using NH4BF4 based electrolyte. • Ripple-free tube walls are obtained due to the mildness of the BF4–. • B, F originate from the decomposition of BF4–are co-doped into BF-TNTs. • BF-TNTs exhibit better PEC and PC performance than those of TNTs. - Abstract: Highly ordered TiO2 nanotube arrays (BF-TNTs) are prepared by anodization method in the unique NH4BF4 based electrolyte. The results show that the tube walls of the BF-TNTs, by first using NH4BF4 based electrolyte, are much smoother than that of TiO2 nanotube arrays (F-TNTs) fabricated with a conventional fluoride containing electrolyte. In the NH4BF4 electrolyte, boron and fluorine elements are simultaneously doped into the obtained BF-TNTs during the anodization process. The BF-TNTs exhibit better photoelectrochemical (PEC) properties and photocatalytic (PC) performance than those of F-TNTs

  10. Selective formation of silver(i) bis-phospholane macrocycles and further evidence that gold(i) is smaller than silver(i).

    Science.gov (United States)

    Streitberger, Markus; Schmied, Andy; Hoy, Reinhard; Hey-Hawkins, Evamarie

    2016-08-01

    A new synthetic approach to highly flexible bis-phospholanes from 1-benzylphospholane (1) as starting material is described. Silver(i) macrocycles containing 16 ([Ag2(μ-3a)2](BF4)2, 4), 20 ([Ag2(μ-3b)2](BF4)2, 5), 24 ([Ag2(μ-3c)2](BF4)2, 6), and 28 ([Ag2(μ-3d)2](BF4)2, 7) atoms in the ring were obtained in one step from AgBF4 and the respective bis-phospholane (C4H8P)(CH2)n(PC4H8) (n = 5, 7, 9, 11; 3a-d) in excellent yields. Comparison of 6 with the previously reported isomorphous complex [Au2(μ-3c)2](BF4)2 gave further evidence that gold(i) is significantly smaller than silver(i). All complexes were fully characterized by NMR and IR spectroscopy, mass spectrometry, and X-ray diffraction. PMID:27221148

  11. Synthesis of cyano-bridged bimetallic complexes of 5-indenyl ruthenium(II): Characterization and spectroscopic studies

    Indian Academy of Sciences (India)

    K Mohan Rao; E K Rymmai

    2001-02-01

    Reactions of the cyanide complexes of the type [(Ind)Ru(PPh3)2CN] (1), [(Ind)Ru(dppe)CN] (2), [(Cp)Ru(PPh3)2CN] (3), with the corresponding chloro complexes [(Ind)Ru(PPh3)2Cl] (4), [(Ind)Ru(dppe)Cl] (5), [(Cp)Ru(PPh3)2Cl] (6), in the presence of NH4PF6 salt give homometallic cyano-bridged compounds of the type [(Ind)(PPh3)2Ru-CN-Ru(PPh3)2(Cp)]PF6 (7), [(Ind)(PPh3)2Ru-CN-Ru(PPh3)2(Ind)] PF6 where Ind = indenyl, 5-C9H7, (8), [(Cp)(PPh3)2Ru-CN-Ru(dppe)(Ind)]PF6, dppe = (Ph2PCH2CH2PPh2) (9), [(Ind(dppe)Ru-CN-Ru(PPh3)2(Ind)PF6 (10) and [(Ind)(dppe)Ru-CN-Ru(PPh3)2(Cp)]PF6 (11) respectively. Reaction of complex 3 with [(p-cymene)RuCl2]2 dimer gave a mixed dimeric complex [(Cp)Ru(PPh3)2-CN-RuCl2(-cymene)] (12). All these complexes have been characterized by IR, 1H, 13C and 31 P NMR spectroscopy and C, H, N analyses.

  12. Long-Range Ruthenium-Amine Electronic Communication through the para-Oligophenylene Wire

    Science.gov (United States)

    Shen, Jun-Jian; Zhong, Yu-Wu

    2015-09-01

    The studies of long-range electronic communication are hampered by solubility and potential-splitting issues. A “hybridized redox-asymmetry” method using a combination of organic and inorganic redox species is proposed and exemplified to overcome these two issues. Complexes 1(PF6)-6(PF6) (from short to long in length) with the organic redox-active amine and inorganic cyclometalated ruthenium termini bridged by the para-oligophenylene wire have been prepared. Complex 6 has the longest Ru-amine geometrical distance of 27.85 Å. Complexes 3(PF6) and 4(PF6) show lamellar crystal packing on the basis of a head-to-tail anti-parallelly aligned dimeric structure. Two redox waves are observed for all complexes in the potential region between +0.2 and +0.9 V vs Ag/AgCl. The electrochemical potential splitting is 410, 220, 143, 112, 107, and 105 mV for 1(PF6) through 6(PF6), respectively. Ruthenium (+2) to aminium (N•+) charge transfer transitions have been identified for the odd-electron compounds 12+-62+ by spectroelectrochemical measurements. The electronic communication between amine and ruthenium decreases exponentially with a decay slope of -0.137 Å-1. DFT calculations have been performed to complement these experimental results.

  13. 锂离子电池电解质锂盐的发展历程和新型锂盐的研究进展%Development of Lithium Ion Battery Electrolyte and Research Progress of Novel Lithium Salts

    Institute of Scientific and Technical Information of China (English)

    闫春生; 李媛媛; 刘园园

    2016-01-01

    LiPF6 has become the most widely used commercial lithium battery electrolyte with brilliant ion-ic conductivity,better oxidation stability and less environmental pollution etc. Because LiPF6 thermal sta-bility is poor,the price is relatively expensive,the development and preparation of new lithium salts be-come a focus of attention for researchers. In this paper,the development of traditional lithium electrolyte is reviewed,the synthesis process of LiPF6 is summarized ,and research progress of new lithium salts is in-troduced.%六氟磷酸锂( LiPF6)因其突出的离子电导率、较优的氧化稳定性和较小的环境污染等优点成为目前使用最广泛的商业化锂电池电解质。由于LiPF6热稳定性较差、价格相对昂贵,使得新型锂盐的开发与制备成为研究者们关注的热点。本文回顾了传统锂盐电解质的发展,对LiPF6的合成工艺进行了综述,并介绍了新型锂盐的研究进展情况。

  14. Studies of radioactive nuclear elements extraction using room-temperature ionic liquids

    International Nuclear Information System (INIS)

    The extractions of U(VI) from nitric acid medium by tri-n-butylphosphate (TBP) dissolved in non-traditional diluent, namely 1-octyl-3-methylimidazolium hexafluorophosphate ([C8mim][PF6]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) ionic liquid (IL), were studied. The experimental results indicated that, TBP/[C8mim][PF6] demonstrated more performance for extracting uranium than TBP/[C4mim][PF6], due to the better hydrophobicity of [C8mim][PF6]. The distribution ratio for the extraction of U(VI) from nitric acid by TBP/IL was increased with gaining nitric acid concentration. Furthermore, the extraction of strontium using t-BAMBP(4-tert-butyl-2-(α-methylbenzyl) phenol) as extractant instead of crown ethers was also studied in this paper. The preliminary results showed that the better extraction efficiency values (ESr2+∼94.26%) can be achieved using [C4mim][PF6] as diluent. (authors)

  15. A study of adsorption equilibrium on quaternary ammonium resin in uranyl sulphate solution by chemical equivalent method

    International Nuclear Information System (INIS)

    The exchange equilibrium between SO42- and HSO4- on quaternary ammonium strong base resin and the effect of ClO4- on the equilibrium are studied by chemical equivalent method. On the basis of the results the adsorption equilibrium of the resin in uranyl sulphate solution which is similar to the solution in uranium hydrometallurgy process is also studied

  16. ISSUES IN MANAGING THE RISKS ASSOCIATED WITH PERCHLORATE IN DRINKING WATER

    Science.gov (United States)

    Perchlorate (ClO4-) contamination of ground and surface waters has placed drinking water supplies at risk in communities throughout the US, especially in the West. Several major assessment studies of that risk in terms of health and environmental impact are ...

  17. Synthetic, structural, spectroscopic and theoretical study of a Mn(III)-Cu(II) dimer containing a Jahn-Teller compressed Mn ion

    DEFF Research Database (Denmark)

    Berg, Nelly; Hooper, Thomas N.; Liu, Junjie;

    2013-01-01

    The heterobimetallic complex [Cu(II)Mn(III)(L)(2)(py)(4)](ClO(4))·EtOH (1) built using the pro-ligand 2,2'-biphenol (LH(2)), contains a rare example of a Jahn-Teller compressed Mn(III) centre. Dc magnetic susceptibility measurements on 1 reveal a strong antiferromagnetic exchange between the Cu(I...

  18. Effect of anions on thermodynamics of extraction of Am (III) and Eu (III) with octyl (phenyl) N, N-diisobutyl carbamoyl methyl phosphine oxide (CMPO)

    International Nuclear Information System (INIS)

    The effect of various anions like nitrate, thiocyanate, perchlorate and a mixture of NO3- and ClO4- on the extraction of Am (III) and Eu (III) by CMPO in xylene has been studied. The correlation of the thermodynamic parameters with some relevant physical properties of the anions in the aqueous media has been done. (author)

  19. High ozone increases soil perchlorate but does not affect foliar perchlorate content

    Science.gov (United States)

    Ozone (O3) is implicated in the natural source inventory of perchlorate (ClO4-), a hydrophilic salt that migrates to ground water and interferes with uptake of iodide in mammals, including humans. Tropospheric O3 is elevated in many areas. We previously showed (Grantz et al., 2013; Environmental Pol...

  20. Enhanced two-photon absorption of hypersensitive transitions induced by coordination field in europium(III) complex

    International Nuclear Information System (INIS)

    The photoluminescence properties of novel europium(III) complex of the form [Eu(L1)(Antipy)3(ClO4)3] are presented in this manuscript. Under the coordination field of C3 symmetry in Eu(L1)(Antipy)3(ClO4)3, the oscillator strength of 7F0→5D2 and 7F1→5D1 hypersensitive transitions enhances two orders of magnitude compared with pseudo-Oh symmetry in Eu(L2)2(ClO4)3. The red fluorescence emission of Eu(L1)(Antipy)3(ClO4)3 can be efficiently induced by the one- and two-photon absorption of 7F0→5D2 and 7F1→5D1. Furthermore, the two-photon excitation band at 929 nm corresponding to TPA of 7F0→5D2 is 8 nm, which makes it sensitive to excitation wavelength and distinguished from other excitation sources. - Highlights: ► We realized two-photon sensitized luminescence based on hypersensitive transitions. ► The significant enhancement of two-photon absorption was observed ► The influence of coordination field was elaborated. ► The two-photon excitation band at 929 nm is 8 nm.

  1. Influence of processes of structure formation in mixed solvent and anion nature on cadmium ions discharge kinetics from water-dimethylformamide electrolyte

    International Nuclear Information System (INIS)

    Electrochemical reaction of cadmium ion discharge in water-dimethylformamide (DMF) solutions is studied. The influence of DMF concentration in the presence of different anions (ClO4-, F-, I-) on both reaction kinetics and mechanism is discussed on the basis of structural transformations in the mixed solvent and near the surface electrode processes

  2. Drug: D03675 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D03675 Drug Delmadinone acetate (USAN) C23H27ClO4 402.1598 402.9111 D03675.gif Prog...ts CAS: 13698-49-2 PubChem: 17397771 LigandBox: D03675 NIKKAJI: J8.444A ATOM 28 1 C1y C 34.5419 -20.1300 2 C

  3. Zero-pressure organic superconductor

    DEFF Research Database (Denmark)

    Bechgaard, K.; Carneiro, K.; Olsen, M.; Jacobsen, C.S.; Rasmussen, Finn Berg

    1981-01-01

    Evidence for superconductivity in the organic conductor di-(tetramethyltetraselenafulvalenium)-perchlorate [(TMTSF)2ClO4] has been found by resistance measurements in the absence of applied pressure. For different crystals the transitions are approximately 0.3 K wide and are centered around...

  4. 高氯酸诺氟沙星铜(Ⅱ)%Norfloxacin Coppe(Ⅱ) Perchlorate

    Institute of Scientific and Technical Information of China (English)

    谢永荣; 叶琼; 熊仁根

    2004-01-01

    The hydrothermal treatment of Cu(ClO4)2·6H2O and Norfloxacin (H-Norf) afforded [Cu(H-Noff)2(ClO4)2] (1) in which center Cu has a square planar geometry while perchlorate just acts as charge balance anions. CCDC:140821.

  5. Mn(II) complexes with bipyridine, phenanthroline and benzoic acid: Biological and catalase-like activity

    Indian Academy of Sciences (India)

    Ibrahim Kani; Özlem Atlier; Kiymet Güven

    2016-04-01

    Five mononuclear Mn(II) complexes, [Mn(phen)2(ClO4)2] (1), [Mn(phen)3](ClO4)2(H2CO3)2(2), [Mn(bipy)2(ClO4)2] (3), [Mn(bipy)3](ClO4)2) (4), and Mn(phen)2(ba)(H2O)](ClO4)(CH3OH) (5), where bipy = 2,2’-bipyridine, phen = 1,10-phenanthroline, and ba = benzoic acid were prepared and characterized by Xray, IR and UV-Vis spectroscopies, and their catalase-like and biological activities were studied. The presence of two different types and the number of chelating NN-donor neutral ligands allowed for analysis of their effects on the catalase and biological activities. It was observed that the presence and number of phen ligands improved the activity more than the bipy ligand. Complexes 1 and 2, which contain more basic phen ligands, disproportionate H2O2 faster than complexes 3 and 4, which contain less basic bipy ligands. The in vitro antimicrobial activities of all the complexes were also tested against seven bacterial strains by microdilution tests. All the bacterial isolates demonstrated sensitivity to the complexes and the antifungal (anticandidal) activities of the Mn(II) complexes were remarkably higher than the reference drug ketoconazole.

  6. Energy-level tailoring in a series of redox-rich quinonoid-bridged diruthenium complexes containing tris2-pyridylmethyl)amine as a co-ligand.

    Science.gov (United States)

    Weisser, Fritz; Huebner, Ralph; Schweinfurth, David; Sarkar, Biprajit

    2011-05-01

    Reactions of [{Ru(tmpa)}2(μ-Cl)2][ClO4]2, (2[ClO4]2, tmpa=tris(2-pyridylmethyl)amine) with 2,5-dihydroxy-1,4-benzoquinone (L1), 2,5-di-[2,6-(dimethyl)-anilino]-1,4-benzoquinone (L2), or 2,5-di-[2,4,6-(trimethyl)-anilino)]-1,4-benzoquinone (L3) in the presence of a base led to the formation of the dinuclear complexes [{Ru(tmpa)}2(μ-L1-2H)][ClO4]2 (3[ClO4]2), [{Ru(tmpa)}2(μ-L2-2H)][ClO4]2 (4[ClO4]2), and [{Ru(tmpa)}2(μ-L3-2H)][ClO4]2 (5[ClO4]2). Structural characterization of 5[ClO4]2 showed the localization of the double bonds within the quinonoid ring and a twisting of the mesityl substituents with respect to the quinonoid plane. Cyclic voltammetry of the complexes show two reversible oxidation and quinonoid-based reduction processes. Results obtained from UV/Vis/NIR and EPR spectroelectrochemistry are invoked to discuss ruthenium- versus quinonoid-ligand-centered redox activity. The complex 3[ClO4]2 is compared to the reported complex [{Ru(bpy)}2(μ-L1-2 H)]2+ (12+, bpy=2,2′-bipyridine). The effects of substituting the bidentate and better π-accepting bpy co-ligands with tetradentate tmpa ligands [pure σ-donating (amine) as well as σ-donating and π-accepting (pyridines)] on the redox and electronic properties of the complexes are discussed. Comparisons are also made between complexes containing the dianionic forms of the all-oxygen-donating L1 ligand with the L2 and L3 ligands containing an [O,N,O,N] donor set. The one-electron oxidized forms of the complexes show absorption in the NIR region. The position as well as the intensity of this band can be tuned by the substituents on the quinonoid bridge. In addition, this band can be switched on and off by using tunable redox potentials, making such systems attractive candidates for NIR electrochromism. PMID:21688408

  7. Microbial perchlorate reduction with elemental sulfur and other inorganic electron donors.

    Science.gov (United States)

    Ju, Xiumin; Sierra-Alvarez, Reyes; Field, Jim A; Byrnes, David J; Bentley, Harold; Bentley, Richard

    2008-03-01

    ClO(4)(-) has recently been recognized as a widespread contaminant of surface and ground water. This research investigated chemolithotrophic perchlorate reduction by bacteria in soils and sludges utilizing inorganic electron-donating substrates such as hydrogen, elemental iron, and elemental sulfur. The bioassays were performed in anaerobic serum bottles with various inocula from anaerobic or aerobic environments. All the tested sludge inocula were capable of reducing perchlorate with H2 as electron donor. Aerobic activated sludge was evaluated further and it supported perchlorate reduction with Fe(0) and S(0) additions under anaerobic conditions. Heat-killed sludge did not convert ClO(4)(-), confirming the reactions were biologically catalyzed. ClO(4)(-) (3mM) was almost completely removed by the first sampling time on d 8 with H2 (> or = 0.37mMd(-1)), after 22d with S(0) (0.18mM d(-1)) and 84% removed after 37d with Fe(0) additions (0.085mMd(-1)). Perchlorate-reduction occurred at a much faster rate (1.12mMd(-1)), when using an enrichment culture developed from the activated sludge with S(0) as an electron donor. The enrichment culture also utilized S(2-) and S(2)O(3)(2-) as electron-donating substrates to support ClO(4)(-) reduction. The mixed cultures also catalyzed the disproportionation of S(0) to S(2-) and SO(4)(2-). Evidence is presented demonstrating that S(0) was directly utilized by microorganisms to support perchlorate-reduction. In all the experiments, ClO(4)(-) was stoichiometrically converted to chloride. The study demonstrates that microorganisms present in wastewater sludges can readily use a variety of inorganic compounds to support perchlorate reduction. PMID:17988714

  8. Molecular simulation and experimental study of CO2 absorption in ionic liquid reverse micelle.

    Science.gov (United States)

    Shi, Wei; Hong, Lei; Damodaran, Krishnan; Nulwala, Hunaid B; Luebke, David R

    2014-12-01

    The structure and dynamics for CO2 absorption in ionic liquid reverse micelle (ILRM) were studied using molecular simulations. The ILRM consisted of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) ionic liquid (IL) as the micelle core, the benzylhexadecyldimethylammonium ([BHD](+)) chloride ([Cl](-)) was the cationic surfactant, and benzene was used as the continuous solvent phase in this study. The diffusivity values of this ILRM system were also experimentally determined. Simulations indicate that there is ion exchange between the IL anion ([BF4](-)) and the surfactant anion ([Cl](-)). It was also found that the [bmim][BF4] IL exhibits small local density at the interface region between the IL core and the [BHD](+) surfactant cation layer, which leads to a smaller density for the [bmim][BF4] IL inside the reverse micelle (RM) compared with the neat IL. These simulation findings are consistent with experimental results. Both our simulations and experimental results show that [bmim][BF4] inside the RM diffuses 5-26 times faster than the neat IL, which is partly due to the fast particle diffusion for the ILRM nanodroplet (IL and surfactant) as a whole in benzene solvent compared with neat [bmim][BF4] diffusion. Additionally, it was found that [bmim][BF4] IL solved in benzene diffuses 2 orders of magnitude faster than the neat IL. Lastly, simulations show that CO2 molecules are absorbed in four different regions of the ILRM system, that is, (I) in the IL inner core, (II) in the [BHD](+) surfactant cation layer, (III) at the interface between the [BHD](+) surfactant cation layer and benzene solvent, and (IV) in the benzene solvent. The CO2 solubility was found to decrease in the order II > III ∼ IV > I, while the CO2 diffusivity and permeability decrease in the following order: IV > III > II > I. PMID:25382316

  9. Ionic liquids as mobile phase additives for the high-performance liquid chromatographic analysis of fluoroquinolone antibiotics in water samples.

    Science.gov (United States)

    Herrera-Herrera, Antonio V; Hernández-Borges, Javier; Rodríguez-Delgado, Miguel Angel

    2008-12-01

    In this work, four ionic liquids differing in the length of the alkyl chain on the imidazolium cation and one ionic liquid containing tetraethylammonium, all with the same counterion, (i.e. 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIm-BF(4)), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIm-BF(4)), 1-hexyl-3-methylimidazolium tetrafluoroborate (HMIm-BF(4)), 1-methyl-3-octylimidazolium tetrafluoroborate (MOIm-BF(4)), and tetraethylammonium tetrafluroborate (Et(4)N-BF(4))) were tested as mobile phase additives for HPLC separation of a group of seven basic fluoroquinolone (FQ) antibiotics for human and veterinary use (i.e. fleroxacin, ciprofloxacin, lomefloxacin, danofloxacin, enrofloxacin, sarafloxacin, and difloxacin) using a conventional reversed-phase Nova-Pak C(18) column. Fluorescence detection was used. Among the ionic liquids selected, use of BMIm-BF(4) enabled effective separation of these compounds with relatively low analysis time (14 min). The best separation was achieved by isocratic elution at 1 mL min(-1) with 5 mmol L(-1) BMIm-BF(4) and 10 mmol L(-1) ammonium acetate at pH 3.0 with 13% (v/v) acetonitrile. Limits of detection (LODs) for fluorescence detection were in the range 0.5-11 microg L(-1). The method was tested by analyzing several water samples after the optimization of a suitable solid-phase extraction (SPE) procedure using Oasis HLB cartridges. Mean recovery values were above 84% for all analytes with LODs in the range 1-29 ng L(-1). PMID:18854988

  10. A new technology for separation and recovery of materials from waste printed circuit boards by dissolving bromine epoxy resins using ionic liquid

    International Nuclear Information System (INIS)

    Highlights: ► WPCBs were heated in [EMIM+][BF4−] for recovering solider at 240 °C. ► The bromine epoxy resins in WPCBs were all dissolved in [EMIM+][BF4−] at 260 °C. ► Used [EMIM+][BF4−] is treated by water to obtain regeneration. - Abstract: Recovery of valuable materials from waste printed circuit boards (WPCBs) is quite difficult because WPCBs is a heterogeneous mixture of polymer materials, glass fibers, and metals. In this study, WPCBs was treated using ionic liquid (1-ethyl-3-methylimizadolium tetrafluoroborate [EMIM+][BF4−]). Experimental results showed that the separation of the solders went to completion, and electronic components (ECs) were removed in WPCBs when [EMIM+][BF4−] solution containing WPCBs was heated to 240 °C. Meanwhile, metallographic observations verified that the WPCBs had an initial delamination. When the temperature increased to 260 °C, the separation of the WPCBs went to completion, and coppers and glass fibers were obtained. The used [EMIM+][BF4−] was treated by water to generate a solid–liquid suspension, which was separated completely to obtain solid residues by filtration. Thermal analyses combined with infrared ray spectra (IR) observed that the solid residues were bromine epoxy resins. NMR (nuclear magnetic resonance) showed that hydrogen bond played an important role for [EMIM+][BF4−] dissolving bromine epoxy resins. This clean and non-polluting technology offers a new way to recycle valuable materials from WPCBs and prevent environmental pollution from WPCBs effectively.

  11. Improvement on the storage performance of LiMn2O4 with the mixed additives of ethanolamine and heptamethyldisilazane

    Science.gov (United States)

    Wu, Xianwen; Li, Xinhai; Wang, Zhixing; Guo, Huajun; Yue, Peng; Zhang, Yunhe

    2013-03-01

    The commercial LiMn2O4 are added into the LiPF6-based electrolyte without or with the mixed additives of ethanolamine and heptamethyldisilazane to be exposed in air at 60 °C for 2-6 h, and the effect of different electrolytes on the storage behavior of LiMn2O4 materials and LiMn2O4/Li cells at elevated temperature is investigated comparatively for the first time by FTIR, SEM, TEM, XRD and charge-discharge measurements. The results show that the electrochemical performances of LiMn2O4 exposed in the LiPF6-based electrolyte become worse gradually with the storage time increasing. However, when the mixture of ethanolamine and heptamethyldisilazane as electrolyte additives is added into the LiPF6-based electrolyte, it can stabilize the original morphology and spinel structure of LiMn2O4 greatly and improve the storage performance of the material and LiMn2O4/Li cells effectively. As the commercial LiMn2O4 is exposed in the LiPF6-based electrolyte with additives for 4 h at 60 °C, the initial discharge capacity of 97.7 mA h g-1 at 0.1 C and the capacity retention of 89.14% at 1 C rate after 150 cycles are much better than that LiMn2O4 exposed in the LiPF6-based electrolyte under the same conditions. Furthermore, the LiMn2O4/Li cells using the LiPF6-based electrolyte with additives exhibit higher initial discharge capacity before storage and higher capacity retention after storage at 60 °C for a week compared to the cells without additives in the LiPF6-based electrolyte.

  12. Synthesis, electrochemical and photophysical properties of heterodinuclear Ru-Mn and Ru-Zn complexes bearing ambident Schiff base ligand.

    Science.gov (United States)

    Guillo, Pascal; Hamelin, Olivier; Loiseau, Frédérique; Pécaut, Jacques; Ménage, Stéphane

    2010-06-28

    While ruthenium tris(diimine) complexes have been extensively studied, this is not the case with ruthenium bis(diimine)X(2) complexes where X represents a pyridinyl-based ligand. The synthesis of a new complex ([2][PF(6)](2)) bearing two ambident Schiff base ligands (HL) constituted by the assembly of phenol and pyridinyl moieties is reported. Thanks to the heteroditopic property of HL, compound [2](2+) was used as an original metalloligand for the coordination of a redox-active (Mn(III)) and redox-inactive (Zn(II)) second metal cation affording three heterodinuclear complexes, namely, [(bpy)(2)Ru(2)Mn(acac)][PF(6)](2) ([3][PF(6)](2); acac = acetylacetonate), [(bpy)(2)Ru(2)Mn(OAc)][PF(6)](2) ([4][PF(6)](2), OAc = acetate), and [(bpy)(2)Ru(2)Zn][PF(6)](2) ([5][PF(6)](2)). The influence of the second metal with regard to the photophysical and electrochemical properties of the ruthenium bis(diimine)X(2) subunit was then investigated. In the case of Ru(II)-Mn(III) heterodinuclear complexes, a partial quenching of the luminescence was observed as a consequence of an efficient electron transfer process from the ruthenium to the manganese. EPR and spectrophotometric analyses of the oxidized species resulting from the one-electron oxidation of compounds [3](2+) and [4](2+) showed the formation of a Mn(IV) species for [3](2+) and an organic free radical for [4](2+). PMID:20485756

  13. Cytotoxicity of Ru(II) piano-stool complexes with chloroquine and chelating ligands against breast and lung tumor cells: Interactions with DNA and BSA.

    Science.gov (United States)

    Colina-Vegas, Legna; Villarreal, Wilmer; Navarro, Maribel; de Oliveira, Clayton Rodrigues; Graminha, Angélica E; Maia, Pedro Ivo da S; Deflon, Victor M; Ferreira, Antonio G; Cominetti, Marcia Regina; Batista, Alzir A

    2015-12-01

    The synthesis and spectroscopic characterization of nine π-arene piano-stool ruthenium (II) complexes with aromatic dinitrogen chelating ligands or containing chloroquine (CQ), are described in this study: [Ru(η(6)-C10H14)(phen)Cl]PF6 (1), [Ru(η(6)-C10H14)(dphphen)Cl]PF6 (2), [Ru(η(6)-C10H14)(bipy)Cl]PF6 (3), [Ru(η(6)-C10H14)(dmebipy)Cl]PF6 (4) and [Ru(η(6)-C10H14)(bdutbipy)Cl]PF6 (5), [Ru(η(6)-C10H14)(phen)CQ](PF6)2 (6), [Ru(η(6)-C10H14)(dphphen)CQ](PF6)2 (7), [Ru(η(6)-C10H14)(bipy)CQ](PF6)2 (8), [Ru(η(6)-C10H14)(dmebipy)CQ](PF6)2 (9): [1,10-phenanthroline (phen), 4,7-diphenyl-1,10-phenanthroline (dphphen), 2,2'-bipyridine (bipy), 5,5'-dimethyl-2,2'-bipyridine (dmebipy), and 4,4'-di-t-butyl-2,2'-bipyridine (dbutbipy)]. The solid state structures of five ruthenium complexes (1-5) were determined by X-ray crystallography. Electrochemical experiments were performed by cyclic voltammetry to estimate the redox potential of the Ru(II)/Ru(III) couple in each case. Their interactions with DNA and BSA, and activity against four cell lines (L929, A549, MDA-MB-231 and MCF-7) were evaluated. Compounds 2, 6 through 9, interact with DNA which was comparable to the one observed for free chloroquine. The results of fluorescence titration revealed that these complexes strongly quenched the intrinsic fluorescence of BSA following a static quenching procedure. Binding constants (Kb) and the number of binding sites (n~1) were calculated using modified Stern-Volmer equations. The thermodynamic parameters ΔG at different temperatures were calculated and subsequently the values of ΔH and ΔS were also calculated, which revealed that hydrophobic and electrostatic interactions play a major role in the BSA-complex association. The MTT assay results indicated that complexes 2, 5 and 7 showed cytostatic effects at appreciably lower concentrations than those needed for cisplatin, chloroquine and doxorubicin. PMID:26277415

  14. Synthesis and characterization of ethylbis(2-pyridylethyl)amineruthenium complexes and two different types of C-H bond cleavage at an ethylene arm.

    Science.gov (United States)

    Fukui, Sohei; Kajihara, Akari; Hirano, Toshiyuki; Sato, Fumitoshi; Suzuki, Noriyuki; Nagao, Hirotaka

    2011-06-01

    Ruthenium complexes bearing ethylbis(2-pyridylethyl)amine (ebpea), which has flexible -C(2)H(4)- arms between the amine and the pyridyl groups and coordinates to a metal center in facial and meridional modes, have been synthesized and characterized. Three trichloro complexes, fac-[Ru(III)Cl(3)(ebpea)] (fac-[1]), mer-[Ru(III)Cl(3)(ebpea)] (mer-[1]), and mer-[Ru(II)Cl(3){η(2)-N(C(2)H(5))(C(2)H(4)py)═CH-CH(2)py}] (mer-[2]), were synthesized using the Ru blue solution. Formation of mer-[2] proceeded via a C-H activation of the CH(2) group next to the amine nitrogen atom of the ethylene arm. Reduction reactions of fac- and mer-[1] afforded a triacetonitrile complex mer-[Ru(II)(CH(3)CN)(3)(ebpea)](PF(6))(2) (mer-[3](PF(6))(2)). Five nitrosyl complexes fac-[RuX(2)(NO)(ebpea)]PF(6) (X = Cl for fac-[4]PF(6); X = ONO(2) for fac-[5]PF(6)) and mer-[RuXY(NO)(ebpea)]PF(6) (X = Cl, Y = Cl for mer-[4]PF(6); X = Cl, Y = CH(3)O for mer-[6]PF(6); X = Cl, Y = OH for mer-[7]PF(6)) were synthesized and characterized by X-ray crystallography. A reaction of mer-[2] in H(2)O-C(2)H(5)OH at room temperature afforded mer-[1]. Oxidation of C(2)H(5)OH in H(2)O-C(2)H(5)OH and i-C(3)H(7)OH in H(2)O-i-C(3)H(7)OH to acetaldehyde and acetone by mer-[2] under stirring at room temperature occurred with formation of mer-[1]. Alternative C-H activation of the CH(2) group occurred next to the pyridyl group, and formation of a C-N bond between the CH moiety and the nitrosyl ligand afforded a nitroso complex [Ru(II)(N(3))(2){N(O)CH(py)CH(2)N(C(2)H(5))C(2)H(4)py}] ([8]) in reactions of nitrosyl complexes with sodium azide in methanol, and reaction of [8] with hydrochloric acid afforded a corresponding chloronitroso complex [Ru(II)Cl(2){N(O)CH(py)CH(2)N(C(2)H(5))C(2)H(4)py}] ([9]). PMID:21517051

  15. Thermodynamic study on the protonation of glycine in different (water + 1-butyl-3-methylimidazolium tetrafluoroborate) mixed solvents and ionic strengths

    International Nuclear Information System (INIS)

    Highlights: • Dependence of glycine protonation constants on ionic strength. • The ionic strength dependence has been modeled with the extended Debye–Hückel equation. • The ionic liquid behaves like a not significantly interacting salt for % IL > 20%. • Kamlet–Abboud–Taft solvatochromic regression coefficients. -- Abstract: The 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim]BF4, is an ionic liquid when pure. The acid base properties of aqueous solutions of [bmim]BF4 were examined by potentiometric titration. Then, protonation constants of glycine in binary mixtures of water and [bmim]BF4 were determined, from potentiometric titration data obtained at T = 298.2 K and various ionic strengths of sodium chloride (0.25 ⩽ I ⩽ 1.00 mol · dm−3). The ionic strength dependence of the equilibrium constants of glycine was fitted to an extended Debye–Hückel equation to derive ionic strength dependence parameters. Comparison with literature data showed that, even at high concentrations, [bmim]BF4 is similar to the electrolyte [(C2H5)4NI], in that it does not interact significantly with other solutes. Solvatochromic parameters in the binary mixtures of water and [bmim]BF4 have been calculated by using Redlich–Kister equation. Kamlet–Abboud–Taft (KAT) solvatochromic equation allows us to determine the values of calculated protonation constants in different media

  16. Temperature-induced microstructural changes in ionic liquid-based microemulsions.

    Science.gov (United States)

    Gao, Yanan; Li, Na; Hilfert, Liane; Zhang, Shaohua; Zheng, Liqiang; Yu, Li

    2009-02-01

    In the present contribution, results concerning the effect of temperature on the nonionic surfactant Triton X-100 based 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4)-in-cyclohexane and bmimBF4-in-toluene ionic liquid (IL) reverse microemulsions are reported. Dynamic light scattering (DLS) along with freeze-fracture transmission electron microscopy (FF-TEM) measurements revealed that the sizes of single microemulsion droplets increased with increasing temperature. However, a decreased temperature led to the appearance of droplet clusters, which have also been observed previously when the single microemulsion droplets were swollen by added bmimBF4 to a certain extent (Gao, Y. A.; Vogit, A.; Hilfert, L.; Sundmacher, K. ChemPhysChem, 2008, 9, 1603-1609). Compared to traditional aqueous microemulsions, IL microemulsions revealed relatively high temperature-independence. The droplet-shaped microstructure was always kept in a large range of temperature. The temperature-independence is ascribed to the temperature-insensitive electrostatic attraction between the solubilized bmimBF4 and Triton X-100, which was considered to be the driving force for solubilizing bmimBF4 into the cores of Triton X-100 aggregates. Two-dimensional rotating frame nuclear Overhauser effect (NOE) experiments (ROESY) further confirmed the microstructural change with temperature. PMID:19132875

  17. E4 Butterfly Complexes (E=P, As) as Chelating Ligands.

    Science.gov (United States)

    Schwarzmaier, Christoph; Heinl, Sebastian; Balázs, Gábor; Scheer, Manfred

    2015-10-26

    The coordination properties of new types of bidentate phosphane and arsane ligands with a narrow bite angle are reported. The reactions of [{Cp'''Fe(CO)2 }2 (μ,η(1:1) -P4 )] (1 a) with the copper salt [Cu(CH3 CN)4 ][BF4 ] leads, depending on the stoichiometry, to the formation of the spiro compound [{{Cp'''Fe(CO)2 }2 (μ3 ,η(1:1:1:1) -P4 )}2 Cu](+) [BF4 ](-) (2) or the monoadduct [{Cp'''Fe(CO)2 }2 (μ3 ,η(1:1:2) -P4 ){Cu(MeCN)}](+) [BF4 ](-) (3). Similarly, the arsane ligand [{Cp'''Fe(CO)2 }2 (μ,η(1:1) -As4 )] (1 b) reacts with [Cu(CH3 CN)4 ][BF4 ] to give [{{Cp'''Fe(CO)2 }2 (μ3 ,η(1:1:1:1) -As4 )}2 Cu](+) [BF4 ](-) (5). Protonation of 1 a occurs at the "wing tip" phosphorus atoms, which is in line with the results of DFT calculations. The compounds are characterized by spectroscopic methods (heteronuclear NMR spectroscopy and IR spectrometry) and by single-crystal X-ray diffraction studies. PMID:26332191

  18. Surface Adsorption and Micelle Formation of Polyoxyethylene-type Nonionic Surfactants in Mixtures of Water and Hydrophilic Imidazolium-type Ionic Liquid.

    Science.gov (United States)

    Misono, Takeshi; Okada, Kohei; Sakai, Kenichi; Abe, Masahiko; Sakai, Hideki

    2016-06-01

    The interfacial properties of polyoxyethylene alkyl ether-type nonionic surfactants (CnEm) were studied in a hydrophilic room-temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), in the presence of water. These properties were assessed using static surface tension, pyrene fluorescence, and dynamic light scattering measurements. The interfacial properties were strongly dependent on the solution composition. Increased water concentration lowered the critical micelle concentration (cmc). The cmc was also affected by the lengths of both the alkyl and polyoxyethylene chains, but a greater impact was observed for the alkyl chain length. These results indicate that micellization occurs as a result of solvophobic interaction between surfactant molecules in the water/bmimBF4 mixed solutions, similar to aqueous surfactant systems. The cloud point phenomenon was observed for CnEm with a relatively low hydrophilic-lipophilic balance (HLB) value, and the relationship between the cloud point and water/bmimBF4 composition exhibited a convex upward curve. Furthermore, the mixing of bmimBF4 with water increased the surfactant solubility for water-rich compositions, suggesting that bmimBF4 acts as a chaotropic salt. PMID:27181249

  19. Electrochemical behavior of aluminum foil in 1-alkyl-3-methylimidazolium tetrafiuoroborate ionic liquids electrolytes

    Institute of Scientific and Technical Information of China (English)

    PENG Chengxin; YANG Li; WANG Baofeng; ZHANG Zhengxi; LI Nan

    2006-01-01

    Aluminum (Al) foil is widely used as a current collector in lithium ion batteries, EDLCs and other electrochemical devices, and its electrochemical behavior in electrolytes has great effect on the cycle performances and safety of the electrochemical devices. In this work, corrosion behavior of Al foil in 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids and its electrolytes containing LiTFSI as salt were studied using cyclic voltammogram method. It was found that a passive film was firmly formed on the surface of Al foil after the anodic polarization in BMI-BF4 compared to those in EMI-BF4 and PMI-BF4.In addition, anodic polarization research showed that the passive film on Al surface in BMI-TFSI did not well exist. A good passive film formed on the surface of Al foil in BMI-BF4 was not broken down until the potential was up to 94.58 V. Moreover, EDX and XPS analysis showed that F and O exist on the Al surface after the anodic polarization in BMI-BF4, which indicated that a passive film like AIF3 and Al2O3 may be formed on its surface.

  20. Catalytic activities of fungal oxidases in hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate-based microemulsion.

    Science.gov (United States)

    Zhou, Gui-Ping; Zhang, Yun; Huang, Xi-Rong; Shi, Chuan-Hong; Liu, Wei-Feng; Li, Yue-Zhong; Qu, Yin-Bo; Gao, Pei-Ji

    2008-10-01

    For hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]), an H(2)O-in-[BMIM][PF(6)] microemulsion could be formed in the presence of nonionic surfactant Triton X-100 (TX-100). In such a medium, both lignin peroxidase (LiP) and laccase could express their catalytic activity with the optimum molar ratio of H(2)O to TX-100 at 8.0 for LiP and >20 for laccase, and the optimum pH values at 3.2 for LiP and 4.2 for laccase, respectively. As compared with pure or water saturated [BMIM][PF(6)], in which the two oxidases had negligible catalytic activity due to the strong inactivating effect of [BMIM][PF(6)] on both enzymes, the use of the [BMIM][PF(6)]-based microemulsion had some advantages. Not only the catalytic activities of both fungal oxidases greatly enhanced, but also the apparent viscosity of the medium decreased. PMID:18602799

  1. Thermal Aging of Anions in Ionic Liquids containing Lithium Salts by IC/ESI-MS

    International Nuclear Information System (INIS)

    Highlights: • Thermal aging investigation of TFSI- and FSI- based ionic liquids and their mixtures with Li salts. • PYR13FSI shows thermal decomposition when mixed with LiPF6 and LiClO4. • PYR13TFSI does not show any decomposition products with the electrolyte salts. • LiPF6 dissolved in ionic liquids suffers of thermal aging as in conventional Li-ion battery electrolytes. - Abstract: The stability of 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR13TFSI) and 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide (PYR13FSI) ionic liquids at elevated temperatures (60 °C) is investigated by ion chromatography. Additionally, the influence of the electrolyte salts, lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium perchlorate (LiClO4), on the decomposition of both the ionic liquids was analysed over a long term stability study. It has been found out that TFSI has a much higher thermal stability than FSI. The addition of LiTFSI did not show any effect on the aging of both ionic liquid anions. However, PYR13FSI degraded when mixed with the electrolyte salts LiPF6 and LiClO4, while PYR13TFSI did not. Finally, LiPF6 forms the same hydrolysis products in the investigated ionic liquids as in the commonly used electrolytes based on organic solvents in lithium-ion batteries

  2. Determination of three physical properties of quinoline ionic liquids with hexafluorophosphate

    Directory of Open Access Journals (Sweden)

    Tang Dan

    2016-01-01

    Full Text Available Densities of one acidic ionic liquid (IL Quinolinum hexafluorophosphate ([HBpy][PF6], and four neutral dicationic ionic liquids (ILs based on quinoline and hexafluoro-phosphate and linked with poly(ethylene glycol (PEG: ([PEG200-DIL][PF6]2, [PEG400-DIL][PF6]2, [PEG800-DIL][PF6]2 and [PEG1000-DIL][PF6]2 were determined. In addition, the solubilities of six ILs in six lower alcohols, water, acetonitrile and diethyl ether were measured at 288.15 K; and the hydroscopicity of above five ILs were measured at the temperature of 298.15 K and relative humidity of 79% for 24 h. Densities of five ionic liquids were determined between 283.15 and 333.15 K. Then the densities of five binary system (ILs/acetonitrile were explored between 283.15 and 333.15 K, the type of the ionic liquid, the concentration of five ILs in CH3CN, and the effect of temperature on the binary systems, were correlated with the measured data.

  3. Research on the LiODFB Electrolyte’s Electrochemical Performance and Its Compatibility with LTO Electrode

    Directory of Open Access Journals (Sweden)

    ZHOU Hong-Ming,LIU Fu-Rong, LI Jian, FANG Zhen-Qi, LI Yan-Fen, ZHU Yu-Hua

    2013-05-01

    Full Text Available 1 mol/L LiODFB (LiPF6 EC+DMC+EMC (1:1:1 (wt% electrolyte’s thermal stability and corrosivity to the aluminum foil were tested by the electrochemical workstation. Cyclic voltammogram, electrochemical impedance spectroscopy rate and cycle performances of LTO/Li battery were measured. The compatibility between LiFePO4/LTO electrode and electrolyte was studied. Results show that at room temperature and 60¡䪠the stability of LiODFB electrolyte and its corrosivity to the aluminum foil are superior to that of LiPF6 electrolyte. LTO/Li cells with either LiODFB or LiPF6 for electrolyte have simple REDOX peak, and their first charge-discharge curves have stable charge-discharge platform. The difference battery performance between LiODFB and LiPF6 with LiFePO4/LTO as electrode at 0.5C and 1C rates is not significant at room temperature. LiODFB battery exhibits better cycle performance than LiPF6 battery at room temperature and especially at 60¡䬍

  4. Acetylcholine-like and trimethylglycine-like PTA (1,3,5-triaza-7-phosphaadamantane) derivatives for the development of innovative Ru- and Pt-based therapeutic agents.

    Science.gov (United States)

    Ferretti, Valeria; Fogagnolo, Marco; Marchi, Andrea; Marvelli, Lorenza; Sforza, Fabio; Bergamini, Paola

    2014-05-19

    The PTA N-alkyl derivatives (PTAC2H4OCOMe)X (1X: 1a, X = Br; 1b, X = I; 1c, X = PF6; 1d, X = BPh4), (PTACH2COOEt)X (2X: 2a, X = Br; 2b, X = Cl; 2c, X = PF6), and (PTACH2CH2COOEt)X (3X: 3a, X = Br; 3c, X = PF6), presenting all the functional groups of the natural cationic compounds acetylcholine or trimethylglycine combined with a P-donor site suitable for metal ion coordination, were prepared and characterized by NMR, ESI-MS, and elemental analysis. The X-ray crystal structures of 1d and 2c were determined. Ligands 1c, 2b, and 3c were coordinated to Pt(II) and Ru(II) to give the cationic complexes cis-[PtCl2(L)2]X2 and [RuCpCl(PPh3)(L)]X (L = 1, 2, 3, X = Cl or PF6) designed with a structure targeted for anticancer activity. The X-ray crystal structure of [CpRu(PPh3)(PTAC2H4OCOMe)Cl]PF6 (1cRu) was determined. The antiproliferative activity of the ligands and the complexes was evaluated on three human cancer cell lines. PMID:24801393

  5. Sub-picosecond time resolved infrared spectroscopy of high-spin state formation in Fe(II) spin crossover complexes

    DEFF Research Database (Denmark)

    Døssing, Anders Rørbæk; Wolf, Matthias M. N.; Gross, Ruth;

    2008-01-01

      The photoinduced low-spin (S = 0) to high-spin (S = 2) transition of the iron(II) spin-crossover systems [Fe(btpa)](PF6)2 and [Fe(b(bdpa))](PF6)2 in solution have been studied for the first time by means of ultrafast transient infrared spectroscopy at room temperature. Negative and positive...... infrared difference bands between 1000 and 1065 cm-1 that appear within the instrumental system response time of 350 fs after excitation at 387 nm display the formation of the vibrationally unrelaxed and hot high-spin 5T2 state. Vibrational relaxation is observed and characterized by the time constants 9.......4 ± 0.7 ps for [Fe(btpa)](PF6)2/acetone and 12.7 ± 0.7 ps for both [Fe(btpa)](PF6)2/acetonitrile and [Fe(b(bdpa)](PF6)2/acetonitrile. Vibrational analysis has been performed via DFT calculations of the low-spin and high-spin state normal modes of both compounds as well as their respective infrared...

  6. Electrochemical behavior of labetalol at an ionic liquid modified carbon paste electrode and its electrochemical determination

    Directory of Open Access Journals (Sweden)

    Zhang Yan-Mei

    2013-01-01

    Full Text Available Electrochemical behavior of labetalol (LBT at carbon paste electrode (CPE and an ionic liquid1-benzyl-3-methylimidazolehexafluorophosphate([BnMIM]PF6modified carbon paste electrode([BnMIM]PF6/CPEin Britton-Robinson buffer solution (pH 2.0 was investigated by cyclic voltammetry (CV and square wave voltammetric (SWV. The experimental results showed that LBT at both the bare CPE and [BnMIM]PF6/CPEshowed an irreversible oxidation process, but at [BnMIM]PF6/CPE its oxidation peak current increased greatly and the oxidation peak potential shifted negatively. The electrode reaction process is a diffusion-controlled process involving one electron transferring accompanied by a participation of one proton at [BnMIM]PF6/CPE. At the same time, the electrochemical kinetic parameters were determined. Under the optimized electrochemical experimental conditions, the oxidation peak currents were proportional to LBT concentration in the range of 7.0 x 10-6-1.0 x 10-4 mol L-1 with the limit of detection(LOD, S/N=3 of 4.810 x 10-8 mol L-1and the limit of quantification(LOQ, S/N=10 of 1.60 x 10-7 mol L-1, respectively. The proposed method was successfully applied in the determination of LBT content in commercial tablet samples.

  7. Phase transition of carbonate solvent mixture solutions at low temperatures

    Science.gov (United States)

    Okumura, Takefumi; Horiba, Tatsuo

    2016-01-01

    The phase transition of carbonate solvent mixture solutions consisting of ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and LiPF6 salt have been studied for improving the low temperature performance of lithium-ion batteries. The Li ion conductivity at 25 °C was maximum at x = 0.3 in a series of 1 M LiPF6 mixed carbonate solvents compositions consisting of ECxDMC0.5-0.5xEMC0.5-0.5x (x = 0 to 0.6), while the maximum tended to shift to x = 0.2 as the temperature lowered. The differential scanning calorimetry results showed that the freezing temperature depressions of EC in the 1 M LiPF6 solution were larger than those of the DMC or EMC. The chemical shift of 7Li nuclear magnetic resonance changed from a constant to increasing at around x = 0.3, which could be reasonably understood by focusing on the change in solvation energy calculated using Born equation. However, in the region of a high EC concentration of over x = 0.3 (EC/LiPF6 > 4) in the 1 M LiPF6 solution, the free EC from the solvation to the lithium ions seems to reduce the freezing temperature depression of the EC, and thus, decreases the ionic conductivity of the solution at low temperatures, due to the EC freezing.

  8. Influence of the organization of water-in-ionic liquid microemulsions on the size of silver particles during photoreduction.

    Science.gov (United States)

    Harada, Masafumi; Yamada, Masako; Kimura, Yoshifumi; Saijo, Kenji

    2013-09-15

    Metal particles of silver (Ag) have been synthesized by the photoreduction of silver nitrate (AgNO3) in water-in-ionic liquid (IL) microemulsions consisting of nonionic surfactant Tween 20 or Triton X-100, water and ionic liquid, 1-octyl-3-methylimidazolium hexafluorophosphate ([OMIm][PF6]). The formation of microemulsions as well as Ag particles produced by the photoreduction has been investigated by UV-vis, cryo-TEM, small-angle X-ray scattering (SAXS), and extended X-ray absorption fine structure (EXAFS) measurements. At the early stage of Ag particle formation under ambient pressure, the size of Ag particles in water/[OMIm][PF6]/TX-100 microemulsions was slightly larger than that in water/[OMIm][PF6]/Tween20 microemulsions. With an increase in photoirradiation time beyond 30 min, precipitation of larger Ag aggregates occurred. In contrast to the preparation under ambient pressure, the growth of Ag particles and aggregates was suppressed in preparing under high pressure (25 MPa) of CO2, leading to no precipitation of Ag aggregates. The average diameters of the finally-obtained metallic Ag particles prepared under high pressure of CO2 in water/[OMIm][PF6]/Tween20 and water/[OMIm][PF6]/TX-100 microemulsions were estimated from cryo-TEM to be 3.7 nm and 2.8 nm, respectively. By using Guinier plots at q (microemulsions. PMID:23791230

  9. Removal of multiple electron acceptors by pilot-scale, two-stage membrane biofilm reactors.

    Science.gov (United States)

    Zhao, He-Ping; Ontiveros-Valencia, Aura; Tang, Youneng; Kim, Bi-O; Vanginkel, Steven; Friese, David; Overstreet, Ryan; Smith, Jennifer; Evans, Patrick; Krajmalnik-Brown, Rosa; Rittmann, Bruce

    2014-05-01

    We studied the performance of a pilot-scale membrane biofilm reactor (MBfR) treating groundwater containing four electron acceptors: nitrate (NO3(-)), perchlorate (ClO4(-)), sulfate (SO4(2-)), and oxygen (O2). The treatment goal was to remove ClO4(-) from ∼200 μg/L to less than 6 μg/L. The pilot system was operated as two MBfRs in series, and the positions of the lead and lag MBfRs were switched regularly. The lead MBfR removed at least 99% of the O2 and 63-88% of NO3(-), depending on loading conditions. The lag MBfR was where most of the ClO4(-) reduction occurred, and the effluent ClO4(-) concentration was driven to as low as 4 μg/L, with most concentrations ≤10 μg/L. However, SO4(2-) reduction occurred in the lag MBfR when its NO3(-) + O2 flux was smaller than ∼0.18 g H2/m(2)-d, and this was accompanied by a lower ClO4(-) flux. We were able to suppress SO4(2-) reduction by lowering the H2 pressure and increasing the NO3(-) + O2 flux. We also monitored the microbial community using the quantitative polymerase chain reaction targeting characteristic reductase genes. Due to regular position switching, the lead and lag MBfRs had similar microbial communities. Denitrifying bacteria dominated the biofilm when the NO3(-) + O2 fluxes were highest, but sulfate-reducing bacteria became more important when SO4(2-) reduction was enhanced in the lag MBfR due to low NO3(-) + O2 flux. The practical two-stage strategy to achieve complete ClO4(-) and NO3(-) reduction while suppressing SO4(2-) reduction involved controlling the NO3(-) + O2 surface loading between 0.18 and 0.34 g H2/m(2)-d and using a low H2 pressure in the lag MBfR. PMID:24565802

  10. Chemistry of a binuclear cadmium(II) hydroxide complex: formation from water, CO(2) reactivity, and comparison to a zinc analog.

    Science.gov (United States)

    Allred, Russell A; McAlexander, Lenore H; Arif, Atta M; Berreau, Lisa M

    2002-12-16

    Treatment of the bmnpa (N,N-bis-2-(methylthio)ethyl-N-((6-neopentylamino-2-pyridyl)methyl)amine) ligand with equimolar amounts of Cd(ClO(4))(2).5H(2)O and Me(4)NOH.5H(2)O in CH(3)CN yielded the binuclear cadmium hydroxide complex [((bmnpa)Cd)(2)(mu-OH)(2)](ClO(4))(2).CH(3)CN (1). Complex 1 may also be prepared (a) by treatment of a CH(3)CN solution of (bmnpa)Cd(ClO(4))(2) (2) with 1 equiv of n-BuLi, followed by treatment with water or (b) from 2 in the presence of 1 equiv each of water and NEt(3). The hydroxide derivative 1 is not produced from 2 and water in the absence of an added base. Complex 1 possesses a binuclear structure in the solid state with hydrogen-bonding and CH/pi interactions involving the bmnpa ligand. The overall structural features of 1 differ from the halide derivative [((bmnpa)Cd)(2)(mu-Cl)(2)](ClO(4))(2) (3), particularly in that the Cd(2)(mu-OH)(2) core of 1 is symmetric whereas the Cd(2)(mu-Cl)(2) core of 3 is asymmetric. In acetonitrile solution, 1 behaves as a 1:2 electrolyte and retains a binuclear structure and secondary hydrogen-bonding and CH/pi interactions, whereas 3 is a 1:1 electrolyte, indicating formation of a mononuclear [(bmnpa)CdCl]ClO(4) species in solution. Treatment of 1 with CO(2) in anhydrous CH(3)CN yields the bridging carbonate complex [((bmnpa)Cd)(2)(mu-CO(3))](ClO(4))(2).CH(3)CN (4). Treatment of a chemically similar zinc hydroxide complex, [((benpa)Zn)(2)(mu-OH)(2)](ClO(4))(2) (benpa = N,N-bis-2-(ethylthio)ethyl-N-((6-neopentylamino-2-pyridyl)methyl)amine, with CO(2) also results in the formation of a carbonate derivative, [((benpa)Zn)(2)(mu-CO(3))](ClO(4))(2) (5), albeit the coordination mode of the bridging carbonate moiety is different. Treatment of 4 with added water results in no reaction, whereas 5 under identical conditions will undergo reaction to yield the zinc hydroxide complex [((benpa)Zn)(2)(mu-OH)(2)](ClO(4))(2). PMID:12470076

  11. The effects of surface oxidation and fluorination of boron-doped diamond anodes on perchlorate formation and organic compound oxidation

    International Nuclear Information System (INIS)

    This research investigated the effects of surface functional groups on both rates of organic compound oxidation (phenol, p-nitrophenol, benzoquinone, and oxalic acid) and perchlorate (ClO4−) formation at boron-doped diamond (BDD) film anodes at 20 °C. X-ray photoelectron spectroscopy measurements determined that various oxygenated functional groups (e.g., C-OH, C=O, COOH) were incorporated on the BDD surface by applying an anodic ageing process, and fluorine functional groups (e.g., C-F, -CnF2n+1) were incorporated by electrochemical oxidation of aqueous perfluorooctanoic acid solutions. Batch oxidation experiments revealed that ClO4− formation via the oxidation of ClO3− was highly variable during anodic ageing, which was attributed to changes in oxygenated functional groups, while organic compound oxidation rates were not significantly affected. The fluorinated electrode showed a lower ClO4− formation rate (19 ± 4 μmoles m−2 min−1) compared to the oxygenated electrode (436 ± 26 μmoles m−2 min−1) indicating the fluorinated surface limits ClO4− production. Measurement of the electrode response to the Fe(CN)63−/4− redox couple using cyclic voltammetry and electrochemical impedance spectroscopy indicated that lower ClO4− formation on the fluorinated electrode was likely a result of dipole-dipole interactions between the negatively charged F atoms and ClO3− and steric hindrance caused by the perfluorocarbon chains. This effect along with the hydrophobicity of the fluorinated electrode resulted in significantly lower ClO4− formation (96% decrease) while slightly enhancing measured oxidation rates of hydrophobic organic compounds. The use of benzoquinone as OH· probe confirmed that the fluorination process did not inhibit OH· production. The rate of benzoquinone oxidation was 2212 ± 183 μmoles m−2 min−1 on the oxygenated electrode and 2926 ± 201 μmoles m−2 min−1 on the fluorinated electrode. Density functional theory calculations indicated that the fluorination of the BDD surface by both F atoms and perfluorinated carbon radicals (·CnF2n+1) of varying chain lengths (n = 1 to 7) was feasible, and that the fluorinated edge sites (=C-CnF2n+1) were more electrochemically stable than fluorinated planar sites (≡C-CnF2n+1)

  12. Department of Nuclear Radiospectroscopy - Overview

    International Nuclear Information System (INIS)

    Research at the Department of Nuclear Radiospectroscopy concerns various aspects of the NMR and its applications to solids and to biosystems. The research activity covers: investigation of molecular dynamics and structures in solids using NMR spectroscopy, and investigation of humans, animals and plants using NMR imaging and localized spectroscopy. The MR Laboratory is equipped with a 7.05 T wide bore vertical superconducting magnet (SCM) with a pulse spectrometer. It allows to measure of deuteron NMR spectra at T ≥ 5 K. NMR high resolution spectra for 29Si, 11B, 27Al and 31P nuclei can be measured using MAS-NMR probe heads. The Magnetic Resonance Imaging Laboratory is equipped with 360 MHz MR microscope based on a 8.4 T narrow bore SCM and a MRI/MRS system based on a 2 T, 31 cm horizontal bore SCM. Magnetic Resonance Laboratory: Molecular reorientation studies aimed at disclosing tunnelling rotation and structural research of amorphous solids were main topics. Realisation of these projects required a development of our NMR pulse spectrometer and theoretical methods. The spectrometer was put into operation in 1997. Recent development was done in the data acquisition by the introduction of a new A/D converter and a pulse programmer. Tunnelling and reorientations of mixed isotope rotors are currently the most interesting topics. For a given deuteration rate of an ammonium compound it was anticipating that deuteron NMR spectra consist of weighted contributions from the following isotopomers: NH3D+, NH2D2+, NH3D+ and ND4+. Each isotopomer provides a characteristic spectral component due to its mobility. Measurements were performed for a number of partially deuterated samples of (NH4)2S2O8, NH4ClO4, NH4PF6, (NH4)2ZnCl4 and (NH4)2TeCl6 in the T = 5-100 K. The spectra of NH3D+ ions are particularly interesting. A new effect of an isotope ordering was observed. The structural investigations of amorphous solids by NMR technique have obtained a major boost this year due a

  13. The low-temperature phase of morpholinium tetra-fluoro-borate.

    Science.gov (United States)

    Owczarek, Magdalena; Szklarz, Przemyslaw; Jakubas, Ryszard; Lis, Tadeusz

    2008-01-01

    The crystal structure of the low-temperature form of the title compound, C(4)H(10)NO(+)·BF(4) (-), was determined at 80 K. Two reversible phase transitions, at 158/158 and 124/126 K (heating/cooling), were detected by differential scanning calorimetry for this compound, and the sequence of phase transitions was subsequently confirmed by single-crystal X-ray diffraction experiments. The asymmetric unit at 80 K consists of three BF(4) (-) tetra-hedral anions and three morpholinium cations (Z' = 3). Hydrogen-bonded morpholinium cations form chains along the [100] direction. The BF(4) (-) anions are connected to these chains by N-H⋯F hydrogen bonds. In the crystal structure, two different layers perpendicular to the [001] direction can be distinguished, which differ in the geometry of the hydrogen bonds between cationic and anionic species. PMID:21202061

  14. The low-temperature phase of morpholinium tetra­fluoro­borate

    Science.gov (United States)

    Owczarek, Magdalena; Szklarz, Przemyslaw; Jakubas, Ryszard; Lis, Tadeusz

    2008-01-01

    The crystal structure of the low-temperature form of the title compound, C4H10NO+·BF4 −, was determined at 80 K. Two reversible phase transitions, at 158/158 and 124/126 K (heating/cooling), were detected by differential scanning calorimetry for this compound, and the sequence of phase transitions was subsequently confirmed by single-crystal X-ray diffraction experiments. The asymmetric unit at 80 K consists of three BF4 − tetra­hedral anions and three morpholinium cations (Z′ = 3). Hydrogen-bonded morpholinium cations form chains along the [100] direction. The BF4 − anions are connected to these chains by N—H⋯F hydrogen bonds. In the crystal structure, two different layers perpendicular to the [001] direction can be distinguished, which differ in the geometry of the hydrogen bonds between cationic and anionic species. PMID:21202061

  15. 直接甲醇燃料电池用离子液体复合膜的制备及性能研究

    Institute of Scientific and Technical Information of China (English)

    苗睿瑛; 方勇; 唐玲; 李建玲; 王新东

    2009-01-01

    制备了直接甲醇燃料电池用的2种离子液体([α-MPyH][Tfa]和[EMIm][BF4])复合膜,并对二者的微观形貌以及电化学特征予以表征.阻抗测试结果表明,[EMIm][BF4]复合膜的电导率高于[α-MPyH][Tfa]复合膜,计时电流法对二者阻醇性能研究结果表明,[EMIm][BF4]复合膜的阻醇性能也好于[α-MPyH][Tfa]复合膜.

  16. Solid polymer electrolyte 49 % poly(methyl methacrylate)-grafted natural rubber-lithium tetrafluoroborate)

    International Nuclear Information System (INIS)

    The potential of 49 % poly(methyl methacrylate) grafted natural rubber (MG49) as a solid polymer electrolyte film for application in electrochemical device system has been investigated. The MG49 films with LiBF4 as a doping salt were prepared by solution casting technique. The ionic conductivity investigated by electrochemical impedance spectroscopy showed the optimum ionic conductivity was given by 25 wt % of LiBF4 salt loading with ionic conductivity value, 1.49 x 10-9 S.cm-1 at room temperature. The observation on structural and morphology studies have been done by X-ray diffraction and scanning electron microscopy. Results showed that complexation and crystallization occurred in polymer electrolyte system. This gave low electrical conductivity value even though the addition of LiBF4 salt has reached the optimum level. (author)

  17. Acceleration effect of ionic liquids on polycyclotrimerization of dicyanate esters

    Directory of Open Access Journals (Sweden)

    A. Fainleib

    2016-09-01

    Full Text Available The polycyclotrimerization reaction of dicyanate ester of bisphenol E (DCBE in the presence of varying amounts (from 0.5 to 5 wt% of 1-octyl-3-methylimidazolium tetrafluoroborate ([OMIm][BF4] ionic liquid has been investigated using differential scanning calorimetry (DSC and Fourier transform infrared spectroscopy (FTIR techniques, after a curing stage at 150 °C for 6 h. It is noteworthy that an amount of [OMIm][BF4] as low as 0.5 wt% accelerates dramatically the thermal curing process leading to the formation of a polycyanurate network. The conversion of DCBE increased with increasing [OMIm][BF4] content in the temperature range studied. A reaction mechanism associated with the ionic liquid-catalyzed DCBE polycyclotrimerization is newly proposed via the involvement of a [CN]δ+–[OMIm]δ– complex as a key intermediate.

  18. Hydrogen production by water electrolysis using tetra-alkyl-ammonium-sulfonic acid ionic liquid electrolytes

    Science.gov (United States)

    Fiegenbaum, Fernanda; Martini, Emilse M.; de Souza, Michèle O.; Becker, Márcia R.; de Souza, Roberto F.

    2013-12-01

    Triethylammonium-propanesulfonic acid tetrafluoroborate (TEA-PS·BF4) is used as an electrolyte in the water electrolysis. The electrolysis of water with this ionic conductor produces high current densities with high efficiencies, even at room temperatures. A system using TEA-PS·BF4 in an electrochemical cell with platinum electrodes has current densities (i) up to 1.77 A cm-2 and efficiencies between 93 and 99% in temperatures ranging from 25 °C to 80 °C. The activation energy observed with TEA-PS·BF4 is ca. 9.3 kJ mol-1, a low value that can be explained by the facilitation of proton transport in the organised aqueous ionic liquid media. The unexpectedly high efficiency of this system is discussed by taking into account the high conductivities associated with the Brönsted and Lewis acidity characteristics associated with these ionic conductive materials.

  19. Mesoporous Silica Materials Synthesized via Sol-Gel Methods Modified with Ionic Liquid and Surfactant Molecules

    Institute of Scientific and Technical Information of China (English)

    Cun-ying Xu; Ru-lan Tang; Yi-xin Hu; Peng-xiang Zhang

    2008-01-01

    Mesoporous silica materials were synthesized via a sol-gel method employing a room temperature ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF4]) as a new solvent medium and further modified with surfactant (hexadecyl-trimethyl-ammonium bromide, CTAB) as a pore templating material. The synthesized samples were characterized by the transmission electron microscopy, X-ray diffraction, and N2 adsorption-desorption techniques. The results indicated that the mesoporous silica synthesized by using [bmim][BF4] and CTAB as mixed templates showed better mesostructural order and smaller pore size, compared with mesoporous silica materials synthesized by using single [bmim][BF4]as template under the same conditions. This indicates that the presence of surfactant can affect the microstructures of silica prepared by the present synthesis method.

  20. Preparation and Characterization of a Novel Benzimidazolium Br(φ)nsted Acid Ionic Liquid and Its Application in the Synthesis of Arylic Esters

    Institute of Scientific and Technical Information of China (English)

    WANG,Yuan-Yuan; LI,Wei; XU,Cheng-Di; DAI,Li-Yi

    2007-01-01

    A novel Brφnsted acid task specific ionic liquid 1-ethylbenzimidazolium tetrafluoroborate ([Hebim]BF4) with functional benzimidazolium cation was synthesized and characterized by 1H NMR, IR, MS spectra and elemental analysis. This novel ionic liquid was successfully used as dual solvent-catalyst for the synthesis of arylic esters.Higher yields were obtained in the presence of [Hebim]BF4 in comparison with other imidazolium ionic liquids because of the good solubility of the aromatic alcohols and aromatic carboxylic acids in [Hebim]BF4. The product could be separated conveniently from the reaction system, and the ionic liquid could be easily reused after removal of water under vacuum. After 10 times reuse, the selectivity of the ester was still 100%.

  1. Studies on gel electrolyte based on nitrile-butadiene copolymers. Final report, 1 November 1991-30 November 1992

    Energy Technology Data Exchange (ETDEWEB)

    Sircar, A.K.; Kumar, B.; Linden, S.M.; Weissman, P.T.

    1993-06-01

    This study is concerned with the preparation of a hybrid electrolyte, suitable for solid-polymer batteries. Based on the study of ionic conductivity in the presence of LiBF4 of a number of nitrile-butadiene copolymers (NBR), hydrogenated NBR (HNBR) was selected as the host polymer. DC conductivity studies with three different lithium salts in different plasticizers showed the highest conductivity for LiBF4. Conductivity of LiBF4 in different plasticizers decreases in the order DMF > DMAC > Gamma butyrolactone > NMP > PC=gamma-valerolactone > glymes. NMP was chosen as the plasticizer for hybrid films based on its moderate conductivity, low vapor pressure, and low freezing point. Polymer electrolytes, Gel electrolytes, Ionic conductivity.

  2. The low-temperature phase of morpholinium tetrafluoroborate

    Directory of Open Access Journals (Sweden)

    Tadeusz Lis

    2008-04-01

    Full Text Available The crystal structure of the low-temperature form of the title compound, C4H10NO+·BF4−, was determined at 80 K. Two reversible phase transitions, at 158/158 and 124/126 K (heating/cooling, were detected by differential scanning calorimetry for this compound, and the sequence of phase transitions was subsequently confirmed by single-crystal X-ray diffraction experiments. The asymmetric unit at 80 K consists of three BF4− tetrahedral anions and three morpholinium cations (Z′ = 3. Hydrogen-bonded morpholinium cations form chains along the [100] direction. The BF4− anions are connected to these chains by N—H...F hydrogen bonds. In the crystal structure, two different layers perpendicular to the [001] direction can be distinguished, which differ in the geometry of the hydrogen bonds between cationic and anionic species.

  3. Generalizations of the Fuoss Approximation for Ion Pairing

    CERN Document Server

    Zhu, P; Pratt, L R; Papadopoulos, K D

    2010-01-01

    An elementary statistical observation identifies generalizations of the Fuoss approximation for the probability distribution function that describes ion clustering in electrolyte solutions. By exploiting measurable inter-ionic correlation functions, this generalization is correct at the closest pair distances, extends beyond primitive electrolyte solution models, and includes non-ionic interactions and solvation effects. The proposed generalization is relevant also for the computational analysis of bi-molecular reactive processes in solution. Comparisons with direct numerical simulation results show that the simplest generalization is accurate for a slightly supersaturated solution of tetraethylammonium tetrafluoroborate in propylene carbonate ([tea][BF4]/PC), and also for a primitive model associated with the [tea][BF4]/PC results. For [tea][BF4]/PC, the atomically detailed results identify solvent-separated nearest-neighbor ion-pairs. This generalization is examined also for the ionic liquid 1-butyl-3-methy...

  4. (2,2′-Bipyridine-κ2N,N′bromido(1,4,7-trithiacyclononane-κ3S,S′,S′′ruthenium(II hexafluoridophosphate

    Directory of Open Access Journals (Sweden)

    José A. Fernandes

    2011-02-01

    Full Text Available The title compound, [RuBr(C10H8N2(C6H12S3]PF6 or [RuBr(bpy([9]aneS3]PF6 ([9]aneS3 is 1,4,7-trithiacyclononane and bpy is 2,2′-bipyridine, exhibits a very similar octahedral coordination geometry for the Ru2+ atom to that of its [RuCl(bpy([9]aneS3]+ analogue, with only the chloride ligand being substituted by a bromide ligand. The presence of a PF6− anion (alongside with the coordinated bromide ligand promotes the existence of an extensive network of weak C—H...X (X = F, Br interactions.

  5. Formation of a robust and stable film comprising ionic liquid and polyoxometalate on glassy carbon electrode modified with multiwalled carbon nanotubes: Toward sensitive and fast detection of hydrogen peroxide and iodate

    International Nuclear Information System (INIS)

    A robust and stable film comprising n-octylpyridinum hexafluorophosphate ([C8Py][PF6]) and 1:12 phosphomolybdic acid (PMo12) was prepared on glassy carbon electrodes modified with multiwall carbon nanotubes (GCE/MWCNTs) by dip-coating. The cyclic voltammograms of the GCE/MWCNTs/[C8Py][PF6]-PMo12 showed three well-defined pairs of redox peaks due to the PMo12 system. The surface coverage for the immobilized PMo12 and the average values of the electron transfer rate constant for three pairs of redox peaks were evaluated. The GCE/MWCNTs/[C8Py][PF6]-PMo12 showed great electrocatalytic activity towards the reduction of H2O2 and iodate. The kinetic parameters of the catalytic reduction of hydrogen peroxide and iodate at the electrode surface and analytical features of the sensor for amperometric determination of hydrogen peroxide and iodate were evaluated.

  6. Low-temperature metallic state and superconductivity in quasi-one-dimensional organic conductors: pressure and irradiation investigations

    International Nuclear Information System (INIS)

    The comparison between the disordered metallic state created by irradiation and the metallic regime stabilised by high pressure in TMTSF-DMTCNQ and TMTSF2-PF6 establishes the existence of a contribution from superconducting fluctuations to the conductivity below 50 K. A calculation using Ginzburg-Landau theory is in very good agreement with the experimental temperature dependence of the paraconductivity. It is shown that the metal-insulator transition in TMTSF2-PF6 is shifted by the disorder to a lower temperature. However, the effect is less for the spin-density-wave transition in TMTSF-PF6 than for the charge-density-wave ordering in TMTSF-DMTCNQ. Finally it is shown that the superconductivity transition is strongly depressed by irradiation-induced defects. (author)

  7. Effects of solvents and salt on the thermal stability of lithiated graphite used in lithium ion battery.

    Science.gov (United States)

    Wang, Qingsong; Sun, Jinhua; Chen, Chunhua

    2009-08-15

    The thermal stability of lithiated graphite in the presence of solvents, electrolytes and LiPF(6) salt was studied using C80 micro-calorimeter. The presence of cyclic carbonates or linear carbonates increases the activity of Li(x)C(6)-solvent coexisting system, especially for the Li(x)C(6)-linear carbonates one. LiPF(6) was detected that it increases the activity greatly of its coexisting system with lithiated graphite. The coexisting system of Li(x)C(6) with the electrolyte of LiPF(6)/ethylene carbonate+diethyl carbonate shows less thermal stability, which is attributed to the activity between diethyl carbonate and Li(x)C(6). This also agrees with the experiment result of Li(x)C(6)-diethyl carbonate coexisting system. PMID:19261386

  8. Structural, NMR, and EPR studies of S = (1)/(2) and S = (3)/(2) Fe(III) bis(4-cyanopyridine) complexes of dodecasubstituted porphyrins.

    Science.gov (United States)

    Yatsunyk, Liliya A; Walker, F Ann

    2004-01-26

    The NMR and EPR spectra for three complexes, iron(III) octamethyltetraphenylporphyrin bis(4-cyanopyridine) perchlorate, [FeOMTPP(4-CNPy)(2)]ClO(4), and its octaethyl- and tetra-beta,beta'-tetramethylenetetraphenylporphyrin analogues, [FeOETPP(4-CNPy)(2)]ClO(4) and [FeTC(6)TPP(4-CNPy)(2)]ClO(4), are presented. The crystal structures of two different forms of [FeOETPP(4-CNPy)(2)]ClO(4) and one form of [FeOMTPP(4-CNPy)(2)]ClO(4) are also reported. Attempts to crystallize [FeTC(6)TPP(4-CNPy)(2)]ClO(4) were not successful. The crystal structure of [FeOMTPP(4-CNPy)(2)]ClO(4) reveals a saddled porphyrin core, a small dihedral angle between the axial ligand planes, 64.3 degrees, and an unusually large tilt angle (24.4 degrees ) of one of the axial 4-cyanopyridine ligands with respect to the normal to the porphyrin mean plane. There are 4 and 2 independent molecules in the asymmetric units of [FeOETPP(4-CNPy)(2)]ClO(4) crystallized from CD(2)Cl(2)/dodecane (1-4) and CDCl(3)/cyclohexane (5-6), respectively. The geometries of the porphyrin cores in 1-6 vary from purely saddled to saddled with 15% ruffling admixture. In all structures, the Fe-N(p) distances (1.958-1.976 A) are very short due to strong nonplanar distortion of the porphyrin cores, while the Fe-N(ax) distances are relatively long ( approximately 2.2 A) compared to the same distances in S = (1)/(2) bis(pyridine)iron(III) porphyrin complexes. An axial EPR signal is observed (g( perpendicular ) = 2.49, g( parallel ) = 1.6) in frozen solutions of both [FeOMTPP(4-CNPy)(2)]ClO(4) and [FeTC(6)TPP(4-CNPy)(2)]ClO(4) at 4.2 K, indicative of the low spin (LS, S = (1)/(2)), (d(yz)d(xz))(4)(d(xy))(1) electronic ground state for these two complexes. In agreement with a recent publication (Ikeue, T.; Ohgo, Y.; Ongayi, O.; Vicente, M. G. H.; Nakamura, M. Inorg. Chem. 2003, 42, 5560-5571), the EPR spectra of [FeOETPP(4-CNPy)(2)]ClO(4) are typical of the S = (3)/(2) state, with g values of 5.21, 4.25, and 2.07. A small amount of LS species with g = 3.03 is also present. However, distinct from previous conclusions, large negative phenyl-H shift differences delta(m) - delta(o) and delta(m) - delta(p) in the (1)H NMR spectra indicate significant negative spin density at the meso-carbons, and the larger than expected positive average CH(2) shifts are also consistent with a significant population of the S = 2 Fe(II), S = (1)/(2) porphyrin pi-cation radical state, with antiferromagnetic coupling between the metal and porphyrin unpaired electrons. This is the first example of this type of porphyrin-to-metal electron transfer to produce a partial or complete porphyrinate radical state, with antiferromagnetic coupling between metal and macrocycle unpaired electrons in an iron porphyrinate. The kinetics of ring inversion were studied for the [FeOETPP(4-CNPy)(2)]ClO(4) complex using NOESY/EXSY techniques and for the [FeTC(6)TPP(4-CNPy)(2)]ClO(4) complex using DNMR techniques. For the former, the free energy of activation, deltaG, and rate of ring inversion in CD(2)Cl(2) extrapolated to 298 K are 63(2) kJ mol(-)(1) and 59 s(-)(1), respectively, while for the latter the rate of ring inversion at 298 K is at least 4.4 x 10(7) s(-)(1), which attests to the much greater flexibility of the TC(6)TPP ring. The NMR and EPR data are consistent with solution magnetic susceptibility measurements that show S = (3)/(2) in the temperature range from 320 to 180 K for [FeOETPP(4-CNPy)(2)](+), while both [FeOMTPP(4-CNPy)(2)](+) and [FeTC(6)TPP(4-CNPy)(2)](+) change their spin state from S = (3)/(2) at room temperature to mainly LS (S = (1)/(2)) upon cooling to 180 K. PMID:14731040

  9. Molecular Simulation on Microstructure of Ionic Liquids in Capture of CO2

    Institute of Scientific and Technical Information of China (English)

    YUE Zhen-uo; LIU Xiao-min; ZHAO Yu-ling; ZHANG Xiao-chun; LU Xing-mei; ZHANG Suo-jiang

    2011-01-01

    Molecular dynamic simulation is used to study the microstructure of four kinds of ionic liquids (ILs),[Emim]PF6,[Emim][Tf2N],[PC6,6,6,14]PF6 and [PC6,6,6,14][Tf2N] in the capture process of CO2.Radial distribution function (RDF) and spatial distribution function (SDF) are used to analyze the microscopic properties of these systems.The calculated results show that the space distribution of CO2 around ILs determines the capability of ionic liquids for capturing CO2.Based on the analysis of SDF,CO2 and PF6- are overlapped partially around [Emim]+ in [Emim]PF6-CO2 mixture.When the anion is [Tf2N]-,cations are mainly distributed on one side of [Tf2N]- near N atom,and CO2 is concentrated on two sides near the fluoroalkylgroup (-CF3),and there is little overlapped district between cation and CO2.In [PC6,6,6,14]PF6-CO2 mixture,layered structure is found and CO2 is much nearer to PF6- than [PC6,6,6,14]+.Based on the analysis of RDF,in the phosphonium-based ILs,the highest distribution densities of anions and CO2 around cations are about 6 and 3 times as their average ones respectively,while in the imidazolium-based ILs,they are about 3 and 2 respectively,this means that the distributions of CO2 and anions around the imidazolium-based ILs are more evenly distributed than those around the phosphonium-bascd ILs.

  10. Oxidative stress in spring barley and common radish exposed to quaternary ammonium salts with hexafluorophosphate anion.

    Science.gov (United States)

    Biczak, Robert; Telesiński, Arkadiusz; Pawłowska, Barbara

    2016-10-01

    Quaternary ammonium salts (QAS), including ionic liquids (ILs), constitute a huge group of substances, which due to their desirable physical and chemical properties still attracts great interest in many industrial sectors. An increased concentration of this compound in the environment may lead to the contamination of the natural environment and may pose a potential threat to all organisms, including terrestrial higher plants. The present study demonstrates the interaction of three QAS with PF6(-) anions - tetramethylammonium [TMA][PF6], tetrabutylammonium [TBA][PF6], and tetrahexylammonium [THA][PF6] hexafluorophosphates - and its impact on the physiological and biochemical changes in spring barley seedlings and common radish plants. A similar study was also carried out by introducing the inorganic salt - ammonium hexafluorophosphate [A][PF6] to the soil; the results showed the soil became highly toxic to both plants. All the salts used led to significant changes in the metabolism of both spring barley and common radish which can be evidenced, for example, by a decrease in the content of chlorophyll a (Chla), chlorophyll b (Chlb), and total chlorophyll (Chla + b), as well as carotenoids (Car). The decrease in assimilation pigments was linearly correlated with an increasing concentration of QAS in the soil. QAS and [A][PF6] led to the formation of oxidative stress in both experimental plants, as evidenced by an increase in malondialdehyde (MDA) content in their cells and the changes in H2O2 level. In response to stress, the plants synthesized enzymatic free radicals (ROS) scavengers that lead to changes in the activity of superoxide dismutase (SOD) and catalase (CAT), as well as significantly increased peroxidase (POD) activity. A decrease in the content of assimilation pigments and an increased POD activity are the most reliable indices of oxidative stress, and concurrently the signs of premature plants aging. Common radish proved to be more resistant to the

  11. Determination of the electrochemical performance and stability of the lithium-salt, lithium 4,5-dicyano-2-(trifluoromethyl) imidazolide, with various anodes in Li-ion cells

    Science.gov (United States)

    Paillet, Sabrina; Schmidt, Gregory; Ladouceur, Sébastien; Fréchette, Joël; Barray, Francis; Clément, Daniel; Hovington, Pierre; Guerfi, Abdelbast; Vijh, Ashok; Cayrefourcq, Ian; Zaghib, Karim

    2015-12-01

    The electrochemical performance and stability of lithium 4,5-dicyano-2-(trifluoromethyl) imidazolide (LiTDI), which is a promising lithium salt for electrolytes in lithium-ion batteries, are discussed. The power capability of LiTDI in EC/DEC (3/7 v/v) in half cells was evaluated with standard anodes used in the lithium-ion battery industry: graphite and Li4Ti5O12 (LTO). The effects of two additives, vinylene carbonate (VC) and fluoro-ethylene carbonate (FEC), were investigated (2% weight in EC/DEC) and compared with a reference electrolyte, 1 M LiPF6 (EC/DEC + 2%VC). LiTDI forms a thin SEI with FEC that is uniformly deposited on graphite, which allows high power capability with 93.9% of the specific capacity at 10C (92.3% for 1 M LiPF6 + 2%VC). Excellent results were also obtained for LiTDI with LTO, 91.1% of the specific capacity was recovered at 10C vs. 91.5% for LiPF6. The stability of LiTDI was evaluated in pouch-cells: LFP/LTO (1C-rate) and NMC/LTO (C/4-rate). The results show that the performance of LiTDI is comparable to that of LiPF6, 85.4% of the capacity was recovered after 900 cycles (87.6% for LiPF6) for LFP/LTO, and 85.8% of capacity was obtained after 450 cycles (86.3% for LiPF6) for NMC/LTO.

  12. Two star-shaped tetranuclear Ru(II) complexes containing uncoordinated imidazole groups: synthesis, characterization, photophysical and pH sensing properties.

    Science.gov (United States)

    Cheng, Feixiang; Yu, Shiwen; He, Chixian; Ren, Mingli; Yin, Hongju

    2016-05-01

    Tetrapodal ligands H4 L(1) and H4 L(2) containing imidazole groups have been synthesized by the reaction of 1,10-phenanthroline-5,6-dione with 1,2,4,5-tetrakis[(4-formylphenoxy)methyl]benzene and 1,2,4,5-tetrakis[(3-formylphenoxy)methyl]benzene, respectively, in presence of NH4 OAc. Two star-shaped complexes [{Ru(bpy)2 }4 (μ4 -H4 L(1) )](PF6 )8 and [{Ru(bpy)2 }4 (μ4 -H4 L(2) )](PF6 )8 (bpy = 2,2'-bipyridine) have been prepared by refluxing Ru(bpy)2 Cl2 ·2H2 O and each ligand in ethylene glycol. The deprotonated complexes [{Ru(bpy)2 }4 (μ4 -L(1) )](PF6 )4 and [{Ru(bpy)2 }4 (μ4 -L(2) )](PF6 )4 have been obtained by the reaction of sodium methoxide with [{Ru(bpy)2 }4 (μ4 -H4 L(1) )](PF6 )8 and [{Ru(bpy)2 }4 (μ4 -H4 L(2) )](PF6 )8 , respectively, in methanol. The pH effects on the UV-vis light absorption and emission spectra of both complexes have been studied, and ground- and excited-state ionization constants of both complexes have been derived. The photophysical properties of both complexes are strongly dependent on the solution pH. They act as proton-induced off-on-off luminescent sensors through two successive deprotonation processes of imidazole groups, with a maximum on-off ratio of 8 in buffer solution at room temperature. Theoretical calculations for the highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital (LOMO) orbitals of bridging ligand are also presented for plausible explanations of the fluorescence changes. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26346924

  13. N-alkyl pyrrolidone ether podands as versatile alkali metal ion chelants.

    Science.gov (United States)

    Perrin, Andrea; Myers, Dominic; Fucke, Katharina; Musa, Osama M; Steed, Jonathan W

    2014-02-28

    This work explores the coordination chemistry of a bis(pyrrolidone) ether ligand. Pyrrolidones are commercially important functional groups because of the high polarity and hence high hydrophilicity and surface affinity. An array of alkali metal ion complexes of a podand bearing two pendant pyrrolidone functionalities, namely 1-{2-[2-(2-oxo-pyrrolid-1-yl)-ethoxy]-ethyl}-pyrrolid-2-one (1) are reported. Reaction of this ligand with sodium hexafluorophosphate gives two discrete species of formulae [Na(1)2]PF6 (3) and [Na3(H2O)2(μ-1)2](PF6)3 (4), and a coordination polymer {[Na3(μ3-1)3(μ2-1)](PF6)3}n (5). The same reaction in methanol gives a 1 : 1 complex, namely [Na2(μ-1)2(MeOH)2](PF6)2 (6). Use of tetraphenyl borate as a less coordinating counter ion gives [Na2(1)2(H2O)4](BPh4)2 (7) and [Na2(1)4](BPh4)2 (8). Two potassium complexes have also been isolated, a monomer [K(1)2]PF6 (9) and a cyclic tetramer [K4(μ4-H2O)2(μ-1)4](PF6)4 (10). The structures illustrate the highly polar nature of the amide carbonyl moiety within bis(pyrrolidone) ethers with longer interactions to the ether oxygen atom. The zinc complex is also reported and {[ZnCl2(μ-1)]}n (11) exhibits bonding only to the carbonyl moieties. The ether oxygen atom is not necessary for Na(+) complexation as exemplified by the structure of the sodium complex of the analogue 1,3-bis(pyrrolid-2-on-1-yl)butane (2). Reaction of compound 1 with lithium salts results in isolation of the protonated ligand. PMID:24336897

  14. Water Phase Diagram Is Significantly Altered by Imidazolium Ionic Liquid

    DEFF Research Database (Denmark)

    Chaban, V. V.; Prezhdo, O. V.

    2014-01-01

    We report unusually large changes in the boiling temperature, saturated vapor pressure, and structure of the liquid-vapor interface for a range of 1-butyl-3-methyl tetrafluoroborate, [C4C1IM][BF4]-water mixtures. Even modest molar fractions of [C4C1IM][BF4] significantly affect the phase behavior...... of water, as represented, for instance, by strong negative deviations from Raoult's law, extending far beyond the standard descriptions. The investigation was carried out using classical molecular dynamics employing a specifically refined force field. The changes in the liquid-vapor interface and...

  15. Ortho-positronium lifetime as a detector of spin crossover

    International Nuclear Information System (INIS)

    Positron lifetime parameters were measured for the spin-crossover complexes [Fe(R-1H-tetrazole)6](BF4)2 (R=1-ethyl, 1-n-propyl) and for the diamagnetic [Zn(1-n-propyl-1H-tetrazole)6](BF4)2. Positronium forms with significant intensity in the studied compounds. The ortho-para conversion of ortho-positronium was used to follow the spin-crossover. Changes of the dynamic structure were found in the propyl tetrazole complex between 150 K and 90 K. (author)

  16. Single-walled carbon nanotubes modified by ionic liquid as antiwear additives of thermoplastics

    OpenAIRE

    Carrión, F.J.; Espejo, C.; Sanes, J.; Bermúdez, M.D.

    2010-01-01

    Abstract Pristine single-walled carbon nanotubes (CNTs) were dispersed in the room-temperature ionic liquid (IL) 1-octyl, 3-methylimidazolium tetrafluoroborate ([OMIM]BF4) by grinding and ultrasounds. Excess IL was removed to obtain single-walled carbon nanotubes modified by [OMIM]BF4 (mCNTs). mCNTs were added in a 1wt.% to polystyrene (PS), polymethylmethacrylate (PMMA) and polycarbonate (PC) to obtain PS+mCNT, PMMA+mCNT and PC+mCNT. The dry tribological performance of the new nan...

  17. Bioactive Phytochemicals: Bioactivity, Sources, Preparations, and/or Modifications via Silver Tetrafluoroborate Mediation

    Directory of Open Access Journals (Sweden)

    Matthew C. Achilonu

    2015-01-01

    Full Text Available This review provides an overview of the biological activities, natural occurrences, and the silver tetrafluoroborate- (AgBF4- mediated synthesis of proanthocyanidins, glycosides, N-heterocyclic alkaloid analogues (of pyrrole, morphine, quinoline, isoquinoline, and indole, furan analogues, and halocompounds. AgBF4 has been reviewed as an effective reaction promoter, used extensively in the synthesis of relevant biologically active compounds via carbon-carbon and carbon-heteroatom bonds formation. The literatures from 1979 to April 2014 were reviewed.

  18. Teil A: Synthese und Reaktivität von diastereomeren Rhenium-Halbsandwich-Thiolat-Komplexen und Teil B: Monoanionische Wolfram-Carbonyl-Komplexe: Synthese, Struktur und Wechselwirkung mit Zellmembranen

    OpenAIRE

    Dilsky, Stefan

    2003-01-01

    Teil A behandelt zunächst die Synthese verschiedener achiraler und chiraler Phosphane. Die Chiralität kann sowohl in der Seitenkette als auch am Phosphoratom selbst vorliegen. Einige Phosphane tragen zusätzlich ein weiteres Donoratom (O oder S) in der organischen Seitenkette. Reaktion der Phosphane mit dem at-metal-chiralen Komplex [CpRe(CO)(NO)(NCCH3)]BF4 liefert diastereomere Komplexe des Typs [CpRe(CO)(NO)(PR3)]BF4 mit Metall- und Ligand-zentrierter Chiralität. Weitere Umsetzungen führen z...

  19. Preparation of Non-Heme {FeNO}7 Models of Cysteine Dioxygenase: Sulfur Versus Nitrogen Ligation and Photorelease of Nitric Oxide

    OpenAIRE

    McQuilken, Alison C.; Ha, Yang; Sutherlin, Kyle D.; Siegler, Maxime A.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; Jameson, Guy N. L.; Goldberg, David P.

    2013-01-01

    The synthesis and spectroscopic characterization of [Fe(NO)(N3PyS)]BF4 (3) is presented, the first structural and electronic model of NO-bound cysteine dioxygenase (CDO). The nearly isostructural all-N-donor analog [Fe(NO)(N4Py)](BF4)2 (4) was also prepared, and comparisons of 3 and 4 provide insight regarding the influence of S versus N ligation in {FeNO}7 species. One key difference occurs upon photoirradiation, which causes the fully reversible release of NO from 3, but not from 4.

  20. A novel ionic liquids-based scrubbing process for efficient CO2 capture

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A novel alkanolamine-based ionic liquid,N-methyl-diethanolammonium tetrafluoroborate ([MDEA][BF4]),was synthesized in our laboratory.The ionic liquid-based composite solution consisting of N-methyl-diethanolamine (MDEA),[MDEA][BF4],piperazine (PZ) and H2O was investigated for CO2 capture.The optimal performance for CO2 capture was found at 45°C,1.50 MPa,probably due to a synergistic action of the reaction and the transport.No apparent corrosion was found on stainless and carbon steel with the above composite solution.This finding is very significant to the promotion of its engineering application.

  1. Oxidative Desulfurization of Fuel Oil by Pyridinium-Based Ionic Liquids

    OpenAIRE

    Erhong Duan; Dishun Zhao; Yanan Wang

    2009-01-01

    In this work, an N-butyl-pyridinium-based ionic liquid [BPy]BF4 was prepared. The effect of extraction desulfurization on model oil with thiophene and dibenzothiophene (DBT) was investigated. Ionic liquids and hydrogen peroxide (30%) were tested in extraction-oxidation desulfurization of model oil. The results show that the ionic liquid [BPy]BF4 has a better desulfurization effect. The best technological conditions are: V(IL)/V(Oil) /V(H2O2) = 1:1:0.4, temperature 55 °C, the time 30 min. The ...

  2. A Novel One-Pot Green Synthesis of Dispirooxindolo-pyrrolidines via 1,3-Dipolar Cycloaddition Reactions of Azomethine Ylides

    Directory of Open Access Journals (Sweden)

    Abdulrahman I. Almansour

    2015-01-01

    Full Text Available A facile synthesis of dispirooxindolopyrrolidines has been accomplished via a one-pot three component 1,3-dipolar cycloaddition reaction. The reaction of azomethine ylides generated in situ from L-phenylalanine and substituted isatins with a series of unusual (E-2-oxoindolino-3-ylidene acetophenone dipolarophiles in the ionic liquid 1-butyl-3-methylimidazolium bromide [bmim]BF4, furnished the cycloadducts in good yields, with the regioisomers 5a–f being obtained with high selectivity. Furthermore, the recyclability of [bmim]BF4, up to five times, was also investigated.

  3. Bis[N-(2-hydroxybenzyladamantan-1-aminium] fluoride tetrafluoroborate monohydrate

    Directory of Open Access Journals (Sweden)

    Ying-Chun Wang

    2012-02-01

    Full Text Available In the title compound, 2C17H24NO+·BF4−·F−·H2O, the asymmetric unit contains two N-(2-hydroxybenzyladamantan-1-aminium cations, one BF4− anion, one F− anion and one water molecule. Both amine N atoms are protonated. The hydroxy O atoms, amino N atoms and water O atom are involved in intermolecular O—H...O, O—H...F, N—H...O and N—H...F hydrogen bonding.

  4. Synthesis of Two Novel Rhenium(I) Bipyridyl Photosensitive Dyes

    Institute of Scientific and Technical Information of China (English)

    Shi Guo SUN; Xiao Jun PENG; Ming Wen FAN; Yong Qian XU; Lei SHI; Li Cheng SUN

    2004-01-01

    Two novel rhenium(I) 2, 2'-bipyridyl complexes, [(4,4'-di-COOEt-bipy) Re(CO)3 (NCCH3)PF6] and [(4,4'-di-COOEt-bipy) Re (CO)3 (NCS)], a model complex [(4,4'-di- COOEt- bipy) Re (CO)3 (pyridine)PF6], were synthesized.Their ground state electronic spectra and emission spectra were measured in acetonitrile.The MLCT absorption maximum of the complex exhibited a considerable red shift as the ligand changed from pyridine to CNCH3, or SCN.

  5. Microwave synthesis of mixed ligand diimine–thiosemicarbazone complexes of ruthenium(ii): biophysical reactivity and cytotoxicity†

    OpenAIRE

    Beckford, Floyd A.; Shaloski, Michael; LeBlanc, Gabriel; Thessing, Jeffrey; Lewis-Alleyne, Lesley C.; Holder, Alvin A.; LI, LIYA; Seeram, Navindra P.

    2009-01-01

    A novel microwave-assisted synthetic method has been used to synthesise a series of mixed ligand ruthenium(ii) compounds containing diimine as well as bidentate thiosemicarbazone ligands. The compounds contain the diimine 1,10-phenanthroline (phen) or 2,2′-bipyridine (bpy) and the thiosemicarbazone is derived from 9-anthraldehyde. Based on elemental analyses and spectroscopic data, the compounds are best formulated as [(phen)2Ru(thiosemicarbazone)](PF6)2 and [(phen)2Ru(thiosemicarbazone)](PF6...

  6. Trinuclear ruthenium dioxolene complexes based on the bridging ligand hexahydroxytriphenylene: electrochemistry, spectroscopy, and near-infrared electrochromic behaviour associated with a reversible seven-membered redox chain.

    Science.gov (United States)

    Grange, Christopher S; Meijer, Anthony J H M; Ward, Michael D

    2010-01-01

    The trinuclear complexes [{(R2bipy)2Ru}3(mu3-HHTP)](PF6)3 [1(PF6)3, R = H; 2(PF6)3, R = 4-tBu] contain three {Ru(R2bipy)2}2+ fragments connected to the triangular tris-chelating ligand hexahydroxytriphenylene (H6HHTP). This bridging ligand contains three dioxolene-type binding sites, each of which can reversibly convert between dianionic catecholate (cat), monoanionic semiquinone (sq) or neutral quinone (q) redox states. The bridging ligand as a whole can therefore exist in seven different redox states from fully reduced [cat,cat,cat]6- through to fully oxidised, neutral [q,q,q]. Cyclic voltammetry of 1(PF6)3 in MeCN reveals six redox processes of which the three at more positive potentials (the sq/q couples) are reversible but the three at more negative potentials (the sq/cat couples) are irreversible with distorted wave shapes due to the insolubility of the reduced forms of the complex. In contrast, the more soluble complex 2(PF6)3 displays six reversible one-electron redox processes making all components of a seven-membered redox chain accessible. UV/Vis/NIR spectro-electrochemical studies reveal rich spectroscopic behaviour, with--in particular--very intense transitions in the near-IR region in many of the oxidation states associated with Ru(II)-->(dioxolene) MLCT and bridging ligand centred pi-pi* transitions. TDDFT calculations were used to analyse the electronic spectra in all seven oxidation states; the calculated spectra generally show very good agreement with experiment, which has allowed a fairly complete assignment of the low-energy transitions. The strong electrochromism of the complexes in the near-IR region has formed the basis of an optical window in which a thin film of 1(PF6)3 or 2(PF6)3 on a conductive glass surface can be reversibly and rapidly switched between redox states that alternate between strongly absorbing or near-transparent at 1100 nm, with--for 2(PF6)3--the switching being stable and reversible in water over thousands of cycles. PMID

  7. Reactions of CH-acids with α,β-unsaturated aldehydes in ionic liquids

    DEFF Research Database (Denmark)

    Kryshtal, G. V.; Zhdankina, G. M.; Astakhova, Irina Kira;

    2004-01-01

    - methylimidazolium hexafluorophosphate [bmim][PF 6], and in a 1-butyl-3-methylimidazolium bromide ([bmim][Br]) - benzene system. The reactions with acrolein and crotonaldehyde afforded Michael addition products, those with citral resulted in Knoevenagel addition products. Sonication increased the yields of the...... Michael adducts. The ionic liquid [bmim][PF 6] can be recovered and repeatedly used in the reactions.......Metal carbonate-catalyzed reactions of CH-acids (diethyl malonate, ethyl acetoacetate, ethyl cyanoacetate, and ethyl 2-acetyl- and 2-ethoxycarbonyl-5,9- dimethyldeca-4,8-dienoates) with α,β-unsaturated aldehydes (acrolein, crotonaldehyde, citral) were studied in an ionic liquid, 1-butyl-3...

  8. Operando High-Pressure NMR and IR Study of the Hydroformylation of 1-Hexene by 1,1’-Bis-(Diarylphosphino)metallocene-Modified Rhodium(I) Catalyst

    OpenAIRE

    BIANCHINI, C.; W. OBERHAUSER; Orlandini, A; C. Giannelli; P. Frediani

    2005-01-01

    Some rhodium(I) complexes of the general formula [Rh(P-P)(COD)]X were synthesized and characterized by multinuclear NMR spectroscopy (COD ) cyclocta-1,5-diene; P-P ) 1,1'-bis(diphenylphosphino)ferrocene, dppf, X ) BPh4, PF6; P-P ) 1,1'-bis(diphenylphosphino) ruthenocene, dppr, X ) BPh4; P-P ) 1,1'-bis(diphenylphosphino)osmocene, dppo, X ) BPh4, PF6; P-P ) 1,1'-bis(diphenylphosphino)octamethylferrocene, dppomf, X ) BAr'4; P-P ) (1,1'-bis(di(o-isopropylphenyl)phosphino)ferrocene, o-iPr-dppf,...

  9. Long-Range Ruthenium-Amine Electronic Communication through the para-Oligophenylene Wire

    OpenAIRE

    Jun-Jian Shen; Yu-Wu Zhong

    2015-01-01

    The studies of long-range electronic communication are hampered by solubility and potential-splitting issues. A “hybridized redox-asymmetry” method using a combination of organic and inorganic redox species is proposed and exemplified to overcome these two issues. Complexes 1(PF6)–6(PF6) (from short to long in length) with the organic redox-active amine and inorganic cyclometalated ruthenium termini bridged by the para-oligophenylene wire have been prepared. Complex 6 has the longest Ru-amine...

  10. Lithium salts for advanced lithium batteries: Li–metal, Li–O2, and Li–S

    OpenAIRE

    Younesi, Reza; Veith, Gabriel M.; Johansson, Patrik; Edström, Kristina; Vegge, Tejs

    2015-01-01

    Presently lithium hexafluorophosphate (LiPF6) is the dominant Li-salt used in commercial rechargeable lithium-ion batteries (LIBs) based on a graphite anode and a 3–4 V cathode material. While LiPF6 is not the ideal Li-salt for every important electrolyte property, it has a uniquely suitable combination of properties (temperature range, passivation, conductivity, etc.) rendering it the overall best Li-salt for LIBs. However, this may not necessarily be true for other types of Li-based batteri...

  11. Biophysical insights into the intercalative interaction of surfactant cobalt(III) complexes of certain diimine ligands bound to yeast tRNA: Effects of hydrophobicity

    Science.gov (United States)

    Nagaraj, Karuppiah; Sakthinathan, Subramanian; Arunachalam, Sankaralingam

    2015-08-01

    The interaction of two surfactant cobalt(III) complexes, cis-[Co(ip)2(DA)2](ClO4)3 1 and cis-[Co(dpq)2(DA)2](ClO4)3 2 where ip = imidazo[4,5-f][1,10]phenanthroline and dpq = dipyrido[3,2-d:2‧-3‧-f]quinoxaline with yeast tRNA have been explored by using electronic absorption, competitive binding, electrochemical studies and viscosity measurements. The results suggest that these complexes can bind to tRNA by intercalation. The presence of hydrophobic diimine ligand and the long aliphatic double chains of these complexes facilitate its intercalative interaction with the hydrophobic interior of the tRNA. The extent of tRNA binding of complex 2 has greater affinity than that of complex containing imidazo[4,5-f][1,10]phenanthroline ligands.

  12. Supramolecular structures constructed from three novel rare earth metal complexes

    Indian Academy of Sciences (India)

    Huaze Dong; Xiaojun Feng; Xia Liu; BiN Zheng; Jianhong Bi; Yan Xue; Shaohua Gou; Yanping Wang

    2015-05-01

    Three rare earth metal supramolecular complexes, {[Tb(2)4](ClO4)3·2H2O(1), [Eu(2)2(H2O)5] (ClO4)3(2) and [Gd(NO3)3(2)2]·2CH3CH2OH(3) ( 2 = 3-Dimethylamino-1-pyridin-2-yl-propenone), have been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction. The crystal structure analysis reveals that the coordination numbers of three complexes (1–3) are 8, 9 and 10, respectively. Three complexes assembled into 3D frameworks based on C-H⋯O, O-H⋯O hydrogen bond linkages.

  13. catena-Poly[[[trans-diaquabis(pyridine-κNcobalt(II]-μ-(4-{N′-[1-(3-acetyl-4-methyl-1H-pyrazol-5-ylethylidene]hydrazino}benzoato-κ3O:N,N′-[bis(pyridine-κNcobalt(III]-μ-(4-{N′-[1-(3-acetyl-4-methyl-1H-pyrazol-5-ylethylidene]hydrazino}benzoato-κ3N,N′:O]perchlorate 3.66-hydrate

    Directory of Open Access Journals (Sweden)

    Igor O. Fritsky

    2008-02-01

    Full Text Available The title compound, {[Co2(C15H14N4O32(C5H5N4(H2O2]ClO4·3.66H2O}n, is a one-dimensional coordination polymer, with both CoII and CoIII centres in its structure. The ligand environment surrounding CoIII is formed by two N,N-chelating pyrazole-containing ligands and two pyridine molecules in axial positions. The high-spin CoII ions, situated at crystallographic centres of inversion, exhibit a distorted octahedral coordination mode. The ClO4− anion is linked to the polymer chain via hydrogen bonds. The chains are connected by hydrogen bonds to produce a three-dimensional structure.

  14. Three new superconducting members of the family of tetramethyltetraselenafulvalene (TMTSF) salts: TMTSF2Cl04, TMTSF2SbF6, TMTSF2TaF6

    International Nuclear Information System (INIS)

    Resistivity against temperature measurements are reported along the high-conductivity a axis of TMTSF2ClO4, TMTSF2SbF6 and TMTSF2TaF6, under pressure and as a function of applied magnetic field, that show that all three compounds exhibit superconducting phase transitions near 1 K, when sufficient pressure is applied. TMTSF2SbF6 and TMTSF2TaF6 become superconducting above critical pressures of the order of 10 and 11 kbar respectively whereas a superconducting phase transition in TMTSF2ClO4 is observed at much lower pressures (<3 kbar). The critical pressure above which the sc phase is stabilised can be correlated with the separation between the sheets of TMTSF molecules and anions. (author)

  15. Synthesis, DNA-binding and photocleavage studies of ruthenium(Ⅱ) complexes [Ru(btz)3]2+ and [Ru(btz)(dppz)2]2+

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Two new ruthenium(Ⅱ) complexes, [Ru(btz)3](ClO4)2 (1) and [Ru(btz)(dppz)2](ClO4)2 (2) (btz = 4,4′-bithi-azole, dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysis, 1H NMR, ES-MS and X-ray crystallography. The DNA binding behaviors of two complexes have been studied by spectroscopic and viscosity measurements. The results suggest that complex 1 binds to CT-DNA via an electrostatic mode, while complex 2 via an intercalative mode. Under irradiation at 365 nm, both complexes were found to promote the cleavage of plasmid pBR 322 DNA from supercoiled form Ⅰ to nicked form Ⅱ. The mechanism studies reveal that singlet oxygen 1O2 and hydroxyl radical (OH-) play a significant role in the photocleavage process.

  16. Ion Channel Behavior of a Supported Bilayer Lipid Membrane Composed of 5,5-Ditetradecyl-2- (2-trimethyl-ammonioethyl)-l, 3-dioxane Bromide Modified Glassy Carbon Electrode

    Institute of Scientific and Technical Information of China (English)

    龚静鸣; 林祥钦

    2003-01-01

    A synthetic cationic surfactant, 5,5-ditetradecyl-2-(2-trimethyl-ammonioethyl)-l,3-dioxane bromide (DTDB), was used to construct a supported bilayer lipid membrane (s-BLM) coatedon an underlying glassy carbon electrode (GCE). Electrochemical impedance spectroscopy (EIS), small-angle X-ray diffraction (SAXD) and cyclic voltammetry were used to characterize the s-BLM. Both EIS and SAXD data indicated that the synthetic lipid exists as a well-oriented bilayer in the membrane.The voltammetric study showed that the lipid membrane can open ion channels in the presence of ClO4- stimulant with Ru(bpy)32+ as marker ions and give distinct channel currents.The channels can be dosed and open up again many times by removing or introducing ClO4- anions.

  17. Complexes of rare-earth perchlorates with ditbutyl amides of di, tri and tetraglycolic acids

    OpenAIRE

    Premlatha, C; Soundararajan, S

    1981-01-01

    New complexes of lanthanide perchlorates with di-t-butyl amides of di, tri and tetraglycolic acids have been synthesised. The complexes have the general formula Ln(DiGA)3(ClO4)3; Ln(TriGA)2 (ClO4)3 and Ln(TetGA)2 (C1O4)3, where Ln = La-Yb and Y and DiGA = N,N′, di-t-butyl diglycolamide, TriGA N,N′, di-t-butyl triglycolamide and TetGA = N,N′ di-t-butyl tetraglycolamide, respectively. The complexes have been characterized by analysis, electrolytic conductance, infrared,1H and13C nuclear magneti...

  18. (2,2 '-Bipyridine-4,4 '-dicarboxylic acid-kappa N-2,N ')chlorido(2,2 ':6 ',2 ''-terpyridyl-kappa N-3,N ',N '')ruthenium(II) perchlorate ethanol monosolvate monohydrate

    DEFF Research Database (Denmark)

    Nielsen, A.; McKenzie, C. J.; Bond, A. D.

    2012-01-01

    In the title compound, [RuCl(C15H11N3)(C12H8N2O4)]ClO4 center dot C2H5OH center dot H2O, the geometry of the ClN5 coordination set around the Ru-II atom is close to octahedral, but distorted on account of the limited bite angles of the polypyridyl ligands. The complexes are linked by O-H center d...

  19. Different Strategies for Biological Remediation of Perchlorate Contaminated Groundwater

    OpenAIRE

    Wang, Yue

    2012-01-01

    Perchlorate (ClO4-) has gained attention recently due to its interference with thyroid gland function. In infants and unborn children, inadequate thyroid hormone production can cause mental retardation and thyroid tumors. Since new perchlorate standards will be proposed in 2013, and if a stricter standard is imposed, cost effective technologies will be in high demand. The overall objective of this research was to evaluate two perchlorate bioremediation strategies using indigenous soil bact...

  20. Natural chlorate in the environment: Application of a new IC-ESI/MS/MS method with a Cl18O3- internal standard

    Science.gov (United States)

    Rao, Balaji; Hatzinger, Paul B.; Böhlke, John Karl; Sturchio, Neil C.; Andraski, Brian J.; Eckardt, Frank D.; Jackson, W. Andrew

    2010-01-01

    A new ion chromatography electrospray tandem mass spectrometry (IC-ESI/MS/MS) method has been developed for quantification and confirmation of chlorate (ClO3-) in environmental samples. The method involves the electro-chemical generation of isotopically labeled chlorate internal standard (Cl18O3-) using 18O water (H218O). The standard was added to all samples prior to analysis thereby minimizing the matrix effects that are associated with common ions without the need for expensive sample pretreatments. The method detection limit (MDL) for ClO3- was 2 ng L-1 for a 1 mL volume sample injection. The proposed method was successfully applied to analyze ClO3- in difficult environmental samples including soil and plant leachates. The IC-ESI/MS/MS method described here was also compared to established EPA method 317.0 for ClO3- analysis. Samples collected from a variety of environments previously shown to contain natural perchlorate (ClO 4-) occurrence were analyzed using the proposed method and ClO3- was found to co-occur with ClO4- at concentrations ranging from 500 mg kg-1 in caliche salt deposits from the Atacama Desert in Chile. Relatively low concentrations of ClO3- in some natural groundwater samples (-1) analyzed in this work may indicate lower stability when compared to ClO4- in the subsurface. The high concentrations of ClO3- in caliches and soils (3-6 orders of magnitude greater) as compared to precipitation samples indicate that ClO3-, like ClO4-, may be atmospherically produced and deposited, then concentrated in dry soils, and is possibly a minor component in the biogeochemical cycle of chlorine.

  1. 2-(2-Chlorophenyl-5-methyl-1,3-dioxane-5-carboxylic acid

    Directory of Open Access Journals (Sweden)

    Guo-Kai Jia

    2012-07-01

    Full Text Available In the title compound, C12H13ClO4, the 1,3-dioxane ring adopts a chair conformation and the 2-chlorobenzene and methyl substituents occupy equatorial sites. The carboxyl group is in an axial inclination. In the crystal, carboxylic acid inversion dimers linked by pairs of O—H...O hydrogen bonds generate R22(8 loops.

  2. Branched polymeric media: Perchlorate-selective resins from hyperbranched polyethyleneimine

    KAUST Repository

    Chen, Dennis P.

    2012-10-02

    Perchlorate (ClO4 -) is a persistent contaminant found in drinking groundwater sources in the United States. Ion exchange (IX) with selective and disposable resins based on cross-linked styrene divinylbenzene (STY-DVB) beads is currently the most commonly utilized process for removing low concentrations of ClO4 - (10-100 ppb) from contaminated drinking water sources. However, due to the low exchange capacity of perchlorate-selective STY-DVB resins (∼0.5-0.8 eq/L), the overall cost becomes prohibitive when treating groundwater with higher concentration of ClO4 - (e.g., 100-1000 ppb). In this article, we describe a new perchlorate-selective resin with high exchange capacity. This new resin was prepared by alkylation of branched polyethyleneimine (PEI) beads obtained from an inverse suspension polymerization process. Batch and column studies show that our new PEI resin with mixed hexyl/ethyl quaternary ammonium chloride exchange sites can selectively extract trace amounts of ClO4 - from a makeup groundwater (to below detection limit) in the presence of competing ions. In addition, this resin has a strong-base exchange capacity of 1.4 eq/L, which is 1.75-2.33 times larger than those of commercial perchlorate-selective STY-DVB resins. The overall results of our studies suggest that branched PEI beads provide versatile and promising building blocks for the preparation of perchlorate-selective resins with high exchange capacity. © 2012 American Chemical Society.

  3. Structure and bonding of some newly synthesized complexes of lanthanide(III) complexes of 4[N-(p-dimetaylaminobenzalidene) amino] antipyrine thiosemicarbazone

    International Nuclear Information System (INIS)

    A series of complexes of the type LnX3.2(DABAAPTS), where Ln = La, Pr, Nd, Sm, Gd, Tb, Dy and Ho, X = ClO4-, or NCS-, DABAAPTS=4[N- (p-dimethylaminobenzalidene) amino] anti pyrine thiosemicarbazone have been synthesized and characterized on the basis of elemental analysis, molecular weight measurements, molar conductance, room temperature magnetic moment, infrared and electronic spectral data. The ligand DABAAPTS behaves as neutral tridentate (N2S) ligand. (author)

  4. Spectroscopic characterization of copper(II) complexes of indoxyl N(4)-methyl thiosemicarbazone

    Science.gov (United States)

    Chandra, Sulekh; Kumar, Umendra

    2004-10-01

    New copper(II) complexes of indoxyl thiosemicarbazone (ITSC) of general composition CuL 2X 2 (where L: ITSC; X: Cl -, NO 3-, ClO 4-, NCS -) have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements and spectral (electronic, IR, EPR, 1H NMR , Mass) studies. Cyclic voltammetry measurements show quasi-reversible Cu 2+/Cu 1+ couple. Various physico-chemical techniques suggest a tetragonal structure for these copper(II) complexes.

  5. Construction of diverse supramolecular assemblies of dimetal subunits differing in coordinated water molecules via strong hydrogen bonding interactions: Synthesis, crystal structures and spectroscopic properties

    Indian Academy of Sciences (India)

    Sadhika Khullar; Sanjay K Mandal

    2014-09-01

    Three new supramolecular assemblies (constructed through strong hydrogen bonding) of [Co2(bpta)2(adc)(H2O)4](ClO4)2.2H2O (1), [Cu2(bpta)2(fum)(H2O)2](ClO4)2 (2) and [Cu2(bpta)2(tdc)(H2O) (ClO4)](ClO4).3H2O (3), which are synthesised by one pot self-assembly of the metal salt, bpta ligand and the corresponding dicarboxylate under the same reaction conditions, are reported (where adc = acetylene dicarboxylate, fum = fumarate, tdc = 2,5-thiophenedicarboxylate and bpta = N,N'-bis(2-pyridylmethyl)-tertbutylamine). These compounds have varying degrees of coordinatedwater molecules per dimetal subunits (four for 1, two for 2 and one for 3, respectively). Furthermore, the orientation of the coordinated water molecules in 1 and 2, with respect to the mono (carboxylato)-bridged dimetal subunit, is different (cis and trans, respectively). On the other hand, there is a coordinated perchlorate ion in 3 making the two metal centers inequivalent. Unlike 1 and 3, there are no lattice water molecules in 2. This difference in the dimetal subunit in 1-3 and the presence or absence of the lattice water molecules are the keys to forming the diverse supramolecular assemblies. In 1 and 3, the involvement of lattice water molecules in the construction of such assemblies is distinctly different. In case of 2, the formation of supramolecular assembly depends on the coordinated water molecule (trans to each other) and thus a ladder shaped supramolecular assembly is the result. The strength of hydrogen bonding observed in the networks of 1-3 is indicated in the O…O distances (2.596 Å to 3.160 Å) and the OH…O angles 124° to 176°. All are characterised by elemental analysis, FTIR spectroscopy and single crystal X-ray diffraction studies.

  6. Evaluation of the natural attenuation potential of a complex pollution plume (chlorate, perchlorate, 1,2dichloroethane and vinyl chloride) by autochthonous microbial communities

    OpenAIRE

    Harris-Hellal, Jennifer; Joulian, Catherine; Hube, Daniel; Coulon, Stéphanie; Guérin, Valérie; Garrido, Françis

    2013-01-01

    Artificially synthetized chloride-based-oxyanions such as perchlorate (ClO4-) and chlorate (ClO3-), are used in a vast number of applications such as military and aerospace industry; they are also used as herbicides and in pyrotechnic applications. Due to their very high solubility, perchlorate and chlorate are readily transported in water systems and can thus end up in drinking water. Ingestion of perchlorate may affect iodine uptake by the human thyroid and thus thyroidal hormone production...

  7. Physiological and Genetic Description of Dissimilatory Perchlorate Reduction by the Novel Marine Bacterium Arcobacter sp. Strain CAB

    OpenAIRE

    Carlström, Charlotte I.; Wang, Ouwei; Melnyk, Ryan A.; Bauer, Stefan; Lee, Joyce; Engelbrektson, Anna; Coates, John D.

    2013-01-01

    ABSTRACT A novel dissimilatory perchlorate-reducing bacterium (DPRB), Arcobacter sp. strain CAB, was isolated from a marina in Berkeley, CA. Phylogenetically, this halophile was most closely related to Arcobacter defluvii strain SW30-2 and Arcobacter ellisii. With acetate as the electron donor, strain CAB completely reduced perchlorate (ClO4 −) or chlorate (ClO3 −) [collectively designated (per)chlorate] to innocuous chloride (Cl−), likely using the perchlorate reductase (Pcr) and chlorite di...

  8. Synthesis, Characterization and Biological Activity of Transition Metals with Schiff Base Derived from Adamantaneamine and o-Vanillin

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Five new solid complexes were synthesized about transition metals with Schiff base(L,C18H23NO2) derived from adamantaneamine and o-vanillin, and characterized by elemental analysis, molar conductance, infrared spectra, UV-vis spectra, thermal analysis. Their chemical formula are [ML2](ClO4)2 (M= Mn,Co,Ni,Cu,Zn),and the coordination numbers are four. The antibacterial activity of Schiff base ligand and its complexes was studied.

  9. Crystal structure of benzobicyclon

    Directory of Open Access Journals (Sweden)

    Gihaeng Kang

    2015-12-01

    Full Text Available In the title compound, C22H19ClO4S2 [systematic name: 3-(2-chloro-4-mesylbenzoyl-4-(phenylsulfanylbicyclo[3.2.1]oct-3-en-2-one], which is an unclassified herbicide, the dihedral angle between the plane of the phenyl and chlorobenzene rings is 19.9 (2°. In the crystal, C—H...O hydrogen bonds link adjacent molecules, generating two-dimensional networks extending parellel to (011.

  10. Corrigendum to "Widespread occurrence of (per)chlorate in the Solar System" [Earth Planet. Sci. Lett. 430 (2015) 470-476

    Science.gov (United States)

    Jackson, W. Andrew; Davila, Alfonso F.; Sears, Derek; Coates, John D.; McKay, Christopher P.; Brundrett, Maeghan; Estrada, Nubia; Böhlke, J. K.

    2016-02-01

    The authors regret that two sets of data (Atacama (Rao et al., 2010) and Mars Meteorite Range (Kounaves et al., 2014)) in Fig. 2 of our article were plotted in the wrong units. The correction does not change the relationship between ClO3- and ClO4- ; it only shifts the magnitude of the concentrations. The conclusions of the article are not affected. The corrected Fig. 2 appears below.

  11. The first characterisation of an anhydrous perchlorato complex of tungsten (VI)

    International Nuclear Information System (INIS)

    Various perchlorating reagents were tested in reaction with WCl6 and WCl4. Only the well controlled reaction of Cl2O6 with WCl6 yields an oxoperchloratotungsten (VI) complex: W2O5(ClO4)2 which cristallises in the monoclinic system. Vibrational spectroscopy corresponds to a complex molecule with W=O and W-O-W bonds, and bidendate and monodendate perchlorato groups. 19 refs

  12. 4-(2-Azaniumylethylpiperazin-1-ium bis(perchlorate

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Reisi

    2011-09-01

    Full Text Available In the title compound, C6H17N32+·2ClO4−, the piperazine ring adopts a chair conformation with the ethylammonium fragment occupying an equatorial position. In the crystal, the dications and perchlorate anions are linked through N—H...O hydrogen bonding and weak C—H...O hydrogen bonding into a three-dimensional supramolecular network.

  13. Cesium ionophore II as an extraordinarily effective macrocyclic receptor for the barium cation

    Science.gov (United States)

    Makrlík, Emanuel; Böhm, Stanislav; Vaňura, Petr

    2015-02-01

    On the basis of extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Ba2+(aq) + 2ClO4-(aq) + 1(nb) ⇄ 1·Ba2+(nb) + 2ClO4- (nb) occurring in the two-phase water-nitrobenzene system (1 = cesium ionophore II; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log Kex (1·Ba2+, 2ClO4-) = 3.4 ± 0.1. Further, the extremely high stability constant of the 1·Ba2+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb (1·Ba2+) = 16.7 ± 0.1. Finally, applying quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1·Ba2+ was derived. In the resulting 1·Ba2+ complex, the "central" cation Ba2+ is bound by four very strong bonding interactions to the respective four oxygen atoms of the parent receptor 1. The interaction energy, E(int), of the considered 1·Ba2+ complex was found to be -1050.4 kJ/mol, confirming also the formation of this significant complex.

  14. Thermochemical Study of Mixed Ligand Complexes of Rare Earths with Glycine and L-alanine

    Institute of Scientific and Technical Information of China (English)

    QU Jing-nian; LIU Yi; YU Hua-guang; LEI Ke-lin; YAN Cheng-nong; QU Song-sheng

    2004-01-01

    In order to obtain the standard molar enthalpies of formation of Rare-Earth amino acid coordination compounds, precise isothermal solution-reaction calorimetric method was used. The value of ΔrHΘm of two coordination reactions was determined at T = 298.2 K. From the experimental results and other auxiliary values, the standard molar enthalpies of formation of Ln(Gly)5/2(Ala)3/2 (ClO4)3·H2O(s) [Ln = La, Yb] at T = 298.2 K were obtained. The values of them is to be ΔrHΘm [La(Gly)5/2(Ala)3/2(ClO4)3·H2O(s)] =-3545.45 kJ/ mol and ΔrHΘm [Yb(Gly)5/2(Ala)3/2(ClO4)3·H2O(s)]= -3793.81 kJ/mol, respectively.

  15. Thermochemical Study of Lanthanum Complex Crystal with β-Alanine

    Institute of Scientific and Technical Information of China (English)

    陈平初; 屈松生; 詹正坤; 吴新明

    2002-01-01

    Lanthanum complex crystal with β-alanine (1∶3) was synthesized. Through the DTA,TG,chemistry analysis and comparison with literature, it shows that its form is {[La2(β-ala)6* (H2O)4](ClO4)6*H2O}n, and its purity is 98.86%. The dissolution enthalpy of the reactants and products in 2 mol*L-1 HCl solution (298.15K) was measured by using the isoperibol reaction calorimetry. ΔrHm was calculated by a designed thermochemical cycle of the coordination reaction. From the results and other auxiliary quantities, the standard molar enthalpy of formation of [La2(β-ala)6*(H2O)4](ClO4)6*H2O is obtained to be ΔfHm°{[La2(β-ala)6*(H2O)4](ClO4)6*H2O} = - 7062.911 kJ*mol-1.

  16. Noninnocence of Indigo: Dehydroindigo Anions as Bridging Electron-Donor Ligands in Diruthenium Complexes.

    Science.gov (United States)

    Mondal, Prasenjit; Chatterjee, Madhumita; Paretzki, Alexa; Beyer, Katharina; Kaim, Wolfgang; Lahiri, Goutam Kumar

    2016-03-21

    Complexes of singly or doubly deprotonated indigo (H2Ind) with one or two [Ru(pap)2](2+) fragments (pap = 2-phenylazopyridine) have been characterized experimentally [molecular structure, voltammetry, electron paramagnetic resonance (EPR), and UV-vis-near-IR spectroelectrochemistry] and by time-dependent density functional theory calculations. The compound [Ru(pap)2(HInd(-))]ClO4 ([1]ClO4) was found to contain an intramolecular NH---O hydrogen bond, whereas [{Ru(pap)2}2(μ-Ind(2-))](ClO4)2 ([2](ClO4)2), isolated as the meso diastereoisomer with near-IR absorptions at 1162 and 991 nm, contains two metals bridged at 6.354 Å distance by the bischelating indigo dianion. The spectroelectrochemical study of multiple reversible reduction and oxidation processes of 2(n) (n = 4+, 3+, 2+, 1+, 0, 1-, 2-, 3-, 4-) reveals the stepwise addition of electrons to the terminal π-accepting pap ligands, whereas the oxidations occur predominantly at the anionic indigo ligand, producing an EPR-identified indigo radical intermediate and revealing the suitability of deprotonated indigo as a σ- and π-donating bischelating bridge. PMID:26931407

  17. Application of ionic liquid to polymorphic transformation of anti-viral/HIV drug adefovir dipivoxil.

    Science.gov (United States)

    An, Ji-Hun; Jin, Feng; Kim, Hak Sung; Ryu, Hyung Chul; Kim, Jae Sun; Kim, Hyuk Min; Kiyonga, Alice Nguvoko; Min, Dong Sun; Youn, Wonno; Kim, Ki Hyun; Jung, Kiwon

    2016-05-01

    Ionic liquids (ILs) are defined as salts with a melting point below 100 °C. ILs have received increasing attention as new alternative to organic solvents because of their unique physicochemical properties. Therefore, this study was conducted in the purpose to present the efficacy of ILs as new solvents capable to control the Polymorphic transformation phenomenon. Here, the polymorphic transformation phenomenon of adefovir dipivoxil, an efficient antiviral active pharmaceutical ingredient on human immunodeficiency virus, was investigated. The phase transformation phenomenon from the metastable polymorph, new form (NF) to the stable polymorph, Form-X in 1-allyl-3-ethylimidazolium tetrafluoroborate (AEImBF4) and 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BDMImBF4) ILs solutions was observed utilizing the solvent-mediated phase transformation method The thermodynamic factors, AEImBF4/BDMImBF4 solvent composition ratio of 3:7-6:4 and the temperature in range of 25-100 °C, as well as the dynamic factor, the rational speed in range of 300-1000 rpm were parameters studied in this experiment. The thermodynamic and dynamic equations involving nucleation and mass transfer were applied for the quantitative analysis. The result of the present study confirmed the use of ILs as substitute solvent for volatile organic solvents, and demonstrated the efficacy of ILs as potential solvent-media to control the polymorphic transformation. PMID:26908332

  18. Immobilization of Pd(Ⅱ) Catalysts for Cyclopropanation in Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    YANG,Fan(杨帆); ZHANG,Yang-Ming(张仰明); QIU,Wen-Wei(仇文卫); TANG,Jie(汤杰); HE,Ming-Yuan(何鸣元)

    2002-01-01

    Cyclopropanation of styrene with ethyl diazoacetate catalyzed by Pd(Ⅱ)in ionic liquid [omim] [BF4] was investigated. Palladium catalysts can be effectively immobilized in ionic liquid.The catalysts PdCl2 and cyclopalladated complex 2 contained in ionic liquid could be recycled for 6 and 7 times, respectively, without losing the efficiency.

  19. C(aryl)-O Bond Formation from Aryl Methanesulfonates via Consecutive Deprotection and SNAr Reactions with Aryl Halides in an Ionic Liquid

    OpenAIRE

    Yang Chen; Hui Xu

    2007-01-01

    An efficient K3PO4-mediated synthesis of unsymmetrical diaryl ethers using the ionic liquid [Bmim]BF4 (1-butyl-3-methylimidazolium tetrafluoroborate) as solvent has been developed. The procedure involves consecutive deprotection of aryl methane-sulfonates and a nucleophilic aromatic substitution (SNAr) with activated aryl halides.

  20. C(aryl-O Bond Formation from Aryl Methanesulfonates via Consecutive Deprotection and SNAr Reactions with Aryl Halides in an Ionic Liquid

    Directory of Open Access Journals (Sweden)

    Yang Chen

    2007-04-01

    Full Text Available An efficient K3PO4-mediated synthesis of unsymmetrical diaryl ethers using the ionic liquid [Bmim]BF4 (1-butyl-3-methylimidazolium tetrafluoroborate as solvent has been developed. The procedure involves consecutive deprotection of aryl methane-sulfonates and a nucleophilic aromatic substitution (SNAr with activated aryl halides.