Sample records for lems30 mfsa ch2

  1. Atmospheric chemistry of CF3CH2CH2OH

    DEFF Research Database (Denmark)

    Hurley, Michael D.; Misner, Jessica A.; Ball, James C.


    Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with CF3CH2C(O)H and CF3CH2CH2OH in 700 Torr of N-2 or air diluent at 296 2 K. The rate constants determined were k(Cl+CF3CH2C(O)H) = (1.81 +/- 0.27) x 10(-11), k(OH+CF3CH2C(O)H) = (2.57 +/- 0.44...

  2. CH2 - Lighting and Physiology

    Directory of Open Access Journals (Sweden)

    Sergio Altomonte


    Full Text Available This paper explains the designed performances of the new CH2 building in Melbourne, Australia. CH2 is an environmentally significant project that involves biomimicry of natural systems to produce indoor conditions that are conducive to user comfort, health and productivity. This paper focuses on lighting and physiology and examines the solutions chosen for artificial and natural lighting and the likely effects these will have on building occupants. The purpose of the paper is to critically comment on the adopted strategy and, cognisance of contemporary thinking in lighting design, to judge the effectiveness of this aspect of the project with a view to later verification and post-occupancy review. The paper concludes that CH2 is an exemplar of lighting innovation that provides valuable lessons to designers of office buildings, particularly in the Melbourne CSD.

  3. Comparison of Three Isoelectronic Multiple-Well Reaction Systems: OH + CH2O, OH + CH2CH2, and OH + CH2NH. (United States)

    Akbar Ali, Mohamad; Barker, John R


    Methylenimine (CH2NH) has been predicted to be a product of the atmospheric photo-oxidation of methylamine, but its atmospheric reactions have not been measured. In this paper, we report potential energy surfaces (PESs) and rate constants for OH + CH2NH and its isoelectronic analogues OH + CH2O and OH + CH2CH2, which are more fully understood. The PESs were computed using the BHandHLYP/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ levels of theory. Canonical variational transition state theory and Rice-Ramsperger-Kassel-Marcus and master equation modeling were used to calculate temperature- and pressure-dependent rate constants, with particular emphasis on the OH + reactant entrance channels and the effects of prereactive complexes. The computed results are in reasonable agreement with experimental data where they can be compared and also with the results of previous theoretical calculations. The results show that to some extent OH radicals both add to the carbon center double bond in CH2NH and abstract methylene hydrogen atoms, as in the OH + CH2O and OH + CH2CH2 reactions, respectively, but the dominant pathway is abstraction of the hydrogen from N-H. The computed rate constants are suitable for both atmospheric and combustion modeling.


    National Aeronautics and Space Administration — This data set consists of HISCALE Low-Energy Magnetic Spectrometer (LEFS) ion counts at 30 degrees from the spacecraft spin axis. These measurements were taken...

  5. New superhindered polydentate polyphosphine ligands P(CH2CH2P(t)Bu2)3, PhP(CH2CH2P(t)Bu2)2, P(CH2CH2CH2P(t)Bu2)3, and their ruthenium(II) chloride complexes. (United States)

    Gilbert-Wilson, Ryan; Field, Leslie D; Bhadbhade, Mohan M


    The synthesis and characterization of the extremely hindered phosphine ligands, P(CH(2)CH(2)P(t)Bu(2))(3) (P(2)P(3)(tBu), 1), PhP(CH(2)CH(2)P(t)Bu(2))(2) (PhP(2)P(2)(tBu), 2), and P(CH(2)CH(2)CH(2)P(t)Bu(2))(3) (P(3)P(3)(tBu), 3) are reported, along with the synthesis and characterization of ruthenium chloro complexes RuCl(2)(P(2)P(3)(tBu)) (4), RuCl(2)(PhP(2)P(2)(tBu)) (5), and RuCl(2)(P(3)P(3)(tBu)) (6). The bulky P(2)P(3)(tBu) (1) and P(3)P(3)(tBu) (3) ligands are the most sterically encumbered PP(3)-type ligands so far synthesized, and in all cases, only three phosphorus donors are able to bind to the metal center. Complexes RuCl(2)(PhP(2)P(2)(tBu)) (5) and RuCl(2)(P(3)P(3)(tBu)) (6) were characterized by crystallography. Low temperature solution and solid state (31)P{(1)H} NMR were used to demonstrate that the structure of RuCl(2)(P(2)P(3)(tBu)) (4) is probably analogous to that of RuCl(2)(PhP(2)P(2)(tBu)) (5) which had been structurally characterized.

  6. Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C4F9CH2CH2OH)

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, M. D.


    Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C4F9CH2CH2OH, 4:2 FTOH) in the presence of NOx in 700 Torr of N-2/O-2 diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy...

  7. Atmospheric Chemistry of CH3CH2OCH3

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Bjørn Svendsen, Sissel; Østerstrøm, Freja From


    The atmospheric chemistry of methyl ethyl ether, CH3CH2OCH3, was examined using FT-IR/relative-rate methods. Hydroxyl radical and chlorine atom rate coefficients of k(CH3CH2OCH3+OH) = (7.53 ± 2.86) × 10−12 cm3 molecule−1 s−1 and k(CH3CH2OCH3+Cl) = (2.35 ± 0.43) × 10−10 cm3 molecule−1 s−1 were...

  8. Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2

    International Nuclear Information System (INIS)

    Tan, Yee Seng; Halim, Siti Nadiah Abdul; Tiekink, Edward R.T.; Sunway Univ., Bandar Sunway


    Crystallization of Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 from ethanol yields the coordination polymer [{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 }.EtOH] ∞ (1) within 3 h. When the solution is allowed to stand for another hour, the needles begin to dissolve and prisms emerge of the supramolecular isomer (SI), binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 .2EtOH (2). These have been fully characterized spectroscopically and by X-ray crystallography. Polymeric 1 has 2-fold symmetry and features dithiocarbamate ligands coordinating two octahedral Cd atoms in a μ 2 κ 2 -tridentate mode. Binuclear 2 is centrosymmetric with two ligands being μ 2 κ 2 -tridentate as for 1 but the other two being κ 2 -chelating leading to square pyramidal geometries. The conversion of the kinetic crystallization product, 1, to thermodynamic 2 is irreversible but transformations mediated by recrystallization (ethanol and acetonitrile) to related literature SI species, namely coordination polymer [{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 3 .MeCN] ∞ and binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 .2H 2 O.2MeCN, are demonstrated, some of which are reversible. Three other crystallization outcomes are described whereby crystal structures were obtained for the 1:2 co-crystal {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 :2[3-(propan-2-yl)-1,3-oxazolidine-2-thione] (3), the salt co-crystal [iPrNH 2 (CH 2 CH 2 OH)] 4 [SO 4 ] 2 {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 (4) and the salt [iPrNH 2 (CH 2 CH 2 OH)]{Cd[S 2 CN(iPr)CH 2 CH 2 OH] 3 } (5). These arise as a result of decomposition/oxidation of the dithiocarbamate ligands. In each of 3 and 4 the binuclear {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 SI, as in 2, is observed strongly suggesting a thermodynamic preference for this form.

  9. Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation

    DEFF Research Database (Denmark)

    Hurley, MD; Ball, JC; Wallington, TJ


    Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH...

  10. Photodissociation and photoisomerization dynamics of CH2=CHCHO in solution

    International Nuclear Information System (INIS)

    Wu Weiqiang; Yang Chunfan; Zhao Hongmei; Liu Kunhui; Su Hongmei


    By means of time-resolved Fourier transform infrared absorption spectroscopy, we have investigated the 193 nm photodissociation and photoisomerization dynamics of the prototype molecule of α,β-enones, acrolein (CH 2 =CHCHO) in CH 3 CN solution. The primary photolysis channels and absolute branching ratios are determined. The most probable reaction mechanisms are clarified by control experiments monitoring the product yields varied with the triplet quencher addition. The predominant channel is the 1,3-H migration yielding the rearrangement product CH 3 CH=C=O with a branching ratio of 0.78 and the less important channel is the α cleavage of C-H bond yielding radical fragments CH 2 =CHCO+H with a branching ratio of only 0.12. The 1,3-H migration is strongly suggested to correlate with the triplet 3 (ππ * ) state rather than the ground S 0 state and the α cleavage of C-H bond is more likely to proceed in the singlet S 1 1 (nπ * ) state. From the solution experiments we have not only acquired clues clarifying the previous controversial mechanisms, but also explored different photochemistry in solution. Compared to the gas phase photolysis which is dominated by photodissociation channels, the most important channel in solution is the photoisomerization of 1,3-H migration. The reason leading to the different photochemistry in solution is further ascribed to the solvent cage effect.

  11. Photodissociation and photoisomerization dynamics of CH2=CHCHO in solution (United States)

    Wu, Weiqiang; Yang, Chunfan; Zhao, Hongmei; Liu, Kunhui; Su, Hongmei


    By means of time-resolved Fourier transform infrared absorption spectroscopy, we have investigated the 193 nm photodissociation and photoisomerization dynamics of the prototype molecule of α,β-enones, acrolein (CH2CHCHO) in CH3CN solution. The primary photolysis channels and absolute branching ratios are determined. The most probable reaction mechanisms are clarified by control experiments monitoring the product yields varied with the triplet quencher addition. The predominant channel is the 1,3-H migration yielding the rearrangement product CH3CHCO with a branching ratio of 0.78 and the less important channel is the α cleavage of CH bond yielding radical fragments CH2CHCO+H with a branching ratio of only 0.12. The 1,3-H migration is strongly suggested to correlate with the triplet (ππ ∗)3 state rather than the ground S0 state and the α cleavage of CH bond is more likely to proceed in the singlet S1 (nπ∗)1 state. From the solution experiments we have not only acquired clues clarifying the previous controversial mechanisms, but also explored different photochemistry in solution. Compared to the gas phase photolysis which is dominated by photodissociation channels, the most important channel in solution is the photoisomerization of 1,3-H migration. The reason leading to the different photochemistry in solution is further ascribed to the solvent cage effect.

  12. A theoretical study of the carbenoids LiCH 2 X (X= Cl, Br, I ...

    Indian Academy of Sciences (India)

    The trend of the lithium carbenoids reaction barrier with ketene is LiCH2Cl < LiCH2Br < LiCH2I. The results show that the reactions could be highly chemical reactivity with low barriers and could be favoured in experiment. The reactions could proceed easily at lower temperature. The computational results are briefly ...

  13. CH2 Energy Harvesting Systems: Economic Use and Efficiency

    Directory of Open Access Journals (Sweden)

    Chun Cheung


    Full Text Available This paper looks at the City of Melbourne's new office development CH2 as a case study of world class energy performance. In particular, the integrated design of conventionally independent systems has led to the potential to deliver significant savings to the Council and to deliver better environmental conditions to building occupants that in turn may contribute to satisfaction, well-being and productivity. It is concluded that this project has the potential to be an iconic example of effective implementation of ESD (environmental sustainable design principles and therefore act as a demonstration project to others. Energy efficiency of more than 50% of current benchmarks for Melbourne is effected. Energy harvesting is defined as arising from squander, waste and nature, which is a new concept introduced in this paper to better describe the design decision process.

  14. Thermodynamic activity of saturated solutions of CsClO4 in ethylene glycol and its analogs of the HOCH2(CH2CH2O)nCH2OH series

    International Nuclear Information System (INIS)

    Krasnoperova, A.P.; Ivanova, E.F.; Kijko, S.M.; Yukhno, G.D.


    Solubility of CsClO 4 in ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with molar mass 300 and 400 in the temperature range of 273.15-318.15 K has been ascertained by the method of radioactive indicators. Dependence of saturated solutions activity on temperature, dielectric permittivity and the number of (CH 2 CH 2 O) ether groups in glycols is discussed

  15. The ground state torsion rotation spectrum of CH2DOH (United States)

    Pearson, John C.; Yu, Shanshan; Drouin, Brian J.


    The ground state torsion rotation spectrum of CH2DOH has been completely characterized through J = 30 and Ka = 10, 9, 9 in the three torsional sub-states of the ground state; e0, e1, and o1, respectively. Additional a-type assignments are presented to Ka = 11 in each of the torsional sub-states. The data has been analyzed with an empirical power series model as well as an empirical internal axis model. Over 8000 transitions have been assigned and fit with near experimental accuracy over the range of 4-1628 GHz. The characterization of the spectrum allows for a complete set of ground state term values enabling a better understanding of the infrared spectrum. Comparison of the torsional contributions of the Hamiltonian with normal methanol provides great insight into the nature of the asymmetric-top asymmetric-frame internal rotation problem. The comparison with normal methanol also provides a relatively straightforward transformation from the well understood C3V internal rotation problem to the completely asymmetric internal rotation problem. The data and analysis provide some practical wisdom on the impacts of breaking the symmetry and the choice of models for addressing the nearly three fold completely asymmetric internal rotation problem.

  16. The Business Case for Sustainable Design - the City of Melbourne CH2 Project

    Directory of Open Access Journals (Sweden)

    Peter Stewart


    Full Text Available The City of Melbourne's landmark building development project.referred to as Council House 2 (CH2 is to be completed during2006. CH2 is a world leading six star environmental buildingincorporating sustainable technologies and producing financial.environmental and societal benefits. The business case forsustainable design within the context of CH2 is examined . Anoverview is carried out of traditional business case decisionmaking tools used in the context of property development. Thecase for the design and construction of ecologically sustainablebuildings is considered . The CH2 project is reviewed in detail andthe "triple bottom line" business case model developed by the Cityof Melbourne. which underpins the development. is investigated.It is concluded that the CH2 development should deliver diversebenefits to all stakeholders; the Council. staff. business andratepayers. Further. the business case model developed by theCH2 project can be utilized as an exemplar for other developments.

  17. Preparation of tetraalkyl phosphine complexes of the f-block metals. Crystal structure of Th(CH2Ph)4(Me2PCH2CH2PMe2) and U(CH2Ph)3Me(Me2PCH2CH2PMe2)

    International Nuclear Information System (INIS)

    Edwards, P.G.; Andersen, R.A.; Zalkin, A.


    Reaction of 4 molar equiv of PhCH 2 Li with MCl 4 (Me 2 PCH 2 CH 2 PMe 2 ) 2 gives M(CH 2 Ph) 4 (Me 2 PCH 2 CH 2 PMe 2 ), where M is Th or U. Reaction of a mixture of 3 molar equiv of PhCH 2 Li and 1 molar equiv of MeLi with MCl 4 (Me 2 PCH 2 CH 2 PMe 2 ) 2 gives the unsymmetrical alkyls M(CH 2 Ph) 3 Me(Me 2 PCH 2 CH 2 PMe 2 ), where M is Th or U. The molecular structure of Th(CH 2 C 6 H 5 ) 4 (Me 2 PCH 2 CH 2 PMe 2 ) and U(CH 2 C 6 H 5 ) 3 Me(Me 2 PCH 2 CH 2 PMe 2 ) were determined by single-crystal X-ray diffraction methods, and the crystal parameters are reported. In the Th complex there are two independent molecules in the unit cell. The Th atoms are each bonded to four benzyl groups and to two phosphorus atoms from the bis(dimethylphosphino)ethane ligand; the average Th-C distance is 2.55 (2) A, and the average Th-P distance is 3.17 (3) A. In the U complex the uranium atom is bonded to a methyl group, three benzyl groups, and the two phosphorus atoms of the bis(dimethylphosphino)ethane ligand. The U-C(methyl) distance is 2.41 (1) A; the average U-C(benzyl) distance is 2.50 (4) A. 23 references, 3 figures, 7 tables

  18. Synthesis and reactivity of tantalum alkylidene complexes containing the C,N,N'-chelating aryldiamine ligand [C6H4(CH2N(Me)CH2CH2NMe2)-2- (CNN). X-ray structurs of [TaCl2(=CH-t-Bu) (CNN)], [Ta{CH2)3-1,3}(CNN)(O-t-Bu)2], and [Ta(CNN)(O-t-Bu)2(H2C=CH2)

    NARCIS (Netherlands)

    Koten, G. van; Rietveld, M.H.P.; Teunissen, Wendy; Hagen, H.; Water, L. van de; Grove, D.M.; Veldman, N.; Spek, A.L.


    The potentially C,N,N'-chelating anionic aryldiamine ligand [C6H4(CH2N(Me)CH2CH2NMe2)-2]- (CNN) has been employed in the preparation of six-coordinate Ta(V) alkylidene complexes. The new dichloro alkylidene complex [TaCl2(=CH-t-Bu)(CNN)], 2, prepared from [TaCl3(=CH-t-Bu)(THF)2] and [Li(CNN)]2, 1,

  19. Catalytic effect of a single water molecule on the OH + CH2NH reaction. (United States)

    Akbar Ali, Mohamad; M, Balaganesh; Lin, K C


    In recent work, there has been considerable speculation about the atmospheric reaction of methylenimine (CH 2 NH), because this compound is highly reactive, soluble in water, and sticky, thus posing severe experimental challenges. In this work, we have revisited the kinetics of the OH + CH 2 NH reaction assisted by a single water molecule. The potential energy surfaces (PESs) for the water-assisted OH + CH 2 NH reaction were calculated using the CCSD(T)//BH&HLYP/aug-cc-pVTZ levels of theory. The rate coefficients for the bimolecular reaction pathways CH 2 NHH 2 O + OH and CH 2 NH + H 2 OHO were computed using canonical variational transition state theory (CVT) with small curvature tunneling correction. The reaction without water has four elementary reaction pathways, depending on how the hydroxyl radical approaches CH 2 NH. In all cases, the reaction begins with the formation of a single pre-reactive complex before producing abstraction and addition products. When water is added, the products of the reaction do not change, and the reaction becomes quite complex, yielding four different pre-reactive complexes and eight reaction pathways. The calculated rate coefficient for the OH + CH 2 NH (water-free) reaction at 300 K is 1.7 × 10 -11 cm 3 molecule -1 s -1 and for OH + CH 2 NH (water-assisted), it is 5.1 × 10 -14 cm 3 molecule -1 s -1 . This result is similar to the isoelectronic analogous reaction OH + CH 2 O (water-assisted). In general, the effective rate coefficients of the water-assisted reaction are 2∼3 orders of magnitude smaller than water-free. Our results show that the water-assisted OH + CH 2 NH reaction cannot accelerate the reaction because the dominated water-assisted process depends parametrically on water concentration. As a result, the overall reaction rate coefficients are smaller.

  20. Collisional excitation of CH2 rotational/fine-structure levels by helium (United States)

    Dagdigian, P. J.; Lique, F.


    Accurate determination of the abundance of CH2 in interstellar media relies on both radiative and collisional rate coefficients. We investigate here the rotational/fine-structure excitation of CH2 induced by collisions with He. We employ a recoupling technique to generate fine-structure-resolved cross-sections and rate coefficients from close coupling spin-free scattering calculations. The calculations are based on a recent, high-accuracy CH2-He potential energy surface computed at the coupled clusters level of theory. The collisional cross-section calculations are performed for all fine-structure transitions among the first 22 and 24 energy levels of ortho- and para-CH2, respectively, and for temperatures up to 300 K. As a first application, we simulate the excitation of CH2 in typical molecular clouds. The excitation temperatures of the CH2 lines are found to be small at typical densities of molecular clouds, showing that the non-local thermodynamic equilibrium approach has to be used to analyse interstellar spectra. We also found that the fine-structure lines connected with the 404 - 313 and 505 - 414 rotational transitions show possible maser emissions so that they can be easily seen in emission. These calculations show that CH2 may have to be detected mainly through absorption spectra.

  1. Radical routes to interstellar glycolaldehyde. The possibility of stereoselectivity in gas-phase polymerization reactions involving CH(2)O and ˙CH(2)OH. (United States)

    Wang, Tianfang; Bowie, John H


    A previous report that the interstellar molecule glycolaldehyde (HOCH(2)CHO) can be made from hydroxymethylene (HOCH:) and formaldehyde has been revisited at the CCSD(T)/6-311++G(3df,2p)//MP2/6-311++G(3df,2p) level of theory. This reaction competes with the formation of acetic acid and methylformate, molecules which have also been detected in interstellar clouds. Other possible modes of formation of glycolaldehyde by radical/radical reactions have been shown to be viable theoretically as follows: HO˙+˙CH2CHO -->HOCH2CHO [ΔG(Γ)(298K)=-303kJ mol⁻¹] HOCH2˙+˙CHO-->HOCH2CHO (-259kJ mol⁻¹). The species in these two processes are known interstellar molecules. Key radicals ˙CH(2)CHO and ˙CH(2)OH in these sequences have been shown to be stable for the microsecond duration of neutralization/reionization experiments in the dual collision cells of a VG ZAB 2HF mass spectrometer. The polymerization reaction HOCH(2)CH˙OH + nCH(2)O → HOCH(2)[CH(OH)](n)˙CHOH (n = 1 to 3) has been studied theoretically and shown to be energetically feasible, as is the cyclization reaction of HOCH(2)[(CH(2)OH)(4)]˙CHOH (in the presence of one molecule of water at the reacting centre) to form glucose. The probability of such a reaction sequence is small even if polymerization were to occur in interstellar ice containing a significant concentration of CH(2)O. The large number of stereoisomers produced by such a reaction sequence makes the formation of a particular sugar, again for example glucose, an inefficient synthesis. The possibility of stereoselectivity occurring during the polymerization was investigated for two diastereoisomers of HOCH(2)[(CHOH)](2)˙CHOH. No significant difference was found in the transition state energies for addition of CH(2)O to these two diastereoisomers, but a barrier difference of 12 kJ mol(-1) was found for the H transfer reactions ˙OCH(2)[(CHOH)](2)CH(2)OH → HOCH(2)[(CHOH)(2)˙CHOH of the two diastereoisomers.


    NARCIS (Netherlands)



    Treatment of C(5)H(4)CH(2)CH(2)OMe.Li(TMEDA) (TMEDA = N, N, N', N' tetramethylethylenediamine) with half an equivalent of YCl3(THF)(3.5) in toluene afforded the salt- and solvent-free dimeric biscyclopentadienyl yttrium chloride [(C(5)H(4)CH(2)CH(2)OMe)(2)Y-(mu-Cl)](2) (1). Reaction of 1 with one

  3. Hydrogenation of interstellar molecules: a survey for methylenimine (CH2NH) (United States)

    Dickens, J. E.; Irvine, W. M.; DeVries, C. H.; Ohishi, M.


    Methylenimine (CH2NH) has been convincingly detected for the first time outside the Galactic center as part of a study of the hydrogenation of interstellar molecules. We have observed transitions from energy levels up to about 100 K above the ground state in the giant molecular clouds W51, Orion KL and G34.3 + 0.15. In addition, CH2NH was found at the " radical-ion peak" on the quiescent ridge of material in the Orion molecular cloud. The abundance ratio CH2NH/HCN at the radical-ion peak agrees with the predictions of recent gas-phase chemical models. This ratio is an order of magnitude higher in the warmer cloud cores, suggesting additional production pathways for CH2NH, probably on interstellar grains.

  4. CH2M Hill Hanford Group Inc (CHG) Information Resource Management (IRM) Strategic Plan

    International Nuclear Information System (INIS)

    NELSON, R.L.


    The CH2M Hill Hanford Group, Inc., Information Resource Management Strategic Plan is the top-level planning document for applying information and information resource management to achieve the CHG mission for the management of the River Protection Project

  5. Anomalous absorption in H2CN and CH2CN molecules

    Indian Academy of Sciences (India)

    Abstract. Structures of H2CN and CH2CN molecules are similar to that of H2CO mole- cule. The H2CO has shown anomalous absorption for its transition 111 − 110 at 4.8 GHz in a number of cool molecular clouds. Though the molecules H2CN and CH2CN have been identified in TMC-1 and Sgr B2 through some ...

  6. Anomalous absorption in H2CN and CH2CN molecules

    Indian Academy of Sciences (India) Keywords. Interstellar molecules; H2CN; CH2CN. Abstract. Structures of H2CN and CH2CN molecules are similar to that of H2CO molecule. The H2CO has shown anomalous absorption for its transition 111 - 110 at 4.8 GHz in a number of cool molecular clouds.

  7. Direct Determination of the Simplest Criegee Intermediate (CH2OO) Self Reaction Rate. (United States)

    Buras, Zachary J; Elsamra, Rehab M I; Green, William H


    The rate of self-reaction of the simplest Criegee intermediate, CH2OO, is of importance in many current laboratory experiments where CH2OO concentrations are high, such as flash photolysis and alkene ozonolysis. Using laser flash photolysis while simultaneously probing both CH2OO and I atom by direct absorption, we can accurately determine absolute CH2OO concentrations as well as the UV absorption cross section of CH2OO at our probe wavelength (λ = 375 nm), which is in agreement with a recently published value. Knowing absolute concentrations we can accurately measure kself = 6.0 ± 2.1 × 10(-11)cm(3) molecule(-1) s(-1) at 297 K. We are also able to put an upper bound on the rate coefficient for CH2OO + I of 1.0 × 10(-11) cm(3) molecule(-1) s(-1). Both of these rate coefficients are at least a factor of 5 smaller than other recent measurements of the same reactions.

  8. Ultraviolet absorption spectra and kinetics of CH3S and CH2SH radicals

    DEFF Research Database (Denmark)

    Anastasi, C.; Broomfield, M.; Nielsen, O.J.


    The ultraviolet absorption spectra of CH3S and CH2SH radicals have been measured between 215 and 380 nm using the pulse-radiolysis/kinetic-absorption method. One absorption band between 250 and 300 nm and one around 215 nm have been tentatively assigned to the CH2SH and CH3S radicals, respectively....... This spectrum has been used to measure the self-reaction rates of these radicals. Rate constants of 4 x 10(-11) and 7 x 10(-11) cm3 molecule-1 s-1 have been measured at 298 K for CH3S and CH2SH recombination, respectively. The possible reaction pathways are discussed....

  9. The reaction of Criegee intermediate CH2OO with water dimer: primary products and atmospheric impact. (United States)

    Sheps, Leonid; Rotavera, Brandon; Eskola, Arkke J; Osborn, David L; Taatjes, Craig A; Au, Kendrew; Shallcross, Dudley E; Khan, M Anwar H; Percival, Carl J


    The rapid reaction of the smallest Criegee intermediate, CH 2 OO, with water dimers is the dominant removal mechanism for CH 2 OO in the Earth's atmosphere, but its products are not well understood. This reaction was recently suggested as a significant source of the most abundant tropospheric organic acid, formic acid (HCOOH), which is consistently underpredicted by atmospheric models. However, using time-resolved measurements of reaction kinetics by UV absorption and product analysis by photoionization mass spectrometry, we show that the primary products of this reaction are formaldehyde and hydroxymethyl hydroperoxide (HMHP), with direct HCOOH yields of less than 10%. Incorporating our results into a global chemistry-transport model further reduces HCOOH levels by 10-90%, relative to previous modeling assumptions, which indicates that the reaction CH 2 OO + water dimer by itself cannot resolve the discrepancy between the measured and predicted HCOOH levels.

  10. Atmospheric deuterium fractionation: HCHO and HCDO yields in the CH2DO + O2 reaction

    Directory of Open Access Journals (Sweden)

    M. D. Hurley


    Full Text Available The formation of formaldehyde via hydrogen atom transfer from the methoxy radical to molecular oxygen is a key step in the atmospheric photochemical oxidation of methane, and in the propagation of deuterium from methane to molecular hydrogen. We report the results of the first investigation of the branching ratio for HCHO and HCDO formation in the CH2DO + O2 reaction. Labeled methoxy radicals (CH2DO were generated in a photochemical reactor by photolysis of CH2DONO. HCHO and HCDO concentrations were measured using FTIR spectroscopy. Significant deuterium enrichment was seen in the formaldehyde product, from which we derive a branching ratio of 88.2±1.1% for HCDO and 11.8±1.1% for HCHO. The implications of this fractionation on the propagation of deuterium in the atmosphere are discussed.

  11. Identification of LDPE Grades Focusing on Specific CH2 Raman Vibration Modes

    Directory of Open Access Journals (Sweden)

    Richard Jumeau


    Full Text Available The possibilities of applications of vibrational spectroscopy techniques (Raman spectroscopy in the analysis and characterization of polymers are more and more used and accurate. In this paper, our purpose is to characterize Low Density Poly(Ethylene (LDPE grades by Raman spectroscopy and in particular with CH2 Raman vibration modes. With temperature measurements, we determine different amorphous and crystalline Raman assignments. From these results and on the basis of the evolution of CH2 bending Raman vibration modes, we develop a phenomenological model in correlation with Differential Scanning Calorimetry and in particular with crystalline lamella thickness determination.

  12. CH2M Hill Hanford Group Inc (CHG) Information Resource Management (IRM) Strategic Plan

    International Nuclear Information System (INIS)

    NELSON, R.L.


    The CH2M HILL Hanford Group, Inc. (CHG), Information Resource Management Strategic Plan is the top-level planning document for applying information and information resource management to achieve the CHG mission for the management of the River Protection Project waste tank farm

  13. First Observation of the Rotational Spectrum of the Bromomethyl Radical, CH2Br

    Czech Academy of Sciences Publication Activity Database

    Bailleux, S.; Dréan, P.; Godon, M.; Zelinger, Zdeněk; Duan, CH.


    Roč. 6, - (2004), s. 3049-3051 ISSN 1463-9076 R&D Projects: GA AV ČR IAA3040101; GA AV ČR IAA1010110 Institutional research plan: CEZ:AV0Z4040901 Keywords : rotational spectrum * bromomethyl radical * CH2Br Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.076, year: 2004

  14. Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide. (United States)

    Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min


    The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

  15. Electronic structure, spectra, and nature of electronically excited states of the bifluorophores stilbene-CH2-coumarine and phenyl-CH2-coumarine (United States)

    Sokolova, I. V.; Vasil'Eva, N. Yu.; Vylegzhanina, Ya. O.; Maier, G. V.


    Quantum-chemical calculations of trans-stilbene and benzene molecules as well as molecules of bifluorophores based on them — trans-stilbene-CH2-coumarine 120 and phenyl-CH2-coumarine — were performed by the INDO/S method. The form of the molecular orbitals, the distribution of the electron density in the ground and excited states, the spectra and nature of the electronically states of bifluorophore molecules were established in relation to the energy donor and acceptor molecules. Three conformations of the bifluorophore molecules were studied (planar, “edge,” “wing”). It was discovered that the energy and type of the molecular orbitals of the bifluorophores are independent of the relative orientation of the donor and acceptor subsystems. It is shown that the mixed character of the three lowest electronically excited states, participating in the formation of the spectrum, of the bifluorophores gives rise to quite appreciable overlapping of their electronic wave functions and, therefore, ensures that the internal-conversion processes are efficient.

  16. Probing the global potential energy minimum of (CH2O)2: THz absorption spectrum of (CH2O)2 in solid neon and para-hydrogen. (United States)

    Andersen, J; Voute, A; Mihrin, D; Heimdal, J; Berg, R W; Torsson, M; Wugt Larsen, R


    The true global potential energy minimum configuration of the formaldehyde dimer (CH 2 O) 2 , including the presence of a single or a double weak intermolecular CH⋯O hydrogen bond motif, has been a long-standing subject among both experimentalists and theoreticians as two different energy minima conformations of C s and C 2h symmetry have almost identical energies. The present work demonstrates how the class of large-amplitude hydrogen bond vibrational motion probed in the THz region provides excellent direct spectroscopic observables for these weak intermolecular CH⋯O hydrogen bond motifs. The combination of concentration dependency measurements, observed isotopic spectral shifts associated with H/D substitutions and dedicated annealing procedures, enables the unambiguous assignment of three large-amplitude infrared active hydrogen bond vibrational modes for the non-planar C s configuration of (CH 2 O) 2 embedded in cryogenic neon and enriched para-hydrogen matrices. A (semi)-empirical value for the change of vibrational zero-point energy of 5.5 ± 0.3 kJ mol -1 is proposed for the dimerization process. These THz spectroscopic observations are complemented by CCSD(T)-F12/aug-cc-pV5Z (electronic energies) and MP2/aug-cc-pVQZ (force fields) electronic structure calculations yielding a (semi)-empirical value of 13.7 ± 0.3 kJ mol -1 for the dissociation energy D 0 of this global potential energy minimum.

  17. Intramolecular solvation effects in the SN2 reaction Cl-+Cl(CH2)nCN

    International Nuclear Information System (INIS)

    Pagliai, Marco; Raugei, Simone; Cardini, Gianni; Schettino, Vincenzo


    The chemical reactions Cl - +Cl(CH 2 ) n CN (n=2-5) have been studied with ab initio molecular dynamics. The effects of the cyano group on the energy profile of the reactions as the length of the alkilic chain increases have been discussed in terms of electrostatics of the systems. The thermal effects have been computed in the Blue Moon Ensemble showing a large influence on the energy barriers. It has been shown that six membered hydrogen-bonded pre-reactive complexes are stable even at room temperature. The results of the simulation allow for an explanation for the increased reactivity of these systems compared to the parent Cl - +Cl(CH 2 ) n CH 3 reactions

  18. A novel resistance gene, lnu(H), conferring resistance to lincosamides in Riemerella anatipestifer CH-2. (United States)

    Luo, Hong-Yan; Liu, Ma-Feng; Wang, Ming-Shu; Zhao, Xin-Xin; Jia, Ren-Yong; Chen, Shun; Sun, Kun-Feng; Yang, Qiao; Wu, Ying; Chen, Xiao-Yue; Biville, Francis; Zou, Yuan-Feng; Jing, Bo; Cheng, An-Chun; Zhu, De-Kang


    The Gram-negative bacterium Riemerella anatipestifer CH-2 is resistant to lincosamides, having a lincomycin (LCM) minimum inhibitory concentration (MIC) of 128 µg/mL. The G148_1775 gene of R. anatipestifer CH-2, designated lnu(H), encodes a 260-amino acid protein with ≤41% identity to other reported lincosamide nucleotidylyltransferases. Escherichia coli Rosetta TM (DE3) containing the pBAD24-lnu(H) plasmid showed four- and two-fold increases in the MICs of LCM and clindamycin (CLI), respectively. A kinetic assay of the purified Lnu(H) enzyme for LCM and CLI showed that the protein could inactive lincosamides. Mass spectrometry analysis demonstrated that the Lnu(H) enzyme catalysed adenylylation of lincosamides. In addition, an lnu(H) gene deletion strain exhibited 512- and 32-fold decreases in LCM and CLI MICs, respectively. The wild-type level of lincosamide resistance could be restored by complementation with a shuttle plasmid carrying the lnu(H) gene. The transformant R. anatipestifer ATCC 11845 [lnu(H)] acquired by natural transformation also exhibited high-level lincosamide resistance. Moreover, among 175 R. anatipestifer field isolates, 56 (32.0%) were positive for the lnu(H) gene by PCR. In conclusion, Lnu(H) is a novel lincosamide nucleotidylyltransferase that inactivates LCM and CLI by nucleotidylylation, thus conferring high-level lincosamide resistance to R. anatipestifer CH-2. Copyright © 2017. Published by Elsevier B.V.

  19. Ultraviolet spectrum and photochemistry of the simplest Criegee intermediate CH2OO. (United States)

    Beames, Joseph M; Liu, Fang; Lu, Lu; Lester, Marsha I


    Ozonolysis of alkenes in the troposphere produces Criegee intermediates, which have eluded detection in the gas phase until very recently. This laboratory has synthesized the simplest Criegee intermediate within a quartz capillary tube affixed to a pulsed valve to cool and isolate CH(2)OO in a supersonic expansion. UV excitation resonant with the B (1)A' ← X (1)A' transition depletes the ground-state population of CH(2)OO, which is detected by single-photon ionization at 118 nm. The large UV-induced depletion (approaching 100%) near the peak of the profile at 335 nm is indicative of rapid dissociation, consistent with the repulsive B (1)A' potential along the O-O coordinate computed theoretically. The experimental spectrum is in very good accord with the absorption spectrum calculated using the one-dimensional reflection principle. The B ← X spectrum is combined with the solar actinic flux to estimate an atmospheric lifetime for CH(2)OO at midday on the order of ∼1 s with respect to photodissociation.

  20. 20  kHz CH2O and OH PLIF with stereo PIV. (United States)

    Hammack, Stephen D; Carter, Campbell D; Skiba, Aaron W; Fugger, Christopher A; Felver, Josef J; Miller, Joseph D; Gord, James R; Lee, Tonghun


    Planar laser-induced fluorescence (PLIF) of hydroxyl (OH) and formaldehyde (CH 2 O) radicals was performed alongside stereo particle image velocimetry (PIV) at a 20 kHz repetition rate in a highly turbulent Bunsen flame. A dual-pulse burst-mode laser generated envelopes of 532 nm pulse pairs for PIV as well as a pair of 355 nm pulses, the first of which was used for CH 2 O PLIF. A diode-pumped solid-state Nd:YAG/dye laser system produced the excitation beam for the OH PLIF. The combined diagnostics produced simultaneous, temporally resolved two-dimensional fields of OH and CH 2 O and two-dimensional, three-component velocity fields, facilitating the observation of the interaction of fluid dynamics with flame fronts and preheat layers. The high-fidelity data acquired surpass the previous state of the art and demonstrate dual-pulse burst-mode laser technology with the ability to provide pulse pairs at both 532 and 355 nm with sufficient energy for scattering and fluorescence measurement at 20 kHz.

  1. Low Temperature Studies of the Removal Reactions of 1CH2 with Relevance to the Atmosphere of Titan (United States)

    Douglas, Kevin; Slater, Eloise; Feng, Wuhu; Blitz, Mark; Plane, John; Heard, Dwayne; Seakins, Paul


    The photolysis of methane by UV photons is the primary source of hydrocarbon radicals in the atmosphere of Titan and the giant planets. Although there is still significant uncertainty in the branching ratios of products, the production of the first singlet excited state of methylene, 1CH2, is thought to be a significant channel. Reactions of 1CH2 with methane (R1a) and hydrogen (R2a) are a significant source of methyl radicals, the recombination of which is the primary route to ethane on Titan (R3). The reaction of 1CH2 with acetylene is also a source of propargyl, C3H3, the recombination of which is the primary route to benzene on Titan. However, in addition to these reactions of 1CH2 leading to chemical products, there is also competition between inelastic electronic relaxation to form ground triplet state methylene, 3CH2 (R1b and R2b). Triplet methylene is much less reactive, and cannot undergo the complex insertion elimination reactions of singlet methylene. The main reaction of 3CH2 occurs with other radical species such as H (R4). 1CH2 + CH4 → CH3 + H2 (R1a) 1CH2 + CH4 → 3CH2 + CH4 (R1b) 1CH2 + H2 → CH3 + H (R2a) 1CH2 + H2 → 3CH2 + H2 (R2a) CH3 + CH3 (+M) → C2H6 (R3) 3CH2 + H → CH + H2 (R4) Using pulsed laser photolysis laser-induced fluorescence, we have studied the reaction kinetics for the removal of 1CH2 with N2, H2, CH4, C2H6, C2H4, C2H6, and O2 as a function of temperature. Low temperatures between 43 and 135 K were obtained using a pulsed Laval nozzle apparatus, while data at 160 K was obtained using a low flow reaction cell with cryogenic cooling. In addition to measuring total removal rates, the fraction of 1CH2 removed via electronic relaxation versus chemical reaction to products has also been investigated for H2 and CH4 at 160 and 73 K. Results show that that removal of 1CH2 by electronic relaxation increases with decreasing temperature. These experimental results indicate that the majority of 1CH2 formed in Titan's atmosphere will be

  2. Methane Provenance Determined by CH2D2 and 13CH3D Abundances (United States)

    Kohl, I. E.; Giunta, T.; Warr, O.; Ash, J. L.; Ruffine, L.; Sherwood Lollar, B.; Young, E. D.


    Determining the provenance of naturally occurring methane gases is of major interest to energy companies and atmospheric climate modelers, among others. Bulk isotopic compositions and other geochemical tracers sometimes fail to provide definitive determinations of sources of methane due to complications from mixing and complicated chemical pathways of origin. Recent measurements of doubly-substituted isotopologues of methane, CH2D2 (UCLA) and 13CH3D (UCLA, CalTech, and MIT) have allowed for major improvements in sourcing natural methane gases. Early work has focused on formation temperatures obtained when the relative abundances of both doubly-substituted mass-18 species are consistent with internal equilibrium. When methane gases do not plot on the thermodynamic equilibrium curve in D12CH2D2 vs D13CH3D space, temperatures determined from D13CH3D values alone are usually spurious, even when appearing reasonable. We find that the equilibrium case is actually rare and almost exclusive to thermogenic gases produced at temperatures exceeding 100°C. All other relevant methane production processes appear to generate gases that are not in isotopologue-temperature equilibrium. When gases show departures from equilibrium as determined by the relationship between CH2D2 and 13CH3D abundances, data fall within empirically defined fields representing formation pathways. These fields are thus far consistent between different geological settings and and between lab experiments and natural samples. We have now defined fields for thermogenic gas production, microbial methanogenesis, low temperature abiotic (Sabatier) synthesis and higher temperature FTT synthesis. The majority of our natural methane data can be explained by mixing between end members originating within these production fields. Mixing can appear complex, resulting in both hyper-clumped and anti-clumped isotopologue abundances. In systems where mixtures dominate and end-members are difficult to sample, mixing models

  3. A theoretical study of the carbenoids LiCH2X (X = Cl, Br, I ...

    Indian Academy of Sciences (India)


    Table 1. Calculated bond lengths and bond elongation in the TSn (n = 1–6) as compared to the bond lengths of the starting materials (LiCH2X, where X = Cl, Br, I), respectively. C. 1. –Li. C. 1. –Li. C. 1. –X. C. 1. –X. Li-X. Li-X. X. TSn r(nm) elong. (%) r (nm) elong. (%) r (nm) elong. (%). Cl. TS1. 0⋅1993. 2⋅63. 0⋅2499. 19⋅57.

  4. The Possible Interstellar Anion CH2CN-: Spectroscopic Constants, Vibrational Frequencies, and Other Considerations (United States)

    Fortenberry, Ryan C.; Crawford, T. Daniel; Lee, Timothy J.


    The A 1B1 interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study we are employing the use of proven quartic force elds and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for X 1A0 CH2CN?? in order to assist in laboratory studies and astronomical observations. Keywords: Astrochemistry, ISM: molecular anions, Quartic force elds, Rotational constants, Vibrational frequencies

  5. Synthesis and Characterization of (η5-C5Me5)2Ti(R)Cl (R = Me, Et, n-Pr, CH=CH2, Ph, O-n-Pr) and Their Salt Metathesis Reactions. Thermal Decomposition Pathways of (η5-C5Me5)2Ti(Me)R' (R' = Et, CH=CH2, Ph, CH2Ph)

    NARCIS (Netherlands)

    Luinstra, Gerrit A.; Teuben, Jan H.


    Complexes Cp*2Ti(R)Cl (Cp* = η5-C5Me5; R = Me (1), Et (2), n-Pr (3), CH=CH2 (41, Ph (5), O-n-Pr (6)) have been prepared by oxidation of Cp*2TiR with lead dichloride. Not every compound Cp*2Ti(R)Cl was accessible and for R = CH2CMe3 and CH2Ph reduction to Cp*2TiCl and R· was observed. Homolysis of


    NARCIS (Netherlands)


    Complexes Cp*2Ti(R)Cl (Cp* = eta-5-C5Me5; R = Me (1), Et (2), n-Pr (3), CH=CH2 (4), Ph (5), O-n-Pr (6)) have been prepared by oxidation Of CP*2TiR with lead dichloride. Not every compound Cp*2Ti(R)Cl was accessible and for R = CH2CMe3 and CH2Ph reduction to Cp*2TiCl and R. was observed. Homolysis of

  7. An Evaluation of a Proposed Ventilation System for Melbourne's CH2 Building

    Directory of Open Access Journals (Sweden)

    Lu Aye


    Full Text Available The understanding of ventilation requirements in commercial buildings has been significantly revised in the last 10-15 years. A link between health, productivity and increased fresh air use has been established by some research and this understanding underpins the ventilation philosophy adopted for the CH2 building. The ventilation system design for CH2 that has been evaluated in this paper envisages a mechanically driven system during the day, using the displacement technique to distribute filtered air. All introduced air will be drawn from outside and no recycling of air will occur. Natural ventilation will be employed at night using the stack effect, enhanced by turbine ventilators. This paper critiques the proposed ventilation system in the light of international experience and the particular conditions of the building's location. The evidence suggests that natural ventilation sometimes may be inadequate to achieve the desired objectives. Minimization of indoor pollutants, adequate filtration and high levels of ventilation should, however, ensure satisfactory air quality during occupied hours.

  8. Rotational Spectra of N2OH+ and CH2CHCNH+ Molecular Ions (United States)

    Martinez, Oscar; , Jr.; Lattanzi, Valerio; McCarthy, Michael C.; Thorwirth, Sven


    Protonated molecular ions of nitrous oxide (N2OH+) and acrylonitrile (CH2CHCNH+) have been detected at high spectral resolution in the molecular beam of a Fourier transform microwave spectrometer on the basis of high-level ab initio calculations. The ions were synthesized in the throat of a pulsed supersonic nozzle by discharging in a flow of the corresponding precursor gas (either N2O or CH2CHCN) heavily diluted in H2. Two isomers of N2OH+ were identified, corresponding to protonation at either the N or O end of NNO. This work contributes precise nitrogen hyperfine coupling constants to existing measurements of ground state NNOH+, and represents the first detection of the higher energy HNNO+ isomer, which is calculated to lie 4.4 kcal/mol above ground. In addition, protonated acrylonitrile has been detected for the first time at high spectral resolution, yielding spectroscopic constants that are in excellent agreement with high-level quantum-chemical calculations. Owing to sizable calculated dipole moments of protonated nitrous oxide and acrylonitrile and the relatively high proton affinities of their neutral counterparts, both cations are plausible candidates for astronomical detection with radio telescopes. At CCSD(T)/cc-pwCVQZ level of theory with zero-point vibrational effects at CCSD(T)/cc-pVQZ. J. M. L. Martin & T. J. Lee, J. Chem. Phys. 98, 7951 (1993)

  9. Formaldehyde mediated proton-transport catalysis in the ketene-water radical cation CH2=C(=O)OH2•+

    NARCIS (Netherlands)

    Lee, R.; Ruttink, P.J.A.; Burgers, P.C.; Terlouw, J.K.


    Previous studies have shown that the solitary ketene-water ion CH2=C(=O)OH2+ (1) does not isomerize into CH2=C(OH)2+ (2), its more stable hydrogen shift isomer. Tandem mass spectrometry based collision experiments reveal that this isomerization does take place in the CH2=O loss from low-energy

  10. Stabilizing the CH2 Domain of an Antibody by Engineering in an Enhanced Aromatic Sequon. (United States)

    Chen, Wentao; Kong, Leopold; Connelly, Stephen; Dendle, Julia M; Liu, Yu; Wilson, Ian A; Powers, Evan T; Kelly, Jeffery W


    Monoclonal antibodies (mAbs) exhibiting highly selective binding to a protein target constitute a large and growing proportion of the therapeutics market. Aggregation of mAbs results in the loss of their therapeutic efficacy and can result in deleterious immune responses. The CH2 domain comprising part of the Fc portion of Immunoglobulin G (IgG) is typically the least stable domain in IgG-type antibodies and therefore influences their aggregation propensity. We stabilized the CH2 domain by engineering an enhanced aromatic sequon (EAS) into the N-glycosylated C'E loop and observed a 4.8 °C increase in the melting temperature of the purified IgG1 Fc fragment. This EAS-stabilized CH2 domain also conferred enhanced stability against thermal and low pH induced aggregation in the context of a full-length monoclonal IgG1 antibody. The crystal structure of the EAS-stabilized (Q295F/Y296A) IgG1 Fc fragment confirms the design principle, i.e., the importance of the GlcNAc1•F295 interaction, and surprisingly reveals that the core fucose attached to GlcNAc1 also engages in an interaction with F295. Inhibition of core fucosylation confirms the contribution of the fucose-Phe interaction to the stabilization. The Q295F/Y296A mutations also modulate the binding affinity of the full-length antibody to Fc receptors by decreasing the binding to low affinity Fc gamma receptors (FcγRIIa, FcγRIIIa, and FcγRIIIb), while maintaining wild-type binding affinity to FcRn and FcγRI. Our results demonstrate that engineering an EAS into the N-glycosylated reverse turn on the C'E loop leads to stabilizing N-glycan-protein interactions in antibodies and that this modification modulates antibody-Fc receptor binding.

  11. Reaction between CH2 and HCCN: a theoretical approach to acrylonitrile formation in the interstellar medium. (United States)

    Shivani; Misra, Alka; Tandon, Poonam


    Acrylonitrile (CH2CHCN) was first detected in dense molecular cloud SgrB2. The synthesis of this interstellar molecule is reported to be quite difficult. Therefore, in the present work an attempt has been made to explore the possibility of formation of acrylonitrile from some simple molecules and radicals detected in interstellar space by radical-radical interaction scheme, both in the gas phase and in the icy grains. All calculations are performed using quantum chemical methods with density functional theory (DFT) at the B3LYP/6-311G (d,p) level and Møller-Plesset perturbation theory at the MP2/6-311G (d,p) level. In the discussed chemical pathway, the reaction is found to be totally exothermic and barrier less giving rise to a high probability of acrylonitrile formation in Interstellar space.

  12. Kinetics of IO Production in the CH2I + O2 Reaction Studied by Cavity Ring-Down Spectroscopy. (United States)

    Foreman, Elizabeth S; Murray, Craig


    Cavity ring-down spectroscopy was used to study the kinetics of formation of IO radicals in the reaction of CH2I + O2 in a flow cell at 52 ± 3 Torr total pressure of N2 diluent and a temperature of 295 K. CH2I was produced by photolysis of CH2I2 at 355 nm and IO probed on the A(2)Π3/2–X(2)Π3/2 (3,0) and (3,1) bands at 435.70 and 448.86 nm, respectively. The rates of formation of IO(v″ = 0) and IO(v″ = 1) were measured as a function of O2 number density using either conventional transient absorption or the simultaneous kinetic and ring-down technique, respectively. IO(v″ = 1) was found to be formed with a significantly larger rate constant, but reached far smaller peak concentrations than IO(v″ = 0). Kinetic modeling supports the conclusion that IO(v″ = 0) is produced both directly and through secondary chemistry, most probably involving the initial formation of the Criegee intermediate CH2OO and subsequent reaction with I atoms, while IO(v″ = 1) is produced exclusively via a direct mechanism. We propose that the reaction mechanism (direct or indirect) depends upon the degree of initial excitation of the photolytically produced CH2I reagent.

  13. Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios. (United States)

    Lakshmanan, Sandhiya; Pratihar, Subha; Machado, Francisco Bolivar Correto; Hase, William Louis


    The reaction of 3CH2 with 3O2 is of fundamental importance in combustion and the reaction is complex as a result of multiple extremely exothermic product channels. In the present study, direct dynamics simulations were performed to study the reaction on both the singlet and triplet potential energy surfaces (PESs). The simulations were performed at the UM06/6-311++G(d,p) level of theory. Trajectories were calculated at a temperature of 300 K and all reactive trajectories proceeded through the carbonyl oxide Criegee intermediate, CH2OO, on both the singlet and triplet PESs. The triplet surface leads to only one product channel, H2CO + O(3P), while the singlet surface leads to 8 product channels with their relative importance as: CO + H2O > CO + OH + H ~ H2CO + O(1D) > HCO + OH ~ CO2 + H2 ~ CO + H2 + O(1D) > CO2 + H + H > HCO + O(1D) + H. Reaction on the singlet PES is barrierless, consistent with experiment and the total rate constant on the singlet surface is 0.93 ± 0.22 x 10-12 cm3molecule-1s-1 in comparison to the recommended experimental rate constant of 3.3 x 10-12 cm3molecule-1s-1. The simulation product yields for the singlet PES are compared with experiment and the most significant differences are for H, CO2, and H2O. Reaction on the triplet surface is also barrierless, inconsistent with experiment. A discussion is given of the need for future calculations to address the: (1) barrier on the triplet PES for 3CH2 + 3O2 → 3CH2OO; (2) temperature dependence of the 3CH2 + 3O2 reaction rate constant and product branching ratios; and (3) possible non-RRKM dynamics of the 1CH2OO Criegee intermediate.

  14. Prebiotic molecules formation through the gas-phase reaction between HNO and CH2CHOH2+ (United States)

    Redondo, Pilar; Martínez, Henar; Largo, Antonio; Barrientos, Carmen


    Context. Knowing how the molecules that are present in the ISM can evolve to more complex ones is an interesting topic in interstellar chemistry. The study of possible reactions between detected species can help to understand the evolution in complexity of the interstellar matter and also allows knowing the formation of new molecules which could be candidates to be detected. We focus our attention on two molecules detected in space, vinyl alcohol (CH2CHOH) and azanone (HNO). Aims: We aim to carry out a theoretical study of the ion-molecule reaction between protonated vinyl alcohol and azanone. The viability of formation of complex organic molecules (COMs) from these reactants is expected to provide some insight into the formation of prebiotic species through gas phase reactions. Methods: The reaction of protonated vinyl alcohol with azanone has been theoretically studied by using ab initio methods. Stationary points on the potential energy surface (PES) were characterized at the second-order Moller-Plesset level in conjunction with the aug-cc-pVTZ (correlation-consistent polarized valence triple-zeta) basis set. In addition, the electronic energies were refined by means of single-point calculations at the CCSD(T) level (coupled cluster single and double excitation model augmented with a non-iterative treatment of triple excitations) with the same basis set. Results: From a thermodynamic point of view, twelve products, composed of carbon, oxygen, nitrogen, and hydrogen which could be precursors in the formation of more complex biological molecules, can be obtained from this reaction. Among these, we focus especially on ionized glycine and two of its isomers. The analysis of the PES shows that only formation of cis- and trans-O-protonated imine acetaldehyde, CH2NHCOH+ and, CHNHCHOH+, are viable under interstellar conditions. Conclusions: The reaction of protonated vinyl alcohol with azanone can evolve in the interstellar medium to more complex organic molecules of

  15. Quantum computing applied to calculations of molecular energies: CH2 benchmark. (United States)

    Veis, Libor; Pittner, Jiří


    Quantum computers are appealing for their ability to solve some tasks much faster than their classical counterparts. It was shown in [Aspuru-Guzik et al., Science 309, 1704 (2005)] that they, if available, would be able to perform the full configuration interaction (FCI) energy calculations with a polynomial scaling. This is in contrast to conventional computers where FCI scales exponentially. We have developed a code for simulation of quantum computers and implemented our version of the quantum FCI algorithm. We provide a detailed description of this algorithm and the results of the assessment of its performance on the four lowest lying electronic states of CH(2) molecule. This molecule was chosen as a benchmark, since its two lowest lying (1)A(1) states exhibit a multireference character at the equilibrium geometry. It has been shown that with a suitably chosen initial state of the quantum register, one is able to achieve the probability amplification regime of the iterative phase estimation algorithm even in this case.

  16. Polymorphism Analysis of Ch1 and Ch2 Genes in the Siberian Cat

    Directory of Open Access Journals (Sweden)

    Stefano Sartore


    Full Text Available Cats are usually spreaders of allergens that are critical for sensitive people; the Siberian cat is a breed supposed to be low level allergenic, according to some breeders’ statements. The sequence of the two genes, namely Ch1 and Ch2, that code for the allergen Fel d 1, the major allergen responsible for outbreaks of allergy symptoms, is not yet known in the Siberian cat, and finding this was the aim of our investigation. Notably, our work is the first survey of the genetic structure of these genes in Siberian cats. The comparison of the sequences of Siberian cats, non-Siberian cats, and sequences present in the National Center for Biotechnology Information database revealed a considerable number of mutations; some of those detected in the Siberian cat, due to their position in exon regions, could affect the Fel d 1 allergenic properties. Therefore, further investigations are recommended to assess if the identified mutations can be responsible for a reduced-allergen synthesis and can be used as markers for selection of low level allergenic cats.

  17. Polymorphism Analysis of Ch1 and Ch2 Genes in the Siberian Cat. (United States)

    Sartore, Stefano; Landoni, Eleonora; Maione, Sandra; Tarducci, Alberto; Borrelli, Antonio; Soglia, Dominga; Rasero, Roberto; Sacchi, Paola


    Cats are usually spreaders of allergens that are critical for sensitive people; the Siberian cat is a breed supposed to be low level allergenic, according to some breeders' statements. The sequence of the two genes, namely Ch1 and Ch2 , that code for the allergen Fel d 1, the major allergen responsible for outbreaks of allergy symptoms, is not yet known in the Siberian cat, and finding this was the aim of our investigation. Notably, our work is the first survey of the genetic structure of these genes in Siberian cats. The comparison of the sequences of Siberian cats, non-Siberian cats, and sequences present in the National Center for Biotechnology Information database revealed a considerable number of mutations; some of those detected in the Siberian cat, due to their position in exon regions, could affect the Fel d 1 allergenic properties. Therefore, further investigations are recommended to assess if the identified mutations can be responsible for a reduced-allergen synthesis and can be used as markers for selection of low level allergenic cats.

  18. Low temperature studies of the removal reactions of 1CH2 with particular relevance to the atmosphere of Titan (United States)

    Douglas, Kevin; Blitz, Mark A.; Feng, Wuhu; Heard, Dwayne E.; Plane, John M. C.; Slater, Eloise; Willacy, Karen; Seakins, Paul W.


    Methylene, CH2, is one of the major photolysis products of methane by Lyman-α radiation and is involved in the photochemistry of the atmospheres of Titan and the giant planets. The kinetics of the reactions of the first excited state of methylene, 1CH2, with He, N2, O2, H2 and CH4 have been measured over the temperature range 43-160 K by pulsed laser photolysis, monitoring 1CH2 removal by laser induced fluorescence. Low temperatures were obtained with either a pulsed Laval expansion (43-134 K) or a, slow flow reaction cell (160 K). The rate coefficients for the reactions with N2, O2, H2 and CH4 all showed a strong negative temperature dependence. In combination with other literature data, the rate coefficients can be parameterised as: kHe(43 chemistry and transport model. A significant decrease (∼40%) in the mixing ratio of ethane between 800 and 1550 km is calculated due to the decrease contribution of methyl production from the reaction of 1CH2 with CH4, with smaller increases in the concentrations of ethene and acetylene. Ethene production is enhanced by more methylene being converted to methylidene, CH, and the subsequent reaction of CH with CH4 to generate ethene. Photolysis of ethene is the major route to acetylene formation.

  19. Synthesis, characterization, structural and biological aspects of copper(II) dithiocarbamate complexes - Part II, [Cu{S2CN(Me)(R1)}2], [Cu{S2CN(Me)(R2)}2] and [Cu{S2CN(R3)(R4)}2] {R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH} (United States)

    Ferreira, Isabella P.; de Lima, Geraldo M.; Paniago, Eucler B.; Takahashi, Jacqueline A.; Krambrock, Klaus; Pinheiro, Carlos B.; Wardell, James L.; Visentin, Lorenzo C.


    Three new copper(II) dithiocarbamates (DTC), [Cu{S2CN(Me)(R1)}2] (1), [Cu{S2CN(Me)(R2)}2] (2) and [Cu{S2CN(R3)(R4)}2] (3) with R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH, have been synthesized and characterized by different spectroscopic techniques. Complexes (1) and (2) display typical EPR spectra for separated Cu(II) centers, and the spectrum of (3) is characteristic of two magnetically coupled Cu(II) ions with S = 1. The X-ray crystallographic determination has shown that complexes (1) and (2) crystallise in the triclinic and monoclinic systems. In addition both complexes are monomers in which the geometry at each Cu(II) is square planar. The in vitro antimicrobial activity of the sodium salts of ligands, and of the Cu(II)-DTC complexes have been screened against Aspergillus flavus, Aspergillus niger, Aspergillus parasiticus, Penicillium citrinum and Curvularia senegalensis, as well as Gram positive and Gram negative bacteria. Finally, the toxic effects of complexes (1)-(3) were performed using Chlorella vulgaris.

  20. Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

    KAUST Repository

    Chen, Yin


    By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

  1. Atmospheric lifetimes and ozone depletion potentials of methyl bromide (CH3Br) and dibromomethane (CH2Br2)

    Energy Technology Data Exchange (ETDEWEB)

    Mellouki, A.; Talukdar, R.K.; Schmoltner, A.; Gierczak, T.; Mills, M.J.; Solomon, S.; Ravishankara, A.R. (NOAA, Boulder, CO (United States))


    The rate coefficients for the reactions of OH radical with CH3Br and CH2Br2 were measured as functions of temperature using the laser photolysis - laser induced fluorescence method. This data was incorporated into a semiempirical model (Solomon et al., 1992) and a 2D model to calculate the steady-state ozone depletion potentials (ODP) and atmospheri lifetimes, tau, with greatly improved accuracy as compared to earlier studies. The calculated ODPs and tau are 0.65 and 1.7 years and 0.17 and 0.41 years for CH3Br and CH2Br2, respectively, using the semiempirical model. These lifetimes agree well with those calculated using a 2D model. This study better quantifies the ODPs and tau of these species which are needed inputs for discussion of possible regulation of human emissions currently under international considerations. 29 refs.

  2. Magnesium replacement in formaldehyde: Theoretical rovibrational analysis of X ∼ 3B1 MgCH2 (United States)

    Bassett, Matthew K.; Fortenberry, Ryan C.


    A full, anharmonic set of fundamental vibrational frequencies as well as spectrosocpic constants are provided at high-level for X ∼ 3B1 MgCH2 for the first time. The present data are in line with previous computational and Ar-matrix results, but the anharmonic data show that two brightest frequencies, ν4 and ν5 , are nearly coincident with one another at 560 cm-1. Hence, this area is the best spectral region to search for signatures of this molecule. The rotational constants are also provided indicating a near-prolate rotational progression which should aid in microwave/millimeter-wave analysis of this molecule. Magnesium is known to be a significant component of the Earth, and molecules containing it may be more common in the interstellar medium/circumstellar media than previously thought. More spectral characterization of such molecules like MgCH2 should be undertaken, and this work is a step in that direction.

  3. Femtosecond photolysis of CH 2Br 2 in acetonitrile: Capturing the bromomethyl radical and bromine-atom charge transfer complex through deep-to-near UV probing (United States)

    Pal, Suman K.; Mereshchenko, Andrey S.; El-Khoury, Patrick Z.; Tarnovsky, Alexander N.


    Dibromomethane (CH 2Br 2) in acetonitrile is a suitable precursor to characterize the absorption signatures of the CH 2Br rad radical and solvent rad Br charge-transfer complexes. Following irradiation of CH 2Br 2 at 255 nm, the iso-H 2C sbnd Br sbnd Br isomer product rapidly converts back to the parent species, and transient absorption spectra reveal the bands of solvent-separated radical species, the CH 2Br rad radical peaking at 235 nm, as well as the CH 3CN·Br complex at 272 nm. The absorption of CH 2Br rad exhibits minor solvatochromic shifts upon going from acetonitrile to cyclohexane, and the molecular decadic extinction coefficient of CH 3CN·Br is estimated to be 1470 M -1 cm -1.

  4. Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH+allene reaction

    International Nuclear Information System (INIS)

    Raman, Arjun S.; Justine Bell, M.; Lau, K.-C.; Butler, Laurie J.


    These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH 2 CCH 2 OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193 nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl+CH 2 CCH 2 OH photofragments, a spin-orbit branching ratio for Cl( 2 P 1/2 ):Cl( 2 P 3/2 ) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH 2 CCH 2 OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH 2 CCH 2 OH radical intermediate to the three most important product channels for the OH+allene reaction expected from this radical intermediate: formaldehyde+C 2 H 3 , H+acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH 3 product channel. We compare our results to a previous theoretical study of the O+allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates

  5. Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH +allene reaction (United States)

    Raman, Arjun S.; Justine Bell, M.; Lau, Kai-Chung; Butler, Laurie J.


    These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH2CCH2OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl +CH2CCH2OH photofragments, a spin-orbit branching ratio for Cl(P1/22):Cl(P3/22) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH2CCH2OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH2CCH2OH radical intermediate to the three most important product channels for the OH +allene reaction expected from this radical intermediate: formaldehyde+C2H3, H +acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH3 product channel. We compare our results to a previous theoretical study of the O +allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates.

  6. Finding the missing stratospheric Bry: a global modeling study of CHBr3 and CH2Br2

    Directory of Open Access Journals (Sweden)

    D. R. Blake


    Full Text Available Recent in situ and satellite measurements suggest a contribution of ~5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3 and dibromomethane (CH2Br2, with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr−1 for CHBr3 and 57 Gg Br yr−1 for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes ~5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from source gas degradation (BryVSLS in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv of the bromine from the inclusion of CHBr3 and CH2Br2 near the tropical tropopause and its contribution rapidly increases to ~100% as altitude increases. More than 85% of the wet scavenging of BryVSLS occurs in large-scale precipitation below 500 hPa. Our sensitivity study with wet scavenging in convective updrafts switched off suggests that BryVSLS in the stratosphere is not sensitive to convection. Convective scavenging only accounts for

  7. Are CH2O measurements in the marine boundary layer suitable for testing the current understanding of CH4 photooxidation?: A model study (United States)

    Wagner, V.; von Glasow, R.; Fischer, H.; Crutzen, P. J.


    On the basis of a data set collected during the Indian Ocean Experiment (INDOEX) campaign 1999, we investigated the formaldehyde (CH2O) budget in the southern Indian Ocean (SIO). With a photochemical box model we simulated the contribution of methane and nonmethane volatile organic compounds to the CH2O budget. To identify the reactions and model constraints that introduce the largest uncertainties in the modeled CH2O concentration, we carried out a local sensitivity analysis. Furthermore, a Monte Carlo method was used to assess the global error of the model predictions. According to this analysis the 2σ uncertainty in the modeled CH2O concentration is 49%. The deviation between observed (200 +/- 70 parts per trillion by volume (pptv) (2σ)) and modeled (224 +/- 110 pptv (2σ)) daily mean CH2O concentration is 12%. However, the combined errors of model and measurement are such that deviations as large as 65% are not significant at the 2σ level. Beyond the ``standard'' photochemistry we analyzed the impact of halogen and aerosol chemistry on the CH2O concentration and investigated the vertical distribution of CH2O in the marine boundary layer (MBL). Calculations with the Model of Chemistry Considering Aerosols indicate that, based on the current understanding, halogen chemistry and aerosol chemistry have no significant impact on the CH2O concentration under conditions encountered in the SIO. However, a detailed investigation including meteorological effects such as precipitation scavenging and convection reveals an uncertainty in state-of-the-art model predictions for CH2O in the MBL that is too large for a meaningful test of the current understanding of CH4 photooxidation.

  8. Velocity map imaging of O-atom products from UV photodissociation of the CH2OO Criegee intermediate (United States)

    Li, Hongwei; Fang, Yi; Beames, Joseph M.; Lester, Marsha I.


    UV excitation of jet-cooled CH2OO X1A' to the excited B1A' electronic states results in dissociation to two spin-allowed product channels: H2CO X1A1 + O 1D and H2CO a3A″ + O 3P. In this study, the higher energy H2CO a3A″ + O 3P channel is characterized by velocity map imaging and UV action spectroscopy, in both cases utilizing 2 + 1 resonance enhanced multiphoton ionization detection of O 3P products, which complements a prior experimental study on the lower energy H2CO X1A1 + O 1D channel [Lehman et al., J. Chem. Phys. 139, 141103 (2013)]. Anisotropic angular distributions indicative of rapid dissociation are obtained at 330 and 350 nm, along with broad and unstructured total kinetic energy distributions that provide insight into the internal excitation of the H2CO a3A″ co-fragment. A harmonic normal mode analysis points to significant vibrational excitation of the CH2 wag and C-O stretch modes of the H2CO a3A″ fragment upon dissociation. At each UV wavelength, the termination of the kinetic energy distribution reveals the energetic threshold for the H2CO a3A″ + O 3P product channel of ca. 76 kcal mol-1 (378 nm) and also establishes the dissociation energy from CH2OO X1A' to H2CO X1A1 + O1D products of D0 ≤ 49.0 ± 0.3 kcal mol-1, which is in accord with prior theoretical studies. The threshold for the H2CO a3A″ + O 3P channel is also evident as a more rapid falloff on the long wavelength side of the O 3P action spectrum as compared to the previously reported UV absorption spectrum for jet-cooled CH2OO [Beames et al., J. Am. Chem. Soc. 134, 20045 (2012)]. Modeling suggests that the O 3P yield increases uniformly from 378 to 300 nm.

  9. Finding the Missing Stratospheric Br(sub y): A Global Modeling Study of CHBr3 and CH2Br2 (United States)

    Liang, Q.; Stolarski, R. S.; Kawa, S. R.; Nielsen, J. E.; Douglass, A. R.; Rodriguez, J. M.; Blake, D. R.; Atlas, E. L.; Ott, L. E.


    Recent in situ and satellite measurements suggest a contribution of 5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3) and dibromomethane (CH2Br2), with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM) to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr(exp -1) for CHBr3 and 57 Gg Br yr(exp -l) for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes 5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from source gas degradation (BrSLS) in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv) of the bromine from the inclusion of CHBr3 and CHzBr2 near the tropical tropopause and its contribution rapidly increases to 100% as altitude increases. More than 85% of the wet scavenging of Br(sub y)(sup VSLS) occurs in large-scale precipitation below 500 hPa. Our sensitivity study with wet scavenging in convective updrafts switched off suggests that Br(sub y)(sup SLS) in the stratosphere is not sensitive to convection. Convective scavenging only

  10. Matrix Infrared Spectra of Insertion and Metallacyclopropane Complexes [CH3CH2-MH and (CH2)2-MH2] Prepared in Reactions of Laser-Ablated Group 3 Metal Atoms with Ethane. (United States)

    Cho, Han-Gook; Andrews, Lester


    CH 3 CH 2 -MH and (CH 2 ) 2 -MH 2 were identified in the matrix IR spectra from reactions of laser-ablated group 3 metal atoms with ethane, and they were characterized via theoretical investigations. The observed products are the most stable in the proposed reaction path. Because of the small number of valence electrons, the group 3 metal high oxidation-state complexes are less stable. The C-C insertion product [(CH 3 ) 2 M], which was predicted to be more stable than the observed ones, was not observed probably because of the high energy barrier and a likely slower rate for insertion into one C-C bond than one of six C-H bonds. The C-C bond of the metallacyclopropanes is the shortest among the early transition-metal analogues, and its stretching frequencies are the highest, revealing the weakest interaction between the metal dihydride and ethylidene groups. The undetected ethylidene is not agostic, parallel to the previously examined methylidene.

  11. State resolved measurements of a (1)CH(2) removal confirm predictions of the gateway model for electronic quenching. (United States)

    Gannon, K L; Blitz, M A; Kovács, T; Pilling, M J; Seakins, P W


    Collisional quenching of electronically excited states by inert gases is a fundamental physical process. For reactive excited species such as singlet methylene, (1)CH(2), the competition between relaxation and reaction has important implications in practical systems such as combustion. The gateway model has previously been applied to the relaxation of (1)CH(2) by inert gases [U. Bley and F. Temps, J. Chem. Phys. 98, 1058 (1993)]. In this model, gateway states with mixed singlet and triplet character allow conversion between the two electronic states. The gateway model makes very specific predictions about the relative relaxation rates of ortho and para quantum states of methylene at low temperatures; relaxation from para gateway states leads to faster deactivation independent of the nature of the collision partner. Experimental data are reported here which for the first time confirm these predictions at low temperatures for helium. However, it was found that in contrast with the model predictions, the magnitude of the effect decreases with increasing size of the collision partner. It is proposed that the attractive potential energy surface for larger colliders allows alternative gateway states to contribute to relaxation removing the dominance of the para gateway states.

  12. Direct experimental probing and theoretical analysis of the reaction between the simplest Criegee intermediate CH2OO and isoprene. (United States)

    Decker, Z C J; Au, K; Vereecken, L; Sheps, L


    Recent advances in the spectroscopy of Criegee intermediates (CI) have enabled direct kinetic studies of these highly reactive chemical species. The impact of CI chemistry is currently being incorporated into atmospheric models, including their reactions with trace organic and inorganic compounds. Isoprene, C 5 H 8 , is a doubly-unsaturated hydrocarbon that accounts for the largest share of all biogenic emissions around the globe and is also a building block of larger volatile organic compounds. We report direct measurements of the reaction of the simplest CI (CH 2 OO) with isoprene, using time-resolved cavity-enhanced UV absorption spectroscopy. We find the reaction to be pressure-independent between 15-100 Torr, with a rate coefficient that varies from (1.5 ± 0.1) × 10 -15 cm 3 molecule -1 s -1 at room temperature to (23 ± 2) × 10 -15 cm 3 molecule -1 s -1 at 540 K. Quantum chemical and transition-state theory calculations of 16 unique channels for CH 2 OO + isoprene somewhat underpredict the observed T-dependence of the total reaction rate coefficient, but are overall in good agreement with the experimental measurements. This reaction is broadly similar to those with smaller alkenes, proceeding by 1,3-dipolar cycloaddition to one of the two conjugated double bonds of isoprene.

  13. Kinetic and theoretical studies on the protonation of [Ni(2-SC6H4N){PhP(CH2CH2PPh2)2}]+: nitrogen versus sulfur as the protonation site. (United States)

    Petrou, Athinoula L; Koutselos, Andreas D; Wahab, Hilal S; Clegg, William; Harrington, Ross W; Henderson, Richard A


    The complexes [Ni(4-Spy)(triphos)]BPh(4) and [Ni(2-Spy)(triphos)]BPh(4) {triphos = PhP(CH(2)CH(2)PPh(2))(2), 4-Spy = 4-pyridinethiolate, 2-Spy = 2-pyridinethiolate} have been prepared and characterized both spectroscopically and using X-ray crystallography. In both complexes the triphos is a tridentate ligand. However, [Ni(4-Spy)(triphos)](+) comprises a 4-coordinate, square-planar nickel with the 4-Spy ligand bound to the nickel through the sulfur while [Ni(2-Spy)(triphos)](+) contains a 5-coordinate, trigonal-bipyramidal nickel with a bidentate 2-Spy ligand bound to the nickel through both sulfur and nitrogen. The kinetics of the reactions of [Ni(4-Spy)(triphos)](+) and [Ni(2-Spy)(triphos)](+) with lutH(+) (lut = 2,6-dimethylpyridine) in MeCN have been studied using stopped-flow spectrophotometry, and the two complexes show very different reactivities. The reaction of [Ni(4-Spy)(triphos)](+) with lutH(+) is complete within the deadtime of the stopped-flow apparatus (2 ms) and corresponds to protonation of the nitrogen. However, upon mixing [Ni(2-Spy)(triphos)](+) and lutH(+) a reaction is observed (on the seconds time scale) to produce an equilibrium mixture. The mechanistic interpretation of the rate law has been aided by the application of MSINDO semiempirical and ADF calculations. The kinetics and calculations are consistent with the reaction between [Ni(2-Spy)(triphos)](+) and lutH(+) involving initial protonation of the sulfur followed by dissociation of the nitrogen and subsequent transfer of the proton from sulfur to nitrogen. The factors affecting the position of protonation and the coupling of the coordination state of the 2-pyridinethiolate ligand to the site of protonation are discussed.

  14. The Proposed Heating and Cooling System in the CH2 Building and Its Impact on Occupant Productivity

    Directory of Open Access Journals (Sweden)

    Lu Aye


    Full Text Available Melbourne's climatic conditions demand that its buildings require both heating and cooling systems. In a multi-storey office building , however, cooling requirements will dominate. How the internal space is cooled and ventilation air is delivered will significantly impact on occupant comfort. This paper discusses the heating and cooling systems proposed for the CH2building. The paper critiques the proposed systems against previous experience, both internationally and in Australia. While the heating system employs proven technologies, less established techniques are proposed for the cooling system. Air movement in the shower towers, for example, is to be naturally induced and this has not always been successful elsewhere. Phase change material for storage of "coolth" does not appear to have been demonstrated previously in a commercial building, so the effectiveness of the proposed system is uncertain. A conventional absorption chiller backs up the untried elements of the cooling system, so that ultimately occupant comfort should not be compromised .

  15. Structural diversity in gallium(III) complexes of the tripodal triarsine MeC(CH2AsMe2)3. (United States)

    Cheng, Fei; Hector, Andrew L; Levason, William; Reid, Gillian; Webster, Michael; Zhang, Wenjian


    The preparation and crystal structures of the first examples of gallium halide complexes with the tripodal arsine, MeC(CH(2)AsMe(2))3, reveal three distinctly different coordination modes for the ligand; the neutral [{micro(3)-MeC(CH(2)AsMe(2))3-kappaAs:kappaAs':kappaAs''}(GaI(3))3] with the triarsine coordinating to three GaI(3) units, [{Me(2)AsCH(2)C(Me)(CH(2)AsMe(2))2-kappa(2)AsAs'}GaCl(2)][GaCl(4)] involving bidentate chelation to a GaCl2+ cationic unit with the third As donor atom uncoordinated, and [{MeC(CH(2)AsMe(2))3-kappaAs:kappa(2)As'As''}(GaCl3)(GaCl2)][GaCl4] in which the triarsine forms a bidentate chelate to the GaCl2+ unit and the third As donor atom binds to a further GaCl3 unit.

  16. Mechanisms and rates of proton transfer to coordinated carboxydithioates: studies on [Ni(S2CR){PhP(CH2CH2PPh2)2}](+) (R = Me, Et, Bu(n) or Ph). (United States)

    Alwaaly, Ahmed; Clegg, William; Henderson, Richard A; Probert, Michael R; Waddell, Paul G


    The complexes [Ni(S2CR)(triphos)]BPh4 (R = Me, Et, Bu(n) or Ph; triphos = PhP{CH2CH2PPh2}2) have been prepared and characterised. X-ray crystallography (for R = Et, Ph, C6H4Me-4, C6H4OMe-4 and C6H4Cl-4) shows that the geometry of the five-coordinate nickel in the cation is best described as distorted trigonal bipyramidal, containing a bidentate carboxydithioate ligand with the two sulfur atoms spanning axial and equatorial sites, the other axial site being occupied by the central phosphorus of triphos. The reactions of [Ni(S2CR)(triphos)](+) with mixtures of HCl and Cl(-) in MeCN to form equilibrium solutions containing [Ni(SH(S)CR)(triphos)](2+) have been studied using stopped-flow spectrophotometry. The kinetics show that proton transfer is slower than the diffusion-controlled limit and involves at least two coupled equilibria. The first step involves the rapid association between [Ni(S2CR)(triphos)](+) and HCl to form the hydrogen-bonded precursor, {[Ni(S2CR)(triphos)](+)HCl} (K) and this is followed by the intramolecular proton transfer (k) to produce [Ni(SH(S)CR)(triphos)](2+). In the reaction of [Ni(S2CMe)(triphos)](+) the rate law is consistent with the carboxydithioate ligand undergoing chelate ring-opening after protonation. It seems likely that chelate ring-opening occurs for all [Ni(S2CR)(triphos)](+), but only with [Ni(S2CMe)(triphos)](+) is the protonation step sufficiently fast that chelate ring-opening is rate-limiting. With all other systems, proton transfer is rate-limiting. DFT calculations indicate that protonation can occur at either sulfur atom, but only protonation at the equatorial sulfur results in chelate ring-opening. The ways in which protonation of either sulfur atom complicates the analyses and interpretation of the kinetics are discussed.

  17. New insights into the column CH2O/NO2 ratio as an indicator of near-surface ozone sensitivity (United States)

    Schroeder, Jason R.; Crawford, James H.; Fried, Alan; Walega, James; Weinheimer, Andrew; Wisthaler, Armin; Müller, Markus; Mikoviny, Tomas; Chen, Gao; Shook, Michael; Blake, Donald R.; Tonnesen, Gail S.


    Satellite-based measurements of the column CH2O/NO2 ratio have previously been used to estimate near-surface ozone (O3) sensitivity (i.e., NOx or VOC limited), and the forthcoming launch of air quality-focused geostationary satellites provides a catalyst for reevaluating the ability of satellite-measured CH2O/NO2 to be used in this manner. In this study, we use a 0-D photochemical box model to evaluate O3 sensitivity and find that the relative rate of radical termination from radical-radical interactions to radical-NOx interactions (referred to as LROx/LNOx) provides a good indicator of maximum O3 production along NOx ridgelines. Using airborne measurements from NASA's Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relative to Air Quality (DISCOVER-AQ) deployments in Colorado, Maryland, and Houston, we show that in situ measurements of CH2O/NO2 can be used to indicate O3 sensitivity, but there is an important "transition/ambiguous" range whereby CH2O/NO2 fails to categorize O3 sensitivity, and the range and span of this transition/ambiguous range varies regionally. Then, we apply these findings to aircraft-derived column density measurements from DISCOVER-AQ and find that inhomogeneities in vertical mixing in the lower troposphere further degrades the ability of column CH2O/NO2 to indicate near-surface O3 sensitivity (i.e., the transition/ambiguous range is much larger than indicated by in situ data alone), and we hypothesize that the global transition/ambiguous range is sufficiently large to make the column CH2O/NO2 ratio unuseful for classifying near-surface O3 sensitivity. Lastly, we present a case study from DISCOVER-AQ-Houston that suggests that O3 sensitivity on exceedance days may be substantially different than on nonexceedance days (which may be observable from space) and explore the diurnal evolution of O3 sensitivity, O3 production, and the column CH2O/NO2 ratio. The results of these studies suggest that

  18. Synthesis and vibrational spectroscopic characterisation of nickel (II) propionate tetrahydrate, Ni(CH 3CH 2COO) 2·4H 2O, and its aqueous solution (United States)

    Bickley, R. I.; Edwards, H. G. M.; Gustar, R.; Rose, S. J.


    A two-stage synthesis for nickel(II) propionate is described. A comprehensive Raman and infrared spectroscopic study of propionic acid, nickel propionate, sodium propionate and barium propionate has been made and the vibrational spectra have been assigned. From comparisons of the Raman and infrared spectra of sodium propionate and nickel propionate, it is concluded that nickel (II) propionate dissociates into the propionate ion CH 3CH 2CO 2-, hexa-aquo nickel(II) ions Ni(H 2O) 2+6, and the monopropionato-nickel(II) species (CH 3CH 2COO)Ni +, in aqueous solution.

  19. Effect of Mycobacterium sp. strain CH1 and mycobacterium sp. strain CH2 on the degradation of four-ring creosote compounds. (United States)

    Harper, Jennifer Paige; Churchill, Perry F; Lokey-Flippo, Laura; Lalor, Melinda M


    The influence of nutrients, Mycobacterium sp. strain CH1 and Mycobacterium sp. strain CH2 on the degradation of aged creosote hydrocarbon contaminants was investigated. The Mycobacterium sp. strain CH2 showed the highest positive influence on the degradation of three- and four-ring PAH compounds. The addition of Mycobacterium sp. strain CH1 had the second highest measured positive influence on the degradation of four-ring compounds. Soluble nitrogen and phosphorus also increased the degradation of aged creosote compounds in the contaminated soil. The addition of bacteria decreased the number of measured bacterial species, indicating competition for limited nutrients in the soil.

  20. Test of GEANT3 and GEANT4 nuclear models for 160 MeV protons stopping in CH2

    International Nuclear Information System (INIS)

    Paganetti, H.; Gottschalk, B.


    Monte Carlo simulations are used for many problems in proton radiation therapy, some of which are sensitive to the nuclear interaction model. The available models have been little tested in the regime of interest, namely in their ability to predict the secondary particle yield, including their angle and energy, when 70-250 MeV protons stop in various materials. The present study provides one such test in carbon, complementing a previous one in copper. Using a multilayer Faraday cup we have measured the projected range distribution of charged nuclear secondaries from 160 MeV protons stopping in polyethylene (CH 2 ). To test the popular GEANT Monte Carlo we have simulated the experiment with GEANT3 using the 'Gheisha' (default) and 'Fluka' models and with GEANT4.5 using the 'low-energy' and 'precompound' models. The GEANT3/Fluka and GEANT4/precompound simulations agree moderately well with the observed range distribution. The data are given in a convenient form for testing other Monte Carlo programs

  1. Accurate high level ab initio-based global potential energy surface and dynamics calculations for ground state of CH2(+). (United States)

    Li, Y Q; Zhang, P Y; Han, K L


    A global many-body expansion potential energy surface is reported for the electronic ground state of CH2 (+) by fitting high level ab initio energies calculated at the multireference configuration interaction level with the aug-cc-pV6Z basis set. The topographical features of the new global potential energy surface are examined in detail and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. In turn, in order to validate the potential energy surface, a test theoretical study of the reaction CH(+)(X(1)Σ(+))+H((2)S)→C(+)((2)P)+H2(X(1)Σg (+)) has been carried out with the method of time dependent wavepacket on the title potential energy surface. The total integral cross sections and the rate coefficients have been calculated; the results determined that the new potential energy surface can both be recommended for dynamics studies of any type and as building blocks for constructing the potential energy surfaces of larger C(+)/H containing systems.

  2. Additional Value of CH4 Measurement in a Combined 13C/H2 Lactose Malabsorption Breath Test: A Retrospective Analysis (United States)

    Houben, Els; De Preter, Vicky; Billen, Jaak; Van Ranst, Marc; Verbeke, Kristin


    The lactose hydrogen breath test is a commonly used, non-invasive method for the detection of lactose malabsorption and is based on an abnormal increase in breath hydrogen (H2) excretion after an oral dose of lactose. We use a combined 13C/H2 lactose breath test that measures breath 13CO2 as a measure of lactose digestion in addition to H2 and that has a better sensitivity and specificity than the standard test. The present retrospective study evaluated the results of 1051 13C/H2 lactose breath tests to assess the impact on the diagnostic accuracy of measuring breath CH4 in addition to H2 and 13CO2. Based on the 13C/H2 breath test, 314 patients were diagnosed with lactase deficiency, 138 with lactose malabsorption or small bowel bacterial overgrowth (SIBO), and 599 with normal lactose digestion. Additional measurement of CH4 further improved the accuracy of the test as 16% subjects with normal lactose digestion and no H2-excretion were found to excrete CH4. These subjects should have been classified as subjects with lactose malabsorption or SIBO. In conclusion, measuring CH4-concentrations has an added value to the 13C/H2 breath test to identify methanogenic subjects with lactose malabsorption or SIBO. PMID:26371034

  3. Additional Value of CH4 Measurement in a Combined 13C/H2 Lactose Malabsorption Breath Test: A Retrospective Analysis

    Directory of Open Access Journals (Sweden)

    Els Houben


    Full Text Available The lactose hydrogen breath test is a commonly used, non-invasive method for the detection of lactose malabsorption and is based on an abnormal increase in breath hydrogen (H2 excretion after an oral dose of lactose. We use a combined 13C/H2 lactose breath test that measures breath 13CO2 as a measure of lactose digestion in addition to H2 and that has a better sensitivity and specificity than the standard test. The present retrospective study evaluated the results of 1051 13C/H2 lactose breath tests to assess the impact on the diagnostic accuracy of measuring breath CH4 in addition to H2 and 13CO2. Based on the 13C/H2 breath test, 314 patients were diagnosed with lactase deficiency, 138 with lactose malabsorption or small bowel bacterial overgrowth (SIBO, and 599 with normal lactose digestion. Additional measurement of CH4 further improved the accuracy of the test as 16% subjects with normal lactose digestion and no H2-excretion were found to excrete CH4. These subjects should have been classified as subjects with lactose malabsorption or SIBO. In conclusion, measuring CH4-concentrations has an added value to the 13C/H2 breath test to identify methanogenic subjects with lactose malabsorption or SIBO.

  4. Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br (United States)

    Hsu, K.-J.; Demore, W. B.


    Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

  5. The acid-catalyzed rearrangement CH3Oo --> oCH2OH and its involvement in the dissociation of the methanol dimer radical cation; A Quid pro Quo reaction

    NARCIS (Netherlands)

    Burgers, P.C.; Ruttink, P.J.A.


    The barrier for the radical isomerization CH3Oo --> oCH2OH is calculated by CBS-QB3 to be 29.7 kcal mol-1 and lies higher (by 5.7 kcal mol-1) than the dissociation limit CH2O+Ho. Hence, CH3Oo does not isomerize to the more stable oCH2OH on its own. However, this barrier is reduced to 15.8 kcal mol-1

  6. Infrared absorption spectra of partially deuterated methoxy radicals CH2DO and CHD2O isolated in solid para-hydrogen. (United States)

    Haupa, Karolina A; Johnson, Britta A; Sibert, Edwin L; Lee, Yuan-Pern


    The investigation of partially deuterated methoxy radicals is important because the symmetry lowering from C 3v to C s provides new insights into the couplings between rovibronic states via Jahn-Teller and spin-orbit interactions. The vibrational spectrum of the partially deuterated methoxy radical CH 2 DO in a matrix of p-H 2 has been recorded. This species was prepared by irradiating a p-H 2 matrix containing deuterated d 1 -nitritomethane (CH 2 DONO) at 3.3 K with laser light at 355 nm. The identification of the radical is based on the photochemical behavior of the precursor and comparison of observed vibrational wavenumbers and infrared (IR) intensities with those predicted from a refined quartic, curvilinear, internal coordinate force field calculated with the coupled-cluster singles and doubles with perturbative triples/cc-pVTZ method. CH 2 DO reacts with H 2 with a rate coefficient (3.5 ± 1.0) × 10 -3 s -1 . Predominantly c-CHDOH and a negligibly small amount of t-CHDOH were produced. This stereoselectivity results from the reaction H + C s -CH 2 DOH, which was demonstrated by an additional experiment on irradiation of a CH 2 DOH/Cl 2 /p-H 2 matrix with ultraviolet and IR light to induce the H + CH 2 DOH reaction; only c-CHDOH was observed from this experiment. Even though the energies of transition states and products for the formation of c-CHDOH and t-CHDOH differ by only ∼10 cm -1 , the selective formation of c-CHDOH can be explained by tunneling of the hydrogen atom via an optimal tunneling path. Similarly, the vibronic spectrum for the partially deuterated specie d 2 -methoxy radical (CHD 2 O) was obtained upon irradiation of d 2 -nitritomethane (CHD 2 ONO) at 355 nm. Lines associated with the fundamental vibrational modes were observed and assigned; line positions agree with theoretically predicted vibrational wavenumbers. CHD 2 O reacts with H 2 with a rate coefficient (6.0 ± 1.4) × 10 -3 s -1 ; CD 2 OH was produced as a major product because

  7. Insertion, isomerization, and cascade reactivity of the tethered silylalkyl uranium metallocene (η(5)-C5Me4SiMe2CH2-κC)2U. (United States)

    Siladke, Nathan A; Ziller, Joseph W; Evans, William J


    Investigation of the insertion reactivity of the tethered silylalkyl complex (η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)(2)U (1) has led to a series of new reactions for U-C bonds. Elemental sulfur reacts with 1 by inserting two sulfur atoms into each of the U-C bonds to form the bis(tethered alkyl disulfide) complex (η(5):η(2)-C(5)Me(4)SiMe(2)CH(2)S(2))(2)U (2). The bulky substrate N,N'-diisopropylcarbodiimide, (i)PrN═C═N(i)Pr, inserts into only one of the U-C bonds of 1 to produce the mixed-tether complex (η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)U[η(5)-C(5)Me(4)SiMe(2)CH(2)C((i)PrN)(2)-κ(2)N,N'] (3). Carbon monoxide did not exclusively undergo a simple insertion into the U-C bond of 3 but instead formed {μ-[η(5)-C(5)Me(4)SiMe(2)CH(2)C(═N(i)Pr)O-κ(2)O,N]U[OC(C(5)Me(4)SiMe(2)CH(2))CN((i)Pr)-κ(2)O,N](2) (4) in a cascade of reactions that formally includes U-C bond cleavage, C-N bond cleavage of the amidinate ligand, alkyl or silyl migration, U-O, C-C, and C-N bond formations, and CO insertion. The reaction of 3 with isoelectronic tert-butyl isocyanide led to insertion of the substrate into the U-C bond, but with a rearrangement of the amidinate ligand binding mode from κ(2) to κ(1) to form [η(5):η(2)-C(5)Me(4)SiMe(2)CH(2)C(═N(t)Bu)]U[η(5)-C(5)Me(4)SiMe(2)CH(2)C(═N(i)Pr)N((i)Pr)-κN] (5). The product of double insertion of (t)BuN≡C into the U-C bonds of 1, namely [η(5):η(2)-C(5)Me(4)SiMe(2)CH(2)C(═N(t)Bu)](2)U (6), was found to undergo an unusual thermal rearrangement that formally involves C-H bond activation, C-C bond cleavage, and C-C bond coupling to form the first formimidoyl actinide complex, [η(5):η(5):η(3)-(t)BuNC(CH(2)SiMe(2)C(5)Me(4))(CHSiMe(2)C(5)Me(4))]U(η(2)-HC═N(t)Bu) (7).

  8. Synthesis, Structure, and Reactivity of the Ethyl Yttrium Metallocene, (C5Me5)2Y(CH2CH3), Including Activation of Methane. (United States)

    MacDonald, Matthew R; Langeslay, Ryan R; Ziller, Joseph W; Evans, William J


    (C5Me5)2Y(μ-Ph)2BPh2, 1, reacted with ethyllithium at -15 °C to make (C5Me5)2Y(CH2CH3), 2, which is thermally unstable at room temperature and formed the C-H bond activation product, (C5Me5)2Y(μ-H)(μ-η(1):η(5)-CH2C5Me4)Y(C5Me5), 3, containing a metalated (C5Me5)(1-) ligand. Spectroscopic evidence for 2 was obtained at low temperature, and trapping experiments with (i)PrNCN(i)Pr and CO2 gave the Y-CH2CH3 insertion products, (C5Me5)2Y[(i)PrNC(Et)N(i)Pr-κ(2)N,N'], 4, and [(C5Me5)2Y(μ-O2CEt)]2, 5. Although 2 is highly reactive, low temperature isolation methods allowed the isolation of single crystals which revealed an 82.6(2)° Y-CH2-CH3 bond angle consistent with an agostic structure in the solid state. Complex 2 reacted with benzene and toluene to make (C5Me5)2YPh, 7, and (C5Me5)2YCH2Ph, 8, respectively. The reaction of 2 with [(C5Me5)2YCl]2 formed (C5Me5)2Y(μ-Cl)(μ-η(1):η(5)-CH2C5Me4)Y(C5Me5) in which a (C5Me5)(1-) ligand was metalated. C-H bond activation also occurred with methane which reacted with 2 to make [(C5Me5)2YMe]2, 9.

  9. Formation of hydroxyacetonitrile (HOCH2CN) and polyoxymethylene (POM)-derivatives in comets from formaldehyde (CH2O) and hydrogen cyanide (HCN) activated by water. (United States)

    Danger, Grégoire; Rimola, Albert; Abou Mrad, Ninette; Duvernay, Fabrice; Roussin, Gaël; Theule, Patrice; Chiavassa, Thierry


    Studying chemical reactivity is an important way to improve our understanding of the origin of organic matter in astrophysical environments such as molecular clouds, protoplanetary disks, and possibly, as a final destination, in our solar system bodies such as in comets. Laboratory simulations on the reactivity of ice analogs can provide important insights into this complex reactivity. Here, the role of water as a catalytic agent is investigated under the conditions of simulated interstellar and cometary grains in the formation of complex organic molecules: the hydroxyacetonitrile (HOCH2CN) and formaldehyde polymers (polyoxymethylene POM). Using infrared spectroscopy and mass spectrometry, we show that HCN reacts with CH2O only in the presence of H2O, whereas in the absence of H2O, HCN is not sufficiently reactive to promote this reaction. Furthermore, depending on the dilution of CH2O and HCN in the water matrix, 1-cyanopolyoxymethylene polymers can also be formed (H-(O-CH2)n-CN, POM-CN), as confirmed by mass spectrometry using the HC(15)N isotopologue. Moreover, quantum chemical calculations allowed us to suggest mechanistic proposals for these reactions, the first step being the activation of HCN by water forming H3O(+) and CN(-), which subsequently condense on a neighbouring CH2O promoting the formation of (-)OCH2CN. Once (-)OCH2CN is formed, it can either recover a proton by reacting with H3O(+) or condense on CH2O molecules leading to POM-CN structures. Implications of this work for the forthcoming Rosetta mission are also addressed.

  10. New cascade laser transitions in CH2F2 pumped with the 9R32 line of a cw CO2 laser

    International Nuclear Information System (INIS)

    Nieswand, C.


    New cascade laser transitions of 12 CH 2 F 2 at 172.50μm, 208.83μm, 220.44μm, 223.99μm,and 250.61μm are reported. A waveguide FIR laser was pumped with a quasi cw 12 C 16 O 2 laser operating on the 9R32 line. Together with the already known lines at 184.3μm, 196.1μm and 235.9μm, the laser lines can be assigned to rotational transitions in the ν 9 vibrational band of 12 CH 2 F 2 and to refill transitions of the vibrational ground state ν 0 . 1 fig., 2 tabs., 6 refs. (author)

  11. Reacción de ligandos azufrados con el complejo au2pt (ch2p(Sph24,cl2

    Directory of Open Access Journals (Sweden)

    Guillermo Garzón


    Full Text Available Se describe la reacción de intercambio del cloro en el complejo au2pt (ch2p(Sph24,cl2 por los ligandos SCH2Ph-,S2CN(CH2CH3,2- y SCN-. Los nuevos derivados azufrados se caracterizan por análisis químico, espectroscopia infrarroja, electrónica y resonancia magnética nuclear protónica. Los ligandos se coordinan por el azufre a los dos átomos sw oro metálico en forma simétrica. El análisis elemental concuerda con las estequiomctrías y estructuras propuestas.

  12. Synthesis and crystal structure of 4-fluorobenzylammonium dihydrogen phosphate, [FC6H4CH2NH3]H2PO4

    Directory of Open Access Journals (Sweden)

    Ali Rayes


    Full Text Available The asymmetric unit of the title salt, [p-FC6H4CH2NH3]+·H2PO4−, contains one 4-fluorobenzylammonium cation and one dihydrogen phosphate anion. In the crystal, the H2PO4− anions are linked by O—H...O hydrogen bonds to build corrugated layers extending parallel to the ab plane. The FC6H4CH2NH3+ cations lie between these anionic layers to maximize the electrostatic interactions and are linked to the H2PO4− anions through N—H...O hydrogen bonds, forming a three-dimensional supramolecular network. Two hydrogen atoms belonging to the dihydrogen phosphate anion are statistically occupied due to disorder along the OH...HO direction.

  13. Molecular structures of CH 2BrCl, CHBrCl 2 and CHBr 2Cl as determined by gas electron diffraction (United States)

    Konaka, Shigehiro; Kiyoto, Kouhei; Yamamoto, Kazunori; Suzuki, Naoe; Kimura, Masao


    The molecular structures of CH 2BrCl, CHBrCl 2 and CHBr 2Cl have been determined by gas electron diffraction and compared with the structures of related halomethanes. The correlation between the structures of halomethanes and the electronegativities of substituted atoms is discussed in connection with the VSEPR model. The observed structures are reproduced fairly well by a molecular mechanics calculation where the reference geometries are chosen to be consistent with the VSEPR model.

  14. High-resolution infrared spectroscopy of CH2D79Br: ro-vibrational analysis of the ν4 and ν8 fundamental bands

    DEFF Research Database (Denmark)

    Stoppa, P.; Visinoni, R.; Baldacci, A.


    The high-resolution Fourier transform infrared spectrum of CH2D79Br has been recorded and analysed in the region of the ν4 and ν8 fundamentals located in the range 1125−1360 cm−1. The strong ν4 band, centred at 1225 cm−1, shows an a/b-hybrid structure with predominant a-type character, whereas ν8...

  15. [(≡SiO)TaV (=CH2)Cl2], the first tantalum methylidene species prepared and identified on the silica surface

    KAUST Repository

    Chen, Yin


    A novel surface tantalum methylidene [(≡SiO)TaV (=CH 2)Cl2] was obtained via thermal decomposition of the well-defined surface species [(≡SiO)TaVCl2Me 2]. This first surface tantalum methylidene ever synthesized has been fully characterized and the kinetics of the a-hydrogen abstraction reaction has also been investigated in the heterogeneous system. © 2013 Elsevier B.V. All rights reserved.

  16. Reversibility of Intersystem Crossing in the {a}1A1(000) and {a}1A1(010) States of Methylene, CH_2 (United States)

    Le, Anh T.; Sears, Trevor; Hall, Gregory


    The lowest energy singlet ( {a}1A1) and triplet ( {X}3B1) electronic states of methylene, CH_2, are only separated by 3150 wn, but differ greatly in chemical reactivity. Overall methylene reaction rates and chemical behavior are therefore strongly dependent on collisionally-mediated singlet-triplet interconversion. Collisions with inert partners tend to depopulate the excited singlet state and populate vibrationally excited triplet levels in CH_2. This process is generally considered as irreversible for large molecules, however, this is not the case for small molecules such as CH_2. An investigation of the decay kinetics of CH_2 in the presence of argon and various amounts of oxygen has been carried out using transient frequency modulation (FM) absorption spectroscopy, to monitor ortho and para rotational levels in both the {a}1A1(000) and {a}1A1(010) states. In the {a}1A1(000) state, all observed rotational levels follow double exponential decay kinetics, a direct consequence of reversible intersystem crossing. The relative amplitude of the slower decay component is an indicator of how quickly the reverse crossing from excited triplet levels becomes significant during the reaction and relaxation of singlet methylene. The para rotational levels show more obvious signs of reversibility than ortho rotational levels. Adding oxygen enhances the visibility of reversibility for both ortho and para levels. However, in the {a}1A1(010) state where the FM signal is 5-10 times smaller than the {a}1A1(000) state, there is no evidence of double exponential decay kinetics. Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886 and DE-SC0012704 with the U.S. Department of Energy and supported by its Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences.

  17. Doppler-limited high-resolution spectrum and VPT2 assisted assignment of the C-H stretch of CH2Br2. (United States)

    Sadiek, Ibrahim; Friedrichs, Gernot


    The Doppler limited non-saturated rotationally resolved infrared spectra of the symmetric and asymmetric CH-stretch bands of CH 2 Br 2 have been measured. A continuous wave cavity ringdown setup with a widely tunable Mid-IR-OPO laser light source yielded a single-shot minimum absorption of 4.9×10 -8 cm -1 . In contrast to the heavily congested ν 1 band, the ν 6 band showed partially resolved rotational features that may serve as suitable absorption targets in future environmental detection schemes for CH 2 Br 2 . A straightforward, VPT2 (second-order vibrational perturbation theory) assisted quantum-chemical approach for assigning the rotational structure has been tested using different model chemistries. The molecular structures, anharmonic frequencies and the structural changes upon vibrational excitation of CH 2 Br 2 have been investigated. The predicted changes of the anharmonic rotational constants have been used together with available spectroscopic ground state constants to simulate the rovibrational structures of the ν 1 and ν 6 bands of CH 2 Br 2 . A refined analysis of the ν 6 band is presented yielding accurate values for the band origin and the rotational constants. A fit of the line positions of 312 prominent transitions of the three isotopologues revealed a low standard error of 0.00056cm -1 , hence within the absolute 0.0009cm -1 wavelength accuracy of the used spectrometer setup. A combined analysis of the predicted line strengths and positions of the strong Q sub-branches of the ν 6 band has been performed to test the ability of the different density functionals for VPT2 prediction of anharmonic molecular constants. The M06/6-311++G(d,p) model chemistry turned out to yield reliable state-dependent rotational constants that are accurate enough to reproduce the overall rotational structure even without fitting. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Operational O3M-SAF trace gas column products: GOME-2 ozone, NO2, BrO, SO2 and CH2O (United States)

    Hao, Nan; Valks, Pieter; Loyola, Diego; de Smedt, Isabelle; van Roozendael, Michel; Theys, Nicolas; Rix, Meike; Koukouli, Mariliza; Balis, Dimitris; Lambert, Jean-Christopher; Pinardi, Gaia; Zimmer, Walter; Emmadi, Sunil

    This contribution focuses on the operational GOME-2 trace gas column products developed at the German Aerospace Centre, in the framework of EUMETSAT's Satellite Application Facility on Ozone and Atmospheric Chemistry Monitoring (O3M-SAF). We present an overview of the retrieval algorithms and exemplary results for ozone, NO2, BrO, SO2 and CH2O. These trace gas column products are retrieved with the GOME Data Processor (GDP) version 4.x algorithm and the UPAS system. Total ozone and NO2 are retrieved with the Differential Optical Absorption Spectroscopy (DOAS) method using the UV wavelength region around 330 nm and 435 nm respectively. An additional algorithm is applied to retrieve the tropospheric NO2 column for polluted con-ditions. The operational ozone and NO2 products are available for the users in near real time, i.e. within two hours after sensing. SO2 emissions from volcanic and anthropogenic sources can be measured by GOME-2 around 320 nm. For BrO and CH2O, optimal DOAS fitting windows have been determined for GOME-2 in the UV wavelength region. The GOME-2 ozone, total and tropospheric NO2, SO2, BrO, CH2O and cloud products from DLR have reached the operational EUMETSAT O3M-SAF status. All these products are routinely available to the users via EUMETCast, WMO/GTS and FTP in HDF5 and BUFR format. We present initial validation results for GOME-2 products using ground-based measurements, as well as comparisons with other satellite products, such as those from SCIAMACHY and OMI. The use of tropospheric NO2, SO2 and CH2O columns for air quality applications will be presented, including temporal evolution analyses for China. Furthermore, we will show examples of BrO under polar winter conditions.

  19. Measurement of Analyzing Powers for the Reaction \\vec{p}+CH_2 at p_p = 1.75-5.3 GeV/c

    CERN Document Server

    Azhgirey, L S; Basilev, S N; Bushuev, Yu P; Glagolev, V V; Kirillov, D A; Korovin, P P; Manyakov, P K; Piskunov, N M; Sitnik, I M; Slepnev, V M; Muvsinsky, J; Tomasi-Gustafsson, E; Pentchev, L; Perdrisat, C F; Punjabi, V; Jones, M K; Kumbartzki, G F; Atanasov, I


    We report a new measurement of analyzing powers for the reaction \\vec{p}+CH_2\\to one charged particle+X at proton momenta of 1.75, 3.8, 4.5 and 5.3 GeV/c. These results extend the existing data basis, necessary for proton polarimetry at intermediate energy, and confirm the feasibility of a large acceptance polarimeter based on this process.

  20. Crystal structure and electrical conduction of the new organic-inorganic compound (CH2)2(NH3)2CdI4 (United States)

    Zhang, Liuqi; Wang, Jilin; Han, Feifei; Mo, Shuyi; Long, Fei; Gao, Yihua


    The new organic-inorganic compound (CH2)2(NH3)2CdI4 was prepared by slow evaporation method using a mixture solution of CdI2 and ethylenediamine iodide (EDAI) in the γ-butyrolactone (GBL). The synthesized compound was further characterized by single crystal diffraction, Infrared (IR) and Raman spectroscopy, energy dispersive spectrometer (EDS), X-Ray photoelectron spectroscopy (XPS) and thermogravimetric analysis. The relaxation behavior and conductivity mechanism of (CH2)2(NH3)2CdI4 was studied by the electrical impedance spectroscopy. The results indicated that (CH2)2(NH3)2CdI4 had a monoclinic structure with space group P21/c at room temperature. The complex impedance plotted as semicircle arcs and the proposed electrical equivalent circuit was to interpret the impedance behavior at different temperatures. The electrical equivalent circuit was made of a parallel combination of resistance (R) and fractal capacitance (CPE). Furthermore, the alternating current conductivity of the sample obeyed the Jonscher's law: σf =σdc + Afs and the conduction could be attributed to the correlated barrier hopping (CBH) model.

  1. Ruthenium(η6,η1-arene-CH2-NHC Catalysts for Direct Arylation of 2-Phenylpyridine with (HeteroAryl Chlorides in Water

    Directory of Open Access Journals (Sweden)

    Nazan Kaloğlu


    Full Text Available A series of new benzimidazolium halides were synthesized in good yields as unsymmetrical N-heterocyclic carbene (NHC precursors containing the N–CH2–arene group. The benzimidazolium halides were readily converted into ruthenium(II–NHC complexes with the general formula [RuCl2(η6,η1–arene–CH2–NHC]. The structures of all new compounds were characterized by 1H NMR (Nuclear Magnetic Resonance, 13C NMR, FT-IR (Fourier Transform Infrared spectroscopy and elemental analysis techniques. The single crystal structure of one benzimidazole ruthenium complex, 2b, was determined. The complex is best thought of as containing an octahedrally coordinated Ru center with the arene residue occupying three sites, the remaining sites being occupied by a (carbeneC–Ru bond and two Ru–Cl bonds. The catalytic activity of [RuCl2(η6,η1–arene–CH2–NHC] complexes was evaluated in the direct (heteroarylation of 2-phenylpyridine with (heteroaryl chlorides in water as the nontoxic reaction medium. These results show that catalysts 2a and 2b were the best for monoarylation with simple phenyl and tolyl chlorides. For functional aryl chlorides, 2d, 2e, and 2c appeared to be the most efficient.

  2. Kinetic study of the reaction CH (X 2Pi) + H2 yields CH2 (X 3B1) + H in the temperature range 372 to 675 K (United States)

    Zabarnick, S.; Fleming, J. W.; Lin, M. C.


    The kinetics of the reversible reaction CH (X 2Pi) + H2 yields CH2 (X 3B1) + H at 372-675 K and total pressure 100 torr (mainly Ar) is investigated experimentally. The ground-state CH radicals are produced by photolysis of CHBr3 using 10-mJ 266-nm laser pulses (repetition rate 10 Hz) and monitored by measuring the fluorescence induced by a 429.8-nm dye laser, in the apparatus described by Berman et al. (1982) and Berman and Lin (1984). The results are presented in tables and graphs and characterized. The absolute rate constants for the forward and reverse reactions are determined, and their temperature dependence is given by Arrhenius expressions and formulas obtained in transition-state-theory calculations. The heat of formation of CH2 at 0 K is estimated (assuming that the recombination reaction CH2 + H has zero activation energy) as 92.6 + or - 0.5 kcal/mol.

  3. The influence of intramolecular coordination on the aggregation of sodium phenolate complexes. X-ray structures of [NaOC6H4(CH2NMe2)-2]6 and [Na(OC6H2(CH2NMe2)2-2,6-Me-4)(HOC6H2NMe2)2-2,6-Me-4)]2

    NARCIS (Netherlands)

    Koten, G. van; Hogerheide, M.P.; Ringelberg, S.N.; Janssen, M.D.; Boersma, J.; Spek, A.L.


    The structural characterization of two new sodium phenolate complexes, containing ortho-amino substituents, enables the influence of intramolecular coordination on the aggregation of sodium phenolate complexes to be determined. Crystals of hexameric [NaOC6H4(CH2NMe2)-2]6 (1a) are monoclinic, space

  4. Synthesis of Fe3O4@SiO2@OSi(CH2)3NHRN(CH2PPh2)2PdCl2 type nanocomposite complexes: Highly efficient and magnetically-recoverable catalysts in vitamin K3 synthesis. (United States)

    Uruş, Serhan


    The synthesis of aminomethylphosphine-metal complexes have opened a new perspective to the catalytic applications of organic compounds. Magnetic Fe3O4 nano-core was synthesized using the closed quartz tube with Teflon cover and microwaved 200°C for 1h with power controlled instrument set to max. 600W. Novel nano-composite supported; Fe3O4@SiO2(CH2)3NHArN(CH2PPh2)2 and Fe3O4@SiO2(CH2)3N(CH2PPh2)2 type bis(diphenylphosphinomethyl)amino ligands and their Pd(II) complexes have been synthesized and characterized with FT-IR, SEM, EDX, TEM, UV-Visible, XRD and TG/DTA techniques. All the complexes were used as heterogeneous catalysts in the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1, 4-naphthoquinone (vitamin K3, menadione, 2MNQ) in the presence of hydrogen peroxide and acetic acid. Selectivity reached about 55-60% with a conversion of 90-96% using the nano-magnetite supported aminomethylphosphine-Pd(II) complexes. The complexes were very active in three times in the catalytic recycling experiments in five catalytic cycles. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Infrared absorption of 1-chloro-2-methyl-2-propyl [⋅C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [⋅CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i-C4H8) in solid para-hydrogen. (United States)

    Chou, Ching-Yin; Lee, Yuan-Pern


    The addition reactions of chlorine atom with isobutene (i-C 4 H 8 ) in solid para-hydrogen (p-H 2 ) were investigated with infrared (IR) absorption spectra. When a p-H 2 matrix containing Cl 2 and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm -1 , and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, ⋅ C(CH 3 ) 2 CH 2 Cl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm -1 due to the 2-chloro-2-methylpropyl radical, ⋅ CH 2 C(CH 3 ) 2 Cl, appeared; the ratio of ⋅ C(CH 3 ) 2 CH 2 Cl to ⋅ CH 2 C(CH 3 ) 2 Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H 2 in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H 2 matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-C 4 H 8 ⋅Cl 2 and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CH 2 ClCCl(CH 3 ) 2 , are also characterized.

  6. Theoretical Kinetic and Mechanistic Studies on the Reactions of CF3CBrCH2 (2-BTP with OH and H Radicals

    Directory of Open Access Journals (Sweden)

    Huiting Bian


    Full Text Available CF3CBrCH2 (2-bromo-3,3,3-trifluoropropene, 2-BTP is a potential replacement for CF3Br; however, it shows conflicted inhibition and enhancement behaviors under different combustion conditions. To better understand the combustion chemistry of 2-BTP, a theoretical study has been performed on its reactions with OH and H radicals. Potential energy surfaces were exhaustively explored by using B3LYP/aug-cc-pVTZ for geometry optimizations and CCSD(T/aug-cc-pVTZ for high level single point energy refinements. Detailed kinetics of the major pathways were predicted by using RRKM/master-equation methodology. The present predictions imply that the –C(Br=CH2 moiety of 2-BTP is most likely to be responsible for its fuel-like property. For 2-BTP + OH, the addition to the initial adduct (CF3CBrCH2OH is the dominant channel at low temperatures, while the substitution reaction (CF3COHCH2 + Br and H abstraction reaction (CF3CBrCH + H2O dominates at high temperatures and elevated pressures. For 2-BTP + H, the addition to the initial adduct (CF3CBrCH3 also dominates the overall kinetics at low temperatures, while Br abstraction reaction (CF3CCH2 + HBr and β-scission of the adduct forming CF3CHCH2 + Br dominates at high temperatures and elevated pressures. Compared to 2-BTP + OH, the 2-BTP + H reaction tends to have a larger effect on flame suppression, given the fact that it produces more inhibition species.

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

    International Nuclear Information System (INIS)

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


    Dielectric properties and phase transitions of the piperazinium tetrafluoroborate ([NH 2 (CH 2 ) 4 NH][BF 4 ], 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 [BF 4 ] − units. The crystal structure of [NH 2 (CH 2 ) 4 NH][BF 4 ] 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. 1 H and 19 F NMR measurements indicate the reorientational motions of [BF 4 ] − 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 [NH 2 (CH 2 ) 4 NH][BF 4 ], phase IV. The dashed lines stand for the hydrogen bonds. The hydrogen bonds to BF4 groups are not included for

  8. -CH2- lengthening of the internucleotide linkage in the ApA dimer can improve its conformational compatibility with its natural polynucleotide counterpart (United States)

    Hanu, J.; Barvík, I.; Ruszová-Chmelová, K.; ŠtÆpánek, J.; Turpin, P.-Y.; Bok, J.; Rosenberg, I.; Petrová-Endová, M.


    The complete family of ApA phosphonate analogues with the internucleotide linkage elongated by insertion of a -CH2- group was prepared and the hybridisation and structural properties of its members in interaction with polyuridylic acid were investigated using an original 2D Raman approach. Except for the conformationally restricted ACHpA(2′3′endo-5′) modification, all of the isopolar, non-isosteric analogues form triplex-like complexes with poly(rU) at room temperature, in which two polymer strands are bound by Watson–Crick and Hoogsteen bonds to a central pseudostrand consisting of a ‘chain’ of A-dimers. For all of these dimers, the overall conformation of the triplexes was found to be similar according to their extracted Raman spectra. A simple semi-empirical model was introduced to explain the observed dependency of the efficiency of triplex formation on the adenine concentration. Apparently, for most of the modifications studied, the creation of a stable complex at room temperature requires the formation of a central pseudostrand, consisting of several adenine dimers. Molecular dynamics calculations were finally performed to interpret the differences in ‘cooperative’ behaviour between the different dimers studied. The results indicate that the exceptional properties of the ApCH2A(3′-5′) dimer could be caused by the 3D conformational compatibility of this modified linkage with the second (Hoogsteen) poly(rU) strand. PMID:11812852

  9. Unexpected consequences of increasing CO2 and ocean acidity on marine production of DMS and CH2ClI: Potential climate impacts (United States)

    Wingenter, Oliver W.; Haase, Karl B.; Zeigler, Max; Blake, Donald R.; Rowland, F. Sherwood; Sive, Barkley C.; Paulino, Ana; Thyrhaug, Runar; Larsen, Aud; Schulz, Kai; Meyerhöfer, Michael; Riebesell, Ulf


    Increasing atmospheric mixing ratios of CO2 have already lowered surface ocean pH by 0.1 units compared to preindustrial values and pH is expected to decrease an additional 0.3 units by the end of this century. Pronounced physiological changes in some phytoplankton have been observed during previous CO2 perturbation experiments. Marine microorganisms are known to consume and produce climate-relevant organic gases. Concentrations of (CH3)2S (DMS) and CH2ClI were quantified during the Third Pelagic Ecosystem CO2 Enrichment Study. Positive feedbacks were observed between control mesocosms and those simulating future CO2. Dimethyl sulfide was 26% (+/-10%) greater than the controls in the 2x ambient CO2 treatments, and 18% (+/-10%) higher in the 3xCO2 mesocosms. For CH2ClI the 2xCO2 treatments were 46% (+/-4%) greater than the controls and the 3xCO2 mesocosms were 131% (+/-11%) higher. These processes may help contribute to the homeostasis of the planet.

  10. Infrared spectra of the CH3-MX and CH2-MHX complexes formed by reactions of laser-ablated group 3 metal atoms with methyl halides. (United States)

    Cho, Han-Gook; Andrews, Lester


    Reactions of laser-ablated group 3 metal atoms with methyl halides have been carried out in excess of Ar during condensation and the matrix infrared spectra studied. The metals are as effective as other early transition metals in providing insertion products (CH3-MX) and higher oxidation state methylidene complexes (CH2-MHX) (X = F, Cl, Br) following alpha-hydrogen migration. Unlike the cases of the group 4-6 metals, the calculated methylidene complex structures show little evidence for agostic distortion, consistent with the previously studied group 3 metal methylidene hydrides, and the C-M bond lengths of the insertion and methylidene complexes are comparable to each other. However, the C-Sc bond lengths are 0.013, 0.025, and 0.029 A shorter for the CH2-ScHX complexes, respectively, and the spin densities are consistent with weak C(2p)-Sc(3d) pi bonding. The present results reconfirm that the number of valence electrons on the metal is important for agostic interaction in simple methylidene complexes.

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

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


    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.

  12. 248 nm photolysis of CH2Br2 by using cavity ring-down absorption spectroscopy: Br2 molecular elimination at room temperature. (United States)

    Wei, Pei-Ying; Chang, Yuan-Ping; Lee, Wei-Bin; Hu, Zhengfa; Huang, Hong-Yi; Lin, King-Chuen; Chen, K T; Chang, A H H


    Following photodissociation of CH2Br2 at 248 nm, Br2 molecular elimination is detected by using a tunable laser beam, as crossed perpendicular to the photolyzing laser beam in a ring-down cell, probing the Br2 fragment in the B 3Piou+ -X 1Sigmag+ transition. The nascent vibrational population is obtained, yielding a population ratio of Br2(v = 1)Br2(v = 0) to be 0.7 +/- 0.2. The quantum yield for the Br2 elimination reaction is determined to be 0.2 +/- 0.1. Nevertheless, when CH2Br2 is prepared in a supersonic molecular beam under cold temperature, photofragmentation gives no Br2 detectable in a time-of-flight mass spectrometer. With the aid of ab initio potential energy calculations, a plausible pathway is proposed. Upon excitation to the 1B1 or 3B1 state, C-Br bond elongation may change the molecular symmetry of Cs and enhance the resultant 1 1,3A'-X 1A' (or 1 1,3B1-X 1A1 as C2v is used) coupling to facilitate the process of internal conversion, followed by asynchronous concerted photodissociation. Temperature dependence measurements lend support to the proposed pathway.

  13. Transformation of Au144(SCH2CH2Ph)60 to Au133(SPh-tBu)52 Nanomolecules: Theoretical and Experimental Study. (United States)

    Nimmala, Praneeth Reddy; Theivendran, Shevanuja; Barcaro, Giovanni; Sementa, Luca; Kumara, Chanaka; Jupally, Vijay Reddy; Apra, Edoardo; Stener, Mauro; Fortunelli, Alessandro; Dass, Amala


    Ultrastable gold nanomolecule Au144(SCH2CH2Ph)60 upon etching with excess tert-butylbenzenethiol undergoes a core-size conversion and compositional change to form an entirely new core of Au133(SPh-tBu)52. This conversion was studied using high-resolution electrospray mass spectrometry which shows that the core size conversion is initiated after 22 ligand exchanges, suggesting a relatively high stability of the Au144(SCH2CH2Ph)38(SPh-tBu)22 intermediate. The Au144 → Au133 core size conversion is surprisingly different from the Au144 → Au99 core conversion reported in the case of thiophenol, -SPh. Theoretical analysis and ab initio molecular dynamics simulations show that rigid p-tBu groups play a crucial role by reducing the cluster structural freedom, and protecting the cluster from adsorption of exogenous and reactive species, thus rationalizing the kinetic factors that stabilize the Au133 core size. This 144-atom to 133-atom nanomolecule's compositional change is reflected in optical spectroscopy and electrochemistry.

  14. Reactivity of the biphasic trichloroacetonitrile-CH2Cl2/H2O2 system in the epoxidation of soybean oil

    Directory of Open Access Journals (Sweden)

    Martinelli, Márcia


    Full Text Available In this work we report on the epoxidation of soybean oil by the trichloroacetonitrile -CH2Cl2/H2O2 byphasic system. The reaction was carried out at room temperature and, most importantly, in non acid conditions which prevent the opening of the oxirane ring. The epoxidized soybean oil was characterized by infrared, 1H and 13C NMR. A maximum conversion of 81 % was achieved in two hours with 86% of selectivity in epoxy groupsEn el presente trabajo informamos sobre la epoxidación de aceite de soja mediante el sistema bifásico tricloroacetonitrilo-CH2Cl2/H2O2. La reacción fue realizada bajo condiciones de temperatura ambiente y, lo más importante, en condición no ácida, lo que evita la apertura del anillo oxirano. El aceite de soja fue caracterizado por infrarrojo y RMN de 1H and 13C. En dos horas se alcanzó una conversión máxima del 81 % obteniéndose una selectividad del 86 % en grupos epóxidos

  15. The Phospha–Michael addition product {(t-BuNHP(μ-N-t-Bu2P(=N-t-Bu—C(=CH2CH(p-CH3O—C6H4-P(O[(OCH2C(CH32CH2O]}

    Directory of Open Access Journals (Sweden)

    G. Gangadhararao


    Full Text Available The title compound, 2-{2-[1,3-di-tert-butyl-4-(tert-butylamino-2-(tert-butylimino-1,3,2λ5,4-diazadiphosphetidin-2-yl]-1-(4-methoxyphenylprop-2-en-1-yl}-5,5-dimethyl-1,3,2λ5-dioxaphosphinan-2-one, C31H57N4O4P3, was synthesized from the Phospha–Michael addition reaction of cyclodiphosphazane [(t-BuNHP(μ-Nt-Bu]2 and allenylphosphonate [(OCH2C(CH32CH2OP(OC(p-CH3O—C6H4=C=CH2]. In the crystal, N—H...O and C—H...O hydrogen bonds link the molecules. The structure exhibits pseudosymmetry but attempts to solve it in a higher (monoclinic space group were unsuccessful.

  16. Human myeloma immunoglobulins of the fourth subclass (IgG4 MAM) contain a fraction with different properties of CH2 domains. (United States)

    Tischenko, V M


    A long-lived metastable minor fraction has been detected and characterized in myeloma protein IgG4 MAM by hydro- and thermodynamic methods. The sedimentation constants of the minor and the major protein fractions are different. The stability of the two CH2 domains in the minor fraction varies. The unique characteristics of these IgG4 MAM conformers arise from the fact that on exchange of the heavy chains between IgG4 molecules, in some of them only one noncanonical bond Cys226-Cys229 is formed in the central part of the "hinge region" instead of two canonical interchain disulfide bonds Cys226-Cys226 and Cys229-Cys229. This leads to asymmetric structure of the IgG4 MAM molecules.

  17. Ozone generation in oxygen-fed wire-to-cylinder ozonizer: effect of CH2Cl2, CHCl3 and CCl4 diluents (United States)

    Skalný, J. D.; Ráheľ, J.; Holubčík, Ľ.


    The inhibition effect of methylene chloride CH2Cl2, chloroform CHCl3 and carbon tetrachloride CCl4 on the ozone generation process from oxygen by negative corona discharge was experimentally investigated. The experiments were performed in a system of coaxial cylindrical electrodes at total gas pressure of 900 mbar and ambient temperature of gaseous mixtures. The rate of ozone generation as well as ozone concentration apparently decreases with a rising number of substituted chlorine atoms in the methane molecule at constant specific energy consumption dissipated in the discharge and at constant concentration of gaseous impurities in oxygen. In addition to experimental results, the paper presents theoretical considerations aimed at identifying the main process responsible for inhibition of ozone generation. The consumption of considerable fraction of oxygen atoms by CH x Cl y-1 radicals formed in discharge, is likely the most important mechanism responsible for the deleterious effect of such compounds on the efficiency of ozone production.

  18. Pro-oxidant and antioxidant response elicited by CH2Cl2, CHCl3 and BrCHCl2 in Goodea gracilis using non-invasive methods. (United States)

    Dzul-Caamal, Ricardo; Olivares-Rubio, Hugo F; López-Tapia, Pamela; Vega-López, Armando


    The development of non-invasive methods aimed to evaluate the effects of many toxicants is required. Although there are some studies conducted in successful ways, a lack of information prevails especially for those substances that could be formed autochthonously in the water bodies, such as halomethanes (HMs). In this study, induction of pro-oxidant forces (CH2O, O2, H2O2), oxidative stress (TBARS, RCO) and antioxidant defenses (superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx) in the skin mucus layer regarding to the liver of Goodea gracilis exposed to CH2Cl2, CHCl3 and BrCHCl2 were evaluated, in addition to the hepatic cytochrome P450 (CYP 2E1) and glutathione S-transferase theta (GSTT) activities. Regardless of the implicit toxicity involved in the bioactivation of the HMs, carried out by the CYP 2E1 and GST, it was noticeable that this process induces oxidative stress. The usefulness of the mucus layer for the evaluation of the oxidative stress response was demonstrated, despite some peculiar characteristics concerning induction of oxidative stress in liver and skin mucous layer. However, for the understanding of the induction of reactive oxygen species in both targets it is essential to evaluate the activity of antioxidant defenses; otherwise the interpretation of toxic effects elicited by HMs would be erroneous. In the skin mucus layer, lower activities of the enzymes involved in antioxidant defense than in liver were observed. The evaluation of the biomarkers in the skin mucus layer involved in the oxidative stress is useful due the consistent response regarding to concentration of the HMs. Copyright © 2013 Elsevier Inc. All rights reserved.

  19. The Reaction of bis(1,2,4-tri-t-butylcyclopentadienyl)ceriumbenzyl, Cp'2CeCH2Ph with Methylhalides: a Metathesis Reaction that does not proceed by a Metathesis Transition State

    Energy Technology Data Exchange (ETDEWEB)

    Werkema, Evan; Andersen, Richard; Maron, Laurent; Eisenstein, Odile


    The experimental reaction between [1,2,4-(Me3C)3C5H2]2CeCH2Ph and CH3X, X = F, Cl, Br, and I, yields the metathetical exchange products, [1,2,4-(Me3C)3C5H2]2CeX and CH3CH2Ph. The reaction is complicated by the equilibrium between the benzyl derivative and the metallacycle [[1,2,4-(Me3C)3C5H2] [(Me3C)2C5H2C(CH3)2CH2]Ce, plus toluene since the metallacycle reacts with CH3X. Labelling studies show that the methyl group of the methylhalide is transferred intact to the benzyl group. The mechanism, as revealed by DFT calculations on (C5H5)2CeCH2Ph and CH3F, does not proceed by way of a four-center mechanism, (sigma-bond metathesis) but a lower barrier process involves a haptotropic shift of the Cp2Ce fragment so that at the transition state the para-carbon of the benzene ring is attached to the Cp2Ce fragment while the CH2 fragment of the benzyl group attacks CH3F that is activated by coordination to the metal ion. As a result the mechanism is classified as an associative interchange process.

  20. Gas phase kinetics of the OH + CH3CH2OH reaction at temperatures of the interstellar medium (T = 21-10^7 K) (United States)

    Ocaña, A. J.; Blázquez, S.; Ballesteros, B.; Canosa, A.; Antiñolo, M.; Albaladejoab, J.; Jiménez, E.


    Ethanol, CH3CH2OH, has been unveiled in the interstellar medium (ISM) by radioastronomy and it is thought to be released into the gas phase after the warm-up phase of the grain surface, where it is formed. Once in the gas phase, it can be destroyed by different reactions with atomic and radical species, such as hydroxyl (OH) radicals. The knowledge of the rate coefficients of all these processes at temperatures of the ISM is essential in the accurate interpretation of the observed abundances. In this work, we have determined the rate coefficient for the reaction of OH with CH3CH2OH (k(T)) between 21 and 10^7 K by employing the pulsed and continuous CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique. The pulsed laser photolysis technique was used for generating OH radicals, whose time evolution was monitored by laser induced fluorescence. An increase of approximately 4 times was observed for k(21 K) with respect to k(10^7 K). With respect to k(300 K), the OH-reactivity at 21 K is enhanced by two orders of magnitude. The obtained T-expression in the investigated temperature range is k(T) = (2.1 ± 0.5) × 10^-11 (T/300 K)-(0.71±0.10) cm^3 molecule^-1 s^-1. In addition, the pressure dependence of k(T) has been investigated at several temperatures between 21 K and 90 K. No pressure dependence of k(T) was observed in the investigated ranges. This may imply that this reaction is purely bimolecular or that the high-pressure limit is reached at the lowest total pressure experimentally accessible in our system. From our results, k(T) at usual IS temperatures (˜10-100 K) is confirmed to be very fast. Typical rate coefficients can be considered to range within about 4 × 10^-11 cm^3 molecule^-1 s^-1 at 100 K and around 1 × 10^-10 cm^3 molecule^-1 s^-1 at 20 K. The extrapolation of k at the lowest temperatures of the dense molecular clouds of ISM is also discussed in this paper.

  1. Gas phase kinetics of the OH + CH3CH2OH reaction at temperatures of the interstellar medium (T = 21-107 K). (United States)

    Ocaña, A J; Blázquez, S; Ballesteros, B; Canosa, A; Antiñolo, M; Albaladejo, J; Jiménez, E


    Ethanol, CH 3 CH 2 OH, has been unveiled in the interstellar medium (ISM) by radioastronomy and it is thought to be released into the gas phase after the warm-up phase of the grain surface, where it is formed. Once in the gas phase, it can be destroyed by different reactions with atomic and radical species, such as hydroxyl (OH) radicals. The knowledge of the rate coefficients of all these processes at temperatures of the ISM is essential in the accurate interpretation of the observed abundances. In this work, we have determined the rate coefficient for the reaction of OH with CH 3 CH 2 OH (k(T)) between 21 and 107 K by employing the pulsed and continuous CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique. The pulsed laser photolysis technique was used for generating OH radicals, whose time evolution was monitored by laser induced fluorescence. An increase of approximately 4 times was observed for k(21 K) with respect to k(107 K). With respect to k(300 K), the OH-reactivity at 21 K is enhanced by two orders of magnitude. The obtained T-expression in the investigated temperature range is k(T) = (2.1 ± 0.5) × 10 -11 (T/300 K) -(0.71±0.10) cm 3 molecule -1 s -1 . In addition, the pressure dependence of k(T) has been investigated at several temperatures between 21 K and 90 K. No pressure dependence of k(T) was observed in the investigated ranges. This may imply that this reaction is purely bimolecular or that the high-pressure limit is reached at the lowest total pressure experimentally accessible in our system. From our results, k(T) at usual IS temperatures (∼10-100 K) is confirmed to be very fast. Typical rate coefficients can be considered to range within about 4 × 10 -11 cm 3 molecule -1 s -1 at 100 K and around 1 × 10 -10 cm 3 molecule -1 s -1 at 20 K. The extrapolation of k at the lowest temperatures of the dense molecular clouds of ISM is also discussed in this paper.

  2. Antimicrobial activities of the CH2Cl2-CH3OH (1:1) extracts and compounds from the roots and fruits of Pycnanthus angolensis (Myristicaceae). (United States)

    Kuete, Victor; Nono, Eric C N; Mkounga, Pierre; Marat, Kirk; Hultin, Philip G; Nkengfack, Augustin E


    This study was designed at evaluating the antimycobacterial, antibacterial and antifungal activities of the CH2Cl2-CH3OH (1:1) extracts and isolated compounds, namely 3,4-dimethoxy-3',4'-methylenedioxy-7,7'-epoxylignan (1), genkwainin (2), pycnanthulignene C (3), 4,5-dimethoxy-3',4'-methylenedioxy-2,7'-cycloligna-7,7'-diene (4), pycnanthulignene A (5) from the roots, and calycosin (6), biochanin A (7) and prunetin (8), from the fruits of Pycnanthus angolensis. The microplate alamar blue assay and the broth microdilution method were used to determine the minimal inhibitory concentration (MIC) and minimal microbicidal concentration of the samples. The H+-ATPase-mediated proton pumping assay was used to evaluate one of the possible mechanisms of action of the extracts and isolated compounds. The results of MIC determinations showed that the extract from roots was able to prevent the growth of all the studied organisms, including mycobacteria, fungi, and Gram-positive and Gram-negative bacteria. All tested compounds showed antimicrobial activities to different extents, compound 1 and 8 exhibiting the best antimicrobial spectrum, with 92.3% of the tested organisms being sensitive. The results obtained in this study also showed that the extracts as well as most of the compounds were able to inhibit the H(+)-ATPase activity. The overall results provided evidence that P. angolensis and some of its components might be potential sources of antimicrobial drugs against tuberculosis, bacterial and fungal diseases.

  3. High-accuracy measurements of OH reaction rate constants and IR absorption spectra: CH2=CF-CF3 and trans-CHF=CH-CF3. (United States)

    Orkin, Vladimir L; Martynova, Larissa E; Ilichev, Alexander N


    Rate constants for the gas phase reactions of OH radicals with two isomers of tetrafluoropropene, CH(2)=CF-CF(3) (k(1)) and trans-CHF=CH-CF(3) (k(2)); were measured using a flash photolysis resonance-fluorescence technique over the temperature range 220 to 370 K. The Arrhenius plots were found to exhibit a noticeable curvature. The temperature dependences of the rate constants are very weak and can be represented by the following expressions over the indicated temperature intervals: k(1)(220-298 K) = 1.145 x 10(-12) x exp{13/T} cm(3) molecule(-1) s(-1), k(1)(298-370 K) = 4.06 x 10(-13) x (T/298)(1.17) x exp{+296/T} cm(3) molecule(-1) s(-1), k(2)(220-370 K) = 1.115 x 10(-13) x (T/298)(2.03) x exp{+522/T} cm(3) molecule(-1) s(-1). The overall accuracy of the rate constant measurements is estimated to be ca. 2% to 2.5% at the 95% confidence level. The uncertainty of the measured reaction rate constants is discussed in detail. The atmospheric lifetimes due to reactions with tropospheric OH were estimated to be 12 and 19 days respectively under the assumption of a well mixed atmosphere. IR absorption cross-sections were measured for both compounds and their global warming potentials were estimated.


    International Nuclear Information System (INIS)

    Vigren, E.; Hamberg, M.; Zhaunerchyk, V.; Kaminska, M.; Thomas, R. D.; Larsson, M.; Geppert, W. D.; Millar, T. J.; Walsh, C.


    Measurements on the dissociative recombination (DR) of protonated acrylonitrile, CH 2 CHCNH + , have been performed at the heavy ion storage ring CRYRING located in the Manne Siegbahn Laboratory in Stockholm, Sweden. It has been found that at ∼2 meV relative kinetic energy about 50% of the DR events involve only ruptures of X-H bonds (where X = C or N) while the rest leads to the production of a pair of fragments each containing two heavy atoms (alongside H and/or H 2 ). The absolute DR cross section has been investigated for relative kinetic energies ranging from ∼1 meV to 1 eV. The thermal rate coefficient has been determined to follow the expression k(T) = 1.78 x 10 -6 (T/300) - 0.80 cm 3 s -1 for electron temperatures ranging from ∼10 to 1000 K. Gas-phase models of the nitrile chemistry in the dark molecular cloud TMC-1 have been run and results are compared with observations. Also, implications of the present results for the nitrile chemistry of Titan's upper atmosphere are discussed.

  5. Molecular elimination of Br2 in photodissociation of CH2BrC(O)Br at 248 nm using cavity ring-down absorption spectroscopy. (United States)

    Fan, He; Tsai, Po-Yu; Lin, King-Chuen; Lin, Cheng-Wei; Yan, Chi-Yu; Yang, Shu-Wei; Chang, A H H


    The primary elimination channel of bromine molecule in one-photon dissociation of CH(2)BrC(O)Br at 248 nm is investigated using cavity ring-down absorption spectroscopy. By means of spectral simulation, the ratio of nascent vibrational population in v = 0, 1, and 2 levels is evaluated to be 1:(0.5 ± 0.1):(0.2 ± 0.1), corresponding to a Boltzmann vibrational temperature of 581 ± 45 K. The quantum yield of the ground state Br(2) elimination reaction is determined to be 0.24 ± 0.08. With the aid of ab initio potential energy calculations, the obtained Br(2) fragments are anticipated to dissociate on the electronic ground state, yielding vibrationally hot Br(2) products. The temperature-dependence measurements support the proposed pathway via internal conversion. For comparison, the Br(2) yields are obtained analogously from CH(3)CHBrC(O)Br and (CH(3))(2)CBrC(O)Br to be 0.03 and 0.06, respectively. The trend of Br(2) yields among the three compounds is consistent with the branching ratio evaluation by Rice-Ramsperger-Kassel-Marcus method. However, the latter result for each molecule is smaller by an order of magnitude than the yield findings. A non-statistical pathway so-called roaming process might be an alternative to the Br(2) production, and its contribution might account for the underestimate of the branching ratio calculations.

  6. Highly selective etching of silicon nitride to physical-vapor-deposited a-C mask in dual-frequency capacitively coupled CH2F2/H2 plasmas

    International Nuclear Information System (INIS)

    Kim, J. S.; Kwon, B. S.; Heo, W.; Jung, C. R.; Park, J. S.; Shon, J. W.; Lee, N.-E.


    A multilevel resist (MLR) structure can be fabricated based on a very thin amorphous carbon (a-C) layer ( congruent with 80 nm) and Si 3 N 4 hard-mask layer ( congruent with 300 nm). The authors investigated the selective etching of the Si 3 N 4 layer using a physical-vapor-deposited (PVD) a-C mask in a dual-frequency superimposed capacitively coupled plasma etcher by varying the process parameters in the CH 2 F 2 /H 2 /Ar plasmas, viz., the etch gas flow ratio, high-frequency source power (P HF ), and low-frequency source power (P LF ). They found that under certain etch conditions they obtain infinitely high etch selectivities of the Si 3 N 4 layers to the PVD a-C on both the blanket and patterned wafers. The etch gas flow ratio played a critical role in determining the process window for infinitely high Si 3 N 4 /PVD a-C etch selectivity because of the change in the degree of polymerization. The etch results of a patterned ArF photoresisit/bottom antireflective coating/SiO x /PVD a-C/Si 3 N 4 MLR structure supported the idea of using a very thin PVD a-C layer as an etch-mask layer for the Si 3 N 4 hard-mask pattern with a pattern width of congruent with 80 nm and high aspect ratio of congruent with 5.

  7. Possible interstellar formation of glycine from the reaction of CH2=NH, CO and H2O: catalysis by extra water molecules through the hydrogen relay transport. (United States)

    Nhlabatsi, Zanele P; Bhasi, Priya; Sitha, Sanyasi


    "How the fundamental life elements are created in the interstellar medium (ISM)?" is one of the intriguing questions related to the genesis of life. Using computational calculations, we have discussed the reaction of CH2=NH, CO and H2O for the formation of glycine, the simplest life element. This reaction proceeds through a concerted mechanism with reasonably large barriers for the cases with one and two water molecules as reactants. For the two water case we found that the extra water molecule exhibits some catalytic role through the hydrogen transport relay effect and the barrier height is reduced substantially compared to the case with one water molecule. These two cases can be treated as ideal cases for the hot-core formation of the interstellar glycine. With an increasing number of water molecules as the reactants, we found that when the numbers of water molecules are three or more than three, the barrier height reduced so drastically that the transition states were more stable than the reactants. Such a situation gives a clear indication that with excess water molecules as the reactants, this reaction will be feasible even under the low temperature conditions existing in the cold interstellar clouds and the exothermic nature of the reaction will be the driving force.

  8. Influence of the choice of internal temperatures on the composition of CxHyOzNt plasmas out of thermodynamic equilibrium: Application to CH2 plasma

    International Nuclear Information System (INIS)

    Koalaga, Zacharie


    The purpose of this paper is to study the influence of the choice of internal temperatures on the composition of C x H y O z N t plasmas out of thermodynamic equilibrium. The numerical calculation is specially performed for CH 2 plasma in the pressure range 0.1-1 MPa and for the electron temperature range 5000-30 000 K. Precisely, the investigation of this plasma allows one to show that the choice of internal temperatures can have more influence on plasma composition than the choice of the form of the two-temperature Saha and Guldberg-Waage laws. Indeed, for one of the supposed hypotheses, it is observed that the two forms of the two-temperature system used here can give the same equilibrium composition by uncoupling the excitation temperature of the diatomic and the monatomic species. Great attention must then be given to the adopted hypothesis for internal temperature and not only to the form of the two temperature system used. An accurate comparison between the two models requires the measurement of plasma parameters such as the various internal temperatures and the species concentration. Therefore, we have also carried out an analysis of the potential experimental diagnostics of these plasma parameters. Such diagnostics can help to test and validate theoretical models

  9. Visible absorption and magnetic-rotation spectroscopy of 1CH2: The analysis of the b˜ 1B1 state (United States)

    Petek, Hrvoje; Nesbitt, David J.; Darwin, David C.; Moore, C. Bradley


    The b˜1B1←ã 1A1 spectrum of CH2 radical has been recorded with Doppler-limited resolution in the 15 600-18 650 cm-1 wavelength region by laser flash-kinetic absorption spectroscopy. Singlet methylene is produced by photolysis of ketene at 308 nm. Assignments for 477 transitions originating from 1A1(0,0,0) and (0,1,0) levels with J≤8 and Ka≤5 are reported from some 10 000 lines observed. Term values are given for these 1A1 levels and 1B1(0,v2,0) levels with 13≤v2≤17. Magnetic-rotation signals were observed for 60% of the 424 lines studied. This anomalous Zeeman effect is explained by singlet-triplet mixing in both ã and b˜ states. Extensive singlet-triplet mixing occurs for 1B1 levels with Ka≠0; this mixing is allowed in second order by Renner-Teller coupling of b˜ 1B1 with ã 1A1 and by spin-orbit coupling via ã 1A1 to X˜ 3B1. The consequent shifts prevent determination of accurate rovibrational structural parameters for the 1B1 state.

  10. Ruthenium-complex catalyzed N-(cyclo)alkylation of aromatic amines with diols. Selective synthesis of N-(n-hydroixyalkyl)anilines of type PhNH(CH2)nOH and of some bioactive arylpiperazines,

    NARCIS (Netherlands)

    Koten, G. van; Abbenhuis, R.A.T.M.; Boersma, J.


    A new class of well-defined neutral mono-, and dicationic ruthenium(II) complexes containing a neutral terdentate donor system [C5H3N(CH2E)(2)-2,6] (E = PPh2 (PNP) or NMe2 (NN'N)) has been found effective as catalyst precursor in N-(cyclo)alkylation reactions of aromatic amines with diols

  11. Metal-free [3+2] cycloaddition of azides with Tf2C=CH2 for the regioselective preparation of elusive 4-(trifluoromethylsulfonyl)-1,2,3-triazoles. (United States)

    Alcaide, Benito; Almendros, Pedro; Lázaro-Milla, Carlos


    1,2-Dipole Tf2C=CH2 is generated in situ and immediately reacts at room temperature with an azide to afford previously unknown 4-trifluoromethanesulfonyl 1,2,3-triazoles through a stepwise [3+2] cycloaddition reaction. Noteworthily, this mild and powerful uncatalyzed protocol is highly regio- and chemoselective.

  12. Phosphinodi(benzylsilane) PhP{(o-C6H4CH2)SiMe2H}2: a versatile "PSi2Hx" pincer-type ligand at ruthenium. (United States)

    Montiel-Palma, Virginia; Muñoz-Hernández, Miguel A; Cuevas-Chávez, Cynthia A; Vendier, Laure; Grellier, Mary; Sabo-Etienne, Sylviane


    The synthesis of the new phosphinodi(benzylsilane) compound PhP{(o-C6H4CH2)SiMe2H}2 (1) is achieved in a one-pot reaction from the corresponding phenylbis(o-tolylphosphine). Compound 1 acts as a pincer-type ligand capable of adopting different coordination modes at Ru through different extents of Si-H bond activation as demonstrated by a combination of X-ray diffraction analysis, density functional theory calculations, and multinuclear NMR spectroscopy. Reaction of 1 with RuH2(H2)2(PCy3)2 (2) yields quantitatively [RuH2{[η(2)-(HSiMe2)-CH2-o-C6H4]2PPh}(PCy3)] (3), a complex stabilized by two rare high order ε-agostic Si-H bonds and involved in terminal hydride/η(2)-Si-H exchange processes. A small free energy of reaction (ΔrG298 = +16.9 kJ mol(-1)) was computed for dihydrogen loss from 3 with concomitant formation of the 16-electron species [RuH{[η(2)-(HSiMe2)-CH2-o-C6H4]PPh[CH2-o-C6H4SiMe2]}(PCy3)] (4). Complex 4 features an unprecedented (29)Si NMR decoalescence process. The dehydrogenation process is fully reversible under standard conditions (1 bar, 298 K).

  13. Combined crossed molecular beam and ab initio investigation of the reaction of boron monoxide (BO; X(2)Σ(+)) with 1,3-butadiene (CH2CHCHCH2; X(1)Ag) and its deuterated counterparts. (United States)

    Maity, Surajit; Dangi, Beni B; Parker, Dorian S N; Kaiser, Ralf I; Lin, Hong-Mao; E, Hai-Ping; Sun, Bing-Jian; Chang, A H H


    The reactions of the boron monoxide ((11)BO; X(2)Σ(+)) radical with 1,3-butadiene (CH2CHCHCH2; X(1)Ag) and its partially deuterated counterparts, 1,3-butadiene-d2 (CH2CDCDCH2; X(1)Ag) and 1,3-butadiene-d4 (CD2CHCHCD2; X(1)Ag), were investigated under single collision conditions exploiting a crossed molecular beams machine. The experimental data were combined with the state-of-the-art ab initio electronic structure calculations and statistical RRKM calculations to investigate the underlying chemical reaction dynamics and reaction mechanisms computationally. Our investigations revealed that the reaction followed indirect scattering dynamics through the formation of (11)BOC4H6 doublet radical intermediates via the barrierless addition of the (11)BO radical to the terminal carbon atom (C1/C4) and/or the central carbon atom (C2/C3) of 1,3-butadiene. The resulting long-lived (11)BOC4H6 intermediate(s) underwent isomerization and/or unimolecular decomposition involving eventually at least two distinct atomic hydrogen loss pathways to 1,3-butadienyl-1-oxoboranes (CH2CHCHCH(11)BO) and 1,3-butadienyl-2-oxoboranes (CH2C ((11)BO)CHCH2) in overall exoergic reactions via tight exit transition states. Utilizing partially deuterated 1,3-butadiene-d2 and -d4, we revealed that the hydrogen loss from the methylene moiety (CH2) dominated with 70 ± 10% compared to an atomic hydrogen loss from the methylidyne group (CH) of only 30 ± 10%; these data agree nicely with the theoretically predicted branching ratio of 80% versus 19%.

  14. Effect of organic chain length on structure, electronic composition, lattice potential energy, and optical properties of 2D hybrid perovskites [(NH3)(CH2) n (NH3)]CuCl4, n = 2-9 (United States)

    Abdel-Aal, Seham K.; Kocher-Oberlehner, Gudrun; Ionov, Andrei; Mozhchil, R. N.


    Diammonium series of Cu hybrid perovskites of the formula [(NH3)(CH2) n (NH3)]CuCl4, n = 6-9 are prepared from an ethanolic solution in stoichiometric ratio 1:1 (organic/inorganic). Formation of the desired material was confirmed and characterizes by microchemical analysis, FTIR, XRD and XPS spectra. The structure consists of corner-shared octahedron [CuCl4]2- anion alternative by organic [(NH3)(CH2) n (NH3)]2+ cations. The organic and inorganic layers form infinite 2D sheet that are connected via NH···Cl hydrogen bond. The calculated lattice potential energy U pot (kJ/mol) and lattice enthalpy Δ H L (kJ/mol) are inversely proportional to the molecular volume V m (nm3) and organic chain length. Optical properties show strong absorption peak at UV-visible range. The band gap energy calculated using Kubelka-Munk equation shows the decrease of the energy gap as organic chain length increases. The introduction of bromide ion to [(NH3)(CH2) n (NH3)]CuCl2Br2 denoted 2C7CuCB hybrid has shifted the energy gap to lower values from 2.6 to 2.18 eV for 2C7CuCl (yellow) and 2C7CuCB (brown), respectively, at the same organic chain length. All elements of [(NH3)(CH2)9(NH3)]CuCl4 and [(NH3)(CH2)7(NH3)]CuCl2Br2 were found in XPS spectra, as well as valence band spectra.


    NARCIS (Netherlands)


    Several C-H activation reactions with (Cp*2YH)2 (1) are reported. Thermolysis of 1 in n-octane, cyclohexane, or benzene leads to formation of the thermodynamically favored product Cp*2Y(mu-H)(mu-eta1,eta'-CH2C5Me4)YCp*(2). The molecular structure of 2 was determined by X-ray diffraction. The

  16. Enthalpies of solvation of ethylene oxide oligomers CH3O(CH2CH2O)nCH3 (n = 1 to 4) in different H-bonding solvents: Methanol, chloroform, and water. Group contribution method as applied to the polar oligomers

    International Nuclear Information System (INIS)

    Barannikov, Vladimir P.; Guseynov, Sabir S.; Vyugin, Anatoliy I.


    Highlights: → Solvation enthalpy is found for ethylene oxide oligomers in chloroform and methanol. → Coefficients of solute-solute interaction are determined for oligomers in methanol. → Enthalpies of hydrogen bonding of oligomers with chloroform and water are estimated. → Additivity scheme is developed for describing enthalpies of solvation of oligomers. - Abstract: The enthalpies of solution and solvation of ethylene oxide oligomers CH 3 O(CH 2 CH 2 O) n CH 3 (n = 1 to 4) in methanol and chloroform have been determined from calorimetric measurements at T = 298.15 K. The enthalpic coefficients of pairwise solute-solute interaction for methanol solutions have been calculated. The enthalpic characteristics of the oligomers in methanol, chloroform, water and tetrachloromethane have been compared. The hydrogen bonding of the oligomers with chloroform and water molecules is exhibited in the values of solvation enthalpy and coefficient of solute-solute interaction. This effect is not observed for methanol solvent. The thermochemical data evidence an existence of multi-centred hydrogen bonds in associates of polyethers with the solvent molecules. Enthalpies of hydrogen bonding of the oligomers with chloroform and water have been estimated. The additivity scheme has been developed to describe the enthalpies of solvation of ethylene oxide oligomers, unbranched monoethers and n-alkanes in chloroform, methanol, water, and tetrachloromethane. The correction parameters for contribution of repeated polar groups and correction term for methoxy-compounds have been introduced. The obtained group contributions permit to describe the enthalpies of solvation of unbranched monoethers and ethylene oxide oligomers in the solvents with standard deviation up to 0.6 kJ . mol -1 . The values of group contributions and corrections are strongly influenced by solvent properties.

  17. Chloroacetone photodissociation at 193 nm and the subsequent dynamics of the CH3C(O)CH2 radical--an intermediate formed in the OH + allene reaction en route to CH3 + ketene. (United States)

    Alligood, Bridget W; FitzPatrick, Benjamin L; Szpunar, David E; Butler, Laurie J


    We use a combination of crossed laser-molecular beam experiments and velocity map imaging experiments to investigate the primary photofission channels of chloroacetone at 193 nm; we also probe the dissociation dynamics of the nascent CH(3)C(O)CH(2) radicals formed from C-Cl bond fission. In addition to the C-Cl bond fission primary photodissociation channel, the data evidence another photodissociation channel of the precursor, C-C bond fission to produce CH(3)CO and CH(2)Cl. The CH(3)C(O)CH(2) radical formed from C-Cl bond fission is one of the intermediates in the OH + allene reaction en route to CH(3) + ketene. The 193 nm photodissociation laser allows us to produce these CH(3)C(O)CH(2) radicals with enough internal energy to span the dissociation barrier leading to the CH(3) + ketene asymptote. Therefore, some of the vibrationally excited CH(3)C(O)CH(2) radicals undergo subsequent dissociation to CH(3) + ketene products; we are able to measure the velocities of these products using both the imaging and scattering apparatuses. The results rule out the presence of a significant contribution from a C-C bond photofission channel that produces CH(3) and COCH(2)Cl fragments. The CH(3)C(O)CH(2) radicals are formed with a considerable amount of energy partitioned into rotation; we use an impulsive model to explicitly characterize the internal energy distribution. The data are better fit by using the C-Cl bond fission transition state on the S(1) surface of chloroacetone as the geometry at which the impulsive force acts, not the Franck-Condon geometry. Our data suggest that, even under atmospheric conditions, the reaction of OH with allene could produce a small branching to CH(3) + ketene products, rather than solely producing inelastically stabilized adducts. This additional channel offers a different pathway for the OH-initiated oxidation of such unsaturated volatile organic compounds, those containing a C=C=C moiety, than is currently included in atmospheric models.

  18. Atmospheric chemistry of CF3CF═CH2 and (Z)-CF3CF═CHF: Cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations. (United States)

    Papadimitriou, Vassileios C; Lazarou, Yannis G; Talukdar, Ranajit K; Burkholder, James B


    Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF

  19. Linear homobimetallic 4-thioacetyl-substituted NCN pincer palladium(II) and platinum(II) complexes with N-bidentate connecting units (NCN = [C6H2(CH2NMe2)2-2,6-R-4]−)

    NARCIS (Netherlands)

    Döring, K.; Taher, D.; Walfort, B.; Lutz, M.; Spek, A.L.; van Klink, G.P.M.; van Koten, G.; Lang, H.


    The synthesis and characterization of homobimetallic palladium and platinum complexes of type [(Me(O)CS-4-NCN–M ← N∩N → M–NCN-4-SC(O)Me](OTf)2 (Me(O)CS-4-NCN = [C6H2(CH2NMe2)2-2,6-SC(O)Me-4]−; N∩N = 4,4′-bipyridine (bipy); M = Pd, 12; M = Pt, 13) is reported. The required bifunctional thio-acetyl

  20. Chemical Complexity in Local Diffuse and Translucent Clouds: Ubiquitous Linear C3H and CH3CN, a Detection of HC3N and an Upper Limit on the Abundance of CH2CN (United States)

    Liszt, Harvey; Gerin, Maryvonne; Beasley, Anthony; Pety, Jerome


    We present Jansky Very Large Array observations of 20–37 GHz absorption lines from nearby Galactic diffuse molecular gas seen against four cosmologically distant compact radio continuum sources. The main new observational results are that l-C3H and CH3CN are ubiqitous in the local diffuse molecular interstellar medium at {\\text{}}{A}{{V}} ≲ 1, while HC3N was seen only toward B0415 at {\\text{}}{A}{{V}} > 4 mag. The linear/cyclic ratio is much larger in C3H than in C3H2 and the ratio CH3CN/HCN is enhanced compared to TMC-1, although not as much as toward the Horsehead Nebula. More consequentially, this work completes a long-term program assessing the abundances of small hydrocarbons (CH, C2H, linear and cyclic C3H and C3 {{{H}}}2, and C4H and C4H‑) and the CN-bearing species (CN, HCN, HNC, HC3N, HC5N, and CH3CN): their systematics in diffuse molecular gas are presented in detail here. We also observed but did not strongly constrain the abundances of a few oxygen-bearing species, most prominently HNCO. We set limits on the column density of CH2CN, such that the anion CH2CN‑ is only viable as a carrier of diffuse interstellar bands if the N(CH2CN)/N(CH2CN‑) abundance ratio is much smaller in this species than in any others for which the anion has been observed. We argue that complex organic molecules (COMS) are not present in clouds meeting a reasonable definition of diffuse molecular gas, i.e., {\\text{}}{A}{{V}} ≲ 1 mag. Based on observations obtained with the NRAO Jansky Very Large Array (VLA).

  1. Kinetics of the gas-phase reactions of chlorine atoms with CH2F2, CH3CCl3 and CF3CFH2 over the temperature range 253 – 551 K

    DEFF Research Database (Denmark)

    Nilsson, Elna Johanna Kristina; Johnson, Matthew Stanley; Nielsen, Ole John


    Relative rate techniques were used to study the title reactions in 930–1200 mbar of N2 diluent. The reaction rate coefficients measured in the present work are summarized by the expressions k(Cl+CH2F2) = 1.19×10-17 T 2 exp(-1023/T ) cm3 molecule-1 s-1 (253– 553 K), k(Cl+CH3CCl3) = 2.41×10-12 exp(...

  2. Axial zero-field splitting in mononuclear Co(ii) 2-N substituted N-confused porphyrin: Co(2-NC3H5-21-Y-CH2C6H4CH3-NCTPP)Cl (Y = o, m, p) and Co(2-NC3H5-21-CH2C6H5-NCTPP)Cl. (United States)

    Lai, Ya-Yuan; Chang, Yu-Chang; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu


    The inner C-benzyl- and C-o-xylyl (or m-xylyl, p-xylyl)-substituted cobalt(ii) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NC3H5NCTPPH (1) and CoCl2·6H2O in toluene (or o-xylene, m-xylene, p-xylene). The crystal structures of diamagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-hydrogen-21-carbaporphyrinato-N,N',N'')zinc(ii) [Zn(2-NC3H5-21-H-NCTPP)Cl; 3 ] and paramagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-benzyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-CH2C6H5NCTPP)Cl; 7], and chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-Y-xylyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-Y-CH2C6H4CH3NCTPP)Cl] [Y = o (8), m (9), p (10)] were determined. The coordination sphere around the Zn(2+) (or Co(2+)) ion in 3 (or 7-10) is a distorted tetrahedron (DT). The free energy of activation at the coalescence temperature Tc for the exchange of phenyl ortho protons o-H (26) with o-H (22) in 3 in a CDCl3 solvent is found to be ΔG = 61.4 kJ mol(-1) through (1)H NMR temperature-dependent measurements. The axial zero-field splitting parameter |D| was found to vary from 35.6 cm(-1) in 7 (or 30.7 cm(-1) in 8) to 42.0 cm(-1) in 9 and 46.9 cm(-1) in 10 through paramagnetic susceptibility measurements. The magnitude of |D| can be related to the coordination sphere at the cobalt sites.

  3. Does dinitrogen hydrogenation follow different mechanisms for [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2) and {[PhP(CH2SiMe2NSiMe2CH2)PPh]Zr}2(mu2,eta2,eta2-N2) complexes? A computational study. (United States)

    Bobadova-Parvanova, Petia; Wang, Qingfang; Quinonero-Santiago, David; Morokuma, Keiji; Musaev, Djamaladdin G


    The mechanisms of dinitrogen hydrogenation by two different complexes--[(eta(5)-C(5)Me(4)H)(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)), synthesized by Chirik and co-workers [Nature 2004, 427, 527], and {[P(2)N(2)]Zr}(2)(mu(2),eta(2),eta(2)-N(2)), where P(2)N(2) = PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh, synthesized by Fryzuk and co-workers [Science 1997, 275, 1445]--are compared with density functional theory calculations. The former complex is experimentally known to be capable of adding more than one H(2) molecule to the side-on coordinated N(2) molecule, while the latter does not add more than one H(2). We have shown that the observed difference in the reactivity of these dizirconium complexes is caused by the fact that the former ligand environment is more rigid than the latter. As a result, the addition of the first H(2) molecule leads to two different products: a non-H-bridged intermediate for the Chirik-type complex and a H-bridged intermediate for the Fryzuk-type complex. The non-H-bridged intermediate requires a smaller energy barrier for the second H(2) addition than the H-bridged intermediate. We have also examined the effect of different numbers of methyl substituents in [(eta(5)-C(5)Me(n)H(5)(-)(n))(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)) for n = 0, 4, and 5 (n = 5 is hypothetical) and [(eta(5)-C(5)H(2)-1,2,4-Me(3))(eta(5)-C(5)Me(5))(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)) and have shown that all complexes of this type would follow a similar H(2) addition mechanism. We have also performed an extensive analysis on the factors (side-on coordination of N(2) to two Zr centers, availability of the frontier orbitals with appropriate symmetry, and inflexibility of the catalyst ligand environment) that are required for successful hydrogenation of the coordinated dinitrogen.

  4. A Mechanistical Study on the Formation of Dimethyl Ether (CH3OCH3) and Ethanol (CH3CH2OH) in Methanol-containing Ices and Implications for the Chemistry of Star-forming Regions (United States)

    Bergantini, Alexandre; Góbi, Sándor; Abplanalp, Matthew J.; Kaiser, Ralf I.


    The underlying formation mechanisms of complex organic molecules (COMs)—in particular, structural isomers—in the interstellar medium (ISM) are largely elusive. Here, we report new experimental findings on the role of methanol (CH3OH) and methane (CH4) ices in the synthesis of two C2H6O isomers upon interaction with ionizing radiation: ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3). The present study reproduces the interstellar abundance ratios of both species with ethanol to dimethyl ether branching ratios of (2.33 ± 0.14):1 suggesting that methanol and methane represents the key precursor to both isomers within interstellar ices. Exploiting isotopic labeling combined with reflectron time-of-flight mass spectrometry (Re-TOF-MS) after isomer selective vacuum ultra-violet (VUV) photoionization of the neutral molecules, we also determine the formation mechanisms of both isomers via radical–radical recombination versus carbene (CH2) insertion with the former pathway being predominant. Formation routes to higher molecular weight reaction products such as ethylene glycol (HOCH2CH2OH), dimethyl peroxide (CH3OOCH3), and methoxymethanol (CH3OCH2OH) are discussed briefly as well.

  5. Hybrid perovskite resulting from the solid-state reaction between the organic cations and perovskite layers of alpha1-(Br-(CH(2))(2)-NH(3))(2)PbI(4). (United States)

    Sourisseau, Sebastien; Louvain, Nicolas; Bi, Wenhua; Mercier, Nicolas; Rondeau, David; Buzaré, Jean-Yves; Legein, Christophe


    The alpha1-(Br-(CH(2))(2)-NH(3))(2)PbI(4) hybrid perovskite undergoes a solid-state transformation, that is, the reaction between the organic cations and the perovskite layers to give the new hybrid perovskite (Br-(CH(2))(2)-NH(3))(2-x)(I-(CH(2))(2)-NH(3))(x)PbBr(x)I(4-x), based on mixed halide inorganic layers. This transformation has been followed by a conventional powder X-ray diffraction system equipped with a super speed detector, and both solid-state (13)C NMR and ESI/MS measurements have been adopted in the estimation of the rate of halide substitution. The first reaction step leads to the special composition of x approximately 1 (A phase), while the complete substitution is not achieved even at elevated temperature (x(max) approximately 1.85 (B phase)). This unprecedented solid-state reaction between organic and inorganic components of a hybrid perovskite can be considered as a completely new strategy to achieve interesting hybrid perovskites.

  6. The first constant-domain (CH1) exon of human IGHG2 is polymorphic and in strong linkage disequilibrium with the CH2 exon polymorphism encoding the G2m(n+) allotype in Caucasians

    DEFF Research Database (Denmark)

    Hougs, L; Svejgaard, A; Barington, T


    , this amino acid position is expected to be surface exposed in IgG2. Besides this structural difference, we identified two silent nucleotide polymorphisms in the CH1 region and seven in the introns. Finally, we developed a sequence-specific PCR typing system detecting the polymorphisms in the CH1 and CH2......Here we describe a hitherto unknown proline/threonine polymorphism at residue 72 of the human IgG2 CH1 domain (EU numbering 189) and show that it is linked to the known valine/methionine polymorphism at residue 52 of CH2 (EU numbering 282) defining the G2m(n+)/G2m(n-) allotypes. We sequenced...... the entire constant region of the heavy-chain gene for secreted IgG2 in five IGHG2*02 homozygous individuals covering CH1, hinge, CH2, and CH3 regions (approximately 2 kb). Proline 72 in CH1 of G2m(n-) is changed to threonine in the G2m(n+) [G2m(23)] allotype. Based on the crystal structure of human IgG1...

  7. Synthesis and reactivity towards diiodine of palladium(II) and platinum(II) complexes with non-cyclic and cyclic ligands (C6H3{CH=NR1R2}2-2,6)-. End-on diiodine-platinum(II) bonding in macrocyclic [PtI(C6H3{CH2NMe(CH2)7MeNCH2}-2,6)(h1-I2)

    NARCIS (Netherlands)

    Koten, G. van; Beek, J.A.M. van; Dekker, G.P.C.M.; Wissing, E.; Zoutberg, M.C.; Stam, C.H.


    Several new organo-platinum(II) and -palladium(II) complexes [MX(C{6}H{3}{CH{2}NR}1{R}2{}{2}-2, 6)] (X = halide, M = Pt, Pd; R}1{ = R}2{ = Et; R}2{ = Me, R}1{ = }t{Bu, M = Pt: R}2{ = Me, R}1{ = Ph) have been synthesized from [PtCl{2}(SEt{2}){2}] or [PdCl{2}(COD)] (COD = 1, 5-cyclooctadiene) by

  8. Silylene hydride complexes of molybdenum with silicon-hydrogen interactions: neutron structure of (eta(5)-C(5)Me(5))(Me(2)PCH(2)CH(2)PMe(2))Mo(H)(SiEt(2)). (United States)

    Mork, Benjamin V; Tilley, T Don; Schultz, Arthur J; Cowan, John A


    Reduction of CpMoCl(4) with 3.1 equiv of Na/Hg amalgam (1.0% w/w) in the presence of 1 equiv of dmpe and 1 equiv of trimethylphosphine afforded the molybdenum(II) chloride complex Cp(dmpe)(PMe(3))MoCl (1) (Cp = 1,2,3,4,5-pentamethylcyclopentadienyl, dmpe = 1,2-bis(dimethylphosphino)ethane). Alkylation of 1 with PhCH(2)MgCl proceeded in high yield to liberate PMe(3) and give the 18-electron pi-benzyl complex Cp(dmpe)Mo(eta(3)-CH(2)Ph) (2). Variable temperature NMR experiments provided evidence that 2 is in equilibrium with its 16-electron eta(1)-benzyl isomer [Cp(dmpe)Mo(eta(1)-CH(2)Ph)]. This was further supported by reaction of 2 with CO to yield the carbonyl benzyl complex Cp(dmpe)(CO)Mo(eta(1)-CH(2)Ph) (3). Complex 2 was found to react with disubstituted silanes H(2)SiRR' (RR' = Me(2), Et(2), MePh, and Ph(2)) to form toluene and the silylene complexes Cp(dmpe)Mo(H)(SiRR') (4a: RR' = Me(2); 4b: RR' = Et(2); 4c: RR' = MePh; 4d: RR' = Ph(2)). Reactions of 2 with monosubstituted silanes H(3)SiR (R = Ph, Mes, Mes = 2,4,6-trimethylphenyl) produced rare examples of hydrosilylene complexes Cp(dmpe)Mo(H)Si(H)R (5a: R = Ph; 5b: R = Mes; 5c: R = CH(2)Ph). Reactivity of complexes 4a-c and 5a-d is dominated by 1,2-hydride migration from metal to silicon, and these complexes possess H.Si bonding interactions, as supported by spectroscopic and structural data. For example, the J(HSi) coupling constants in these species range in value from 30 to 48 Hz and are larger than would be expected in the absence of H.Si bonding. A neutron diffraction study on a single crystal of diethylsilylene complex 4b unequivocally determined the hydride ligand to be in a bridging position across the molybdenum-silicon bond (Mo-H 1.85(1) A, Si-H 1.68(1) A). The synthesis and reactivity properties of these complexes are described in detail.

  9. Densities, viscosities, and refractive indexes for {C2H5CO2(CH2)2CH3+C6H13OH+C6H6} at T=308.15 K

    International Nuclear Information System (INIS)

    Casas, Herminio; Garcia-Garabal, Sandra; Segade, Luisa; Cabeza, Oscar.; Franjo, Carlos; Jimenez, Eulogio


    In this work we present densities, kinematic viscosities, and refractive indexes of the ternary system {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 13 OH+C 6 H 6 } and the corresponding binary mixtures {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 6 }, {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 13 OH}, and {C 6 H 13 OH+C 6 H 6 }. All data have been measured at T=308.15 K and atmospheric pressure over the whole composition range. The excess molar volumes, dynamic viscosity deviations, and changes of the refractive index on mixing were calculated from experimental measurements. The results for binary mixtures were fitted to a polynomial relationship to estimate the coefficients and standard deviations. The Cibulka equation has been used to correlate the experimental values of ternary mixtures. Also, the experimental values obtained for the ternary mixture were used to test the empirical methods of Kohler, Jacob and Fitzner, Colinet, Tsao and Smith, Toop, Scatchard et al., and Hillert. These methods predict excess properties of the ternary mixtures from those of the involved binary mixtures. The results obtained for dynamic viscosities of the binary mixtures were used to test the semi-empirical relations of Grunberg-Nissan, McAllister, Auslaender, and Teja-Rice. Finally, the experimental refractive indexes were compared with the predicted results for the Lorentz-Lorenz, Gladstone-Dale, Wiener, Heller, and Arago-Biot equations. In all cases, we give the standard deviation between the experimental data and that calculated with the above named relations

  10. The reaction of fluorine atoms with methanol: yield of CH3O/CH2OH and rate constant of the reactions CH3O + CH3O and CH3O + HO2. (United States)

    Assaf, Emmanuel; Schoemaecker, Coralie; Vereecken, Luc; Fittschen, Christa


    Xenondifluoride, XeF2, has been photolysed in the presence of methanol, CH3OH. Two reaction pathways are possible: F + CH3OH → CH2OH + HF and F + CH3OH → CH3O + HF. Both products, CH2OH and CH3O, will be converted to HO2 in the presence of O2. The rate constants for the reaction of both radicals with O2 differ by more than 3 orders of magnitude, which allows an unequivocal distinction between the two reactions when measuring HO2 concentrations in the presence of different O2 concentrations. The following yields have then been determined from time-resolved HO2 profiles: φCH2OH = (0.497 ± 0.013) and φCH3O = (0.503 ± 0.013). Experiments under low O2 concentrations lead to reaction mixtures containing nearly equal amounts of HO2 (converted from the first reaction) and CH3O (from the second reaction). The subsequent HO2 decays are very sensitive to the rate constants of the reaction between these two radicals and the following rate constants have been obtained: k(CH3O + CH3O) = (7.0 ± 1.4) × 10-11 cm3 s-1 and k(CH3O + HO2) = (1.1 ± 0.2) × 10-10 cm3 s-1. The latter reaction has also been theoretically investigated on the CCSD(T)//M06-2X/aug-cc-pVTZ level of theory and CH3OH + O2 have been identified as the main products. Using μVTST, a virtually pressure independent rate constant of k(CH3O + HO2) = 4.7 × 10-11 cm3 s-1 has been obtained, in good agreement with the experiment.

  11. Differing reactivities of (trimpsi)M(CO)(2)(NO) complexes [M = V, Nb, Ta; trimpsi = (t)BuSi(CH(2)PMe(2))(3)] with halogens and halogen sources. (United States)

    Hayton, Trevor W; Legzdins, Peter; Patrick, Brian O


    Treatment of (trimpsi)V(CO)(2)(NO) (trimpsi = (t)BuSi(CH(2)PMe(2))(3)) with 1 equiv of PhICl(2) or C(2)Cl(6) or 2 equiv of AgCl affords (trimpsi)V(NO)Cl(2) (1) in moderate yields. Likewise, (trimpsi)V(NO)Br(2) (2) and (trimpsi)V(NO)I(2) (3) are formed by the reactions of (trimpsi)V(CO)(2)(NO) with Br(2) and I(2), respectively. The complexes (trimpsi)M(NO)I(2)(PMe(3)) (M = Nb, 4; Ta, 5) can be isolated in moderate to low yields when the (trimpsi)M(CO)(2)(NO) compounds are sequentially treated with 1 equiv of I(2) and excess PMe(3). The reaction of (trimpsi)V(CO)(2)(NO) with 2 equiv of ClNO forms 1 in low yield, but the reactions of (trimpsi)M(CO)(2)(NO) (M = Nb, Ta) with 1 equiv of ClNO generate (trimpsi)M(NO)(2)Cl (M = Nb, 6; Ta, 7). Complexes 6 and 7 are thermally unstable and decompose quickly at room temperature; consequently, they have been characterized solely by IR and (31)P[(1)H] NMR spectroscopies. All other new complexes have been fully characterized by standard methods, and the solid-state molecular structures of 1.3CH(2)Cl(2), 4.(3/4)CH(2)Cl(2), and 5.THF have been established by single-crystal X-ray diffraction analyses. A convenient method of generating Cl(15)NO has also been developed during the course of these investigations.

  12. Unveiling the non-covalent interactions of molecular homodimers by dispersion-corrected DFT calculations and collision-induced broadening of ro-vibrational transitions: application to (CH2F2)2 and (SO2)2. (United States)

    Tasinato, Nicola; Grimme, Stefan


    Thermodynamic and spectroscopic properties of molecular complexes featuring non-covalent interactions, such as van der Waals forces and hydrogen bonds, are of fundamental interest in many fields, ranging from chemistry and biology to nanotechnology. In the present work the homodimers of difluoromethane (CH2F2) and sulfur dioxide (SO2) are investigated theoretically using dispersion-corrected density functional theory (DFT-D3) and experimentally by tunable diode laser (TDL) infrared (IR) spectroscopy. The dissociation energies of (CH2F2)2 and (SO2)2 are determined experimentally from the broadening of the ro-vibrational transitions of the corresponding monomers collisionally perturbed by a range of damping gases. The resulting dissociation energies are 2.79 ± 0.32 and 2.62 ± 0.16 kcal mol(-1) for the CH2F2 and SO2 dimers, respectively. Six to nine different stationary points on the PES of the two complexes are investigated theoretically at the DFT-D3 level, retrieving the corresponding dissociation energies, structures and rotational constants. Computations are carried out by employing six different density functionals (BLYP, TPSS, B3LYP, PBE0, TPSSh, and PW6B95) in conjunction with def2-TZVP and in a few cases def2-QZVP basis sets. DFT-D3 dissociation energies are benchmarked against reference values from CCSD(T)/CBS computations, and furthermore compared to experimental ones. A very good agreement between theory and experiment is attained, showing that DFT-D3 provides a significant improvement over standard DFT. This work shows that dissociation energies of homodimers can be consistently derived from collisional broadening cross sections and that interaction energies at various DFT-D3 levels (nearly) reach the accuracy of highly correlated wavefunction methods.

  13. The Deceptively Simple Thermolysis of Trivalent Permethyltitanocene Derivatives (η5-C5Me5)2TiR. Formation of a Tetramethylfulvene Titanium Compound (η6-C5Me4CH2)(η5-C5Me5)Ti and RH, Catalyzed by Permethyltitanocene Hydride, (η5-C5Me5)2TiH

    NARCIS (Netherlands)

    Luinstra, Gerrit A.; Teuben, Jan H.


    The complexes Cp*2TiR (Cp* = η5-C5Me5; R = Me, Et, n-Pr, C2H3, CH2CMe3, Ph) undergo thermolysis to yield the fulvene complex Cp*FvTi (Fv = η6-C5Me4CH2) and RH. Kinetic measurements and deuterium labeling studies show that the decomposition is catalyzed by Cp*2TiH, which is formed either by


    NARCIS (Netherlands)



    The complexes Cp*2TiR (Cp* = eta-5-C5Me5; R = Me, Et, n-Pr, C2H3, CH2CMe3, Ph) undergo thermolysis to yield the fulvene complex Cp*FvTi (Fv = eta-6-C5Me4CH2) and RH. Kinetic measurements and deuterium labeling studies show that the decomposition is catalyzed by Cp*2TiH, which is formed either by

  15. Low-Temperature Photoelectron Spectroscopy of Aliphatic Dicarboxylate Monoanions, HO2C(CH2)nCO2-(n=1-10): Hydrogen Bond Induced Cyclization and Strain Energies

    Energy Technology Data Exchange (ETDEWEB)

    Woo, Hin-koon; Wang, Xue B.; Lau, Kai Chung; Wang, Lai S.


    Photoelectron spectra of singly-charged dicarboxylate anions HO2C(CH2)nCO2 - (n = 1 – 10) are obtained at two different temperatures (300 and 70 K) at 193 nm. The electron binding energies of these species are observed to be much higher than the singly-charged monocarboxylate anions, suggesting the singly-charged dicarboxylate anions are cyclic due to strong intramolecular hydrogen bonding between the terminal –CO2H and –CO2 - groups. The measured electron binding energies are observed to depend on the chain length, reflecting the different –CO2H…-O2C– hydrogen bonding strength as a result of strain in the cyclic conformation. A minimum binding energy is found at n = 5, indicating that its intramolecular hydrogen bond is the weakest. At 70 K, all spectra are blue-shifted relative to the room temperature spectra with the maximum binding energy shift occurring at n = 5. These observations suggest that the cyclic conformation of HO2C(CH2)5CO2 - (a ten-membered ring) is the most strained among the ten anions. The present study shows that the –CO2H…-O2C– hydrogen bonding strength is different among the ten anions and it is very sensitive to the strain in the cyclic conformations.

  16. Relative rate study of the kinetics, mechanism, and thermodynamics of the reaction of chlorine atoms with CF3CF═CH2 (HFO-1234yf) in 650-950 Torr of N2 or N2/O2 diluent at 296-462 K. (United States)

    Kaiser, E W; Wallington, T J


    The rate constant of the reaction Cl + CF(3)CF═CH(2) (k(1)) has been measured relative to several reference species using the relative rate technique with either gas chromatographic analysis with flame-ionization detection (GC/FID) or Fourier transform infrared (FTIR) analysis. Cl atoms were generated by UV irradiation of Cl(2)/CF(3)CF═CH(2)/reference/N(2)/O(2) mixtures. At 300-400 K in the presence of >20 Torr O(2), k(1) = 1.2 × 10(-11) e((+1100/RT)) cm(3) molecule(-1) s(-1). In N(2) diluent, k(1) has a sharp negative temperature coefficient resulting from the relatively small exothermicity of the following reactions: (1a) Cl + CF(3)CF═CH(2) ↔ CF(3)CFClCH(2)(•); (1b) Cl + CF(3)CF═CH(2) ↔ CF(3)CF(•)CH(2)Cl (reaction 1), which were determined in these experiments to be ∼16.5 (±2.0) kcal mol(-1). This low exothermicity causes reaction 1 to become significantly reversible even at ambient temperature. The rate constant ratio for the reaction of the chloroalkyl radicals formed in reaction 1 with Cl(2) (k(2)) or O(2) (k(3)) was measured to be k(2)/k(3) = 0.4 e(-(3000/RT)) for 300-400 K. At 300 K, k(2)/k(3) = 0.0026. The reversibility of reaction 1 combined with the small value of k(2)/k(3) leads to a sensitive dependence of k(1) on the O(2) concentration. Products measured by GC/FID as a function of temperature are CF(3)CFClCH(2)Cl, CF(3)COF, and CH(2)Cl(2). The mechanism leading to these products is discussed. The rate constant for the reaction Cl + CF(3)CFClCH(2)Cl (k(11)) was measured as a function of temperature (300-462 K) at 760 Torr to be k(11) = 8.2 × 10(-12) e(-(4065/RT)) cm(3) molecule(-1) s(-1). Rate constants relative to CH(4) for the reactions of Cl with the reference compounds CH(3)Cl, CH(2)Cl(2), and CHCl(3) were measured at 470 K to resolve a literature discrepancy. (R = 1.986 cal K(-1) mol(-1)).

  17. Formation of CH3TiX, CH2=TiHX, and (CH3)2TiX2 by reaction of methyl chloride and bromide with laser-ablated titanium atoms: photoreversible alpha-hydrogen migration. (United States)

    Cho, Han-Gook; Andrews, Lester


    The simple methylidene (CH2=TiHX) and Grignard-type (CH3TiX) complexes are produced by reaction of methyl chloride and bromide with laser-ablated Ti atoms and isolated in a solid Ar matrix, and they form a persistent photoreversible system via alpha-hydrogen migration between the carbon and titanium atoms. The Grignard-type product is transformed to the methylidene complex upon UV (240 nm lambda lambda > 530 nm) irradiation. More stable dimethyl dihalide complexes [(CH3)2TiX2] are also identified, whose relative concentration increases upon annealing and at high methyl halide concentration. The reaction products are identified with three different groups of absorptions on the basis of the behaviors upon broadband photolysis and annealing, and the vibrational characteristics are in a good agreement with DFT computation results.

  18. An ab initio/Rice-Ramsperger-Kassel-Marcus prediction of rate constant and product branching ratios for unimolecular decomposition of propen-2-ol and related H+CH2COHCH2 reaction (United States)

    Zhou, Chong-Wen; Li, Ze-Rong; Liu, Cun-Xi; Li, Xiang-Yuan


    Enols have been found to be important intermediates in the combustion flames of hydrocarbon [C. A. Taatjes et al., Science 308, 1887 (2005)]. The removal mechanism of enols in combustion flame has not been established yet. In this work, the potential energy surface for the unimolecular decomposition of syn-propen-2-ol and H+CH2COHCH2 recombination reactions have been first investigated by CCSD(T) method. The barrier heights, reaction energies, and geometrical parameters of the reactants, products, intermediates, and transition states have been investigated theoretically. The results show that the formation of CH3CO+CH3 via the CH3COCH3 intermediate is dominant for the unimolecular decomposition of syn-propen-2-ol and its branching ratio is over 99% in the whole temperature range from 700 to 3000 K, and its rate constant can be expressed as an analytical form in the range of T =700-3000 K at atmospheric pressure. This can be attributed to the lower energy barrier of this channel compared to the other channels. The association reaction of H with CH2COHCH2 is shown to be a little more complicated than the unimolecular decomposition of syn-propen-2-ol. The channel leading to CH3CO+CH3 takes a key role in the whole temperature range at atmospheric pressure. However at the higher pressure of 100 atm, the recombination by direct formation of syn-propen-2-ol through H addition is important at T 1400 K, the recombination channel leading to CH3CO+CH3 turns out to be significant.

  19. Skeleton polyhedral rearrangements of 8-alkyl-7,9-dicarba-nido-undecaborate(-1) anion to 11-alkyl-2,7-dicarba-nido-undecaborane(13) and to 9-alkyl-7,8-dicarba-nido-undecaborate(-1) anion. Molecular structure of 2,7-Me2-11-PhCH2-2,7-C2B9H10

    International Nuclear Information System (INIS)

    Zakharkin, K.I.; Zhigareva, G.G.; Antonovich, V.A.; Yanovskij, A.I.; Struchkov, Yu.T.


    Using the methods of 1 H and 11 B NMR-spectroscopy and X-ray diffraction analysis skeleton polyhedral rearrangements of carboranes are studied. During protonation of anion 8-R-7, 9-R' 2 -7, 9-C 2 B 9 H 9 - the skeleton polyhedral rearrangement in the series of nido-carboranes, resulting in 2,7-R' 2 -11-R-2, 7-C 2 B 9 H 10 (R=Me, PhCH 2 , R'=H, Me) is observed. The rearrangement is reversible. On the detachment of two protons from 2,7-Me 2 -11-PhCH 2 -2,7-C 2 B 9 H 10 and during subsequent protonation the skeleton polyhedral rearrangement with the formation of anion 9-PhCH 2 -7,8-Me 2 -7,8-C 2 B 9 H 9 - takes place

  20. Crystal structure of an ethylene sorption complex of fully vacuum-dehydrated fully Ag+-exchanged zeolite X (FAU). Silver atoms have reduced ethylene to give CH2 2- carbanions at framework oxide vacancies. (United States)

    Lee, Young Mi; Choi, Seo Jung; Kim, Yang; Seff, Karl


    of the 384 framework oxide ions were oxidized to O2(g), leaving lattice vacancies. The sorption of C(2)H(4) at 21 degrees C reoxidized about 7 of the 30 Ag(0) atoms to Ag(+) and reduced 1.75 ethylene molecules to give CH(2)(2-) groups which refilled 3.5 of these 15 lattice vacancies. The remaining vacancies may have been filled with H(2)C=C(2-) ions. The unit cell formula, which originally contained 384 oxygen atoms, may be |Ag(92)(C2H4)17|[Si(100)Al(92)O(369)(CH2)3.5] or |Ag(92)H(23)(C2H4)17|[Si(100)Al(92)O(369)(CH2)3.5(C2H2)11.5].

  1. Effects of the [OC6F5] moiety upon structural geometry: crystal structures of half-sandwich tantalum(V) aryloxide complexes from reaction of Cp*Ta(N(t)Bu)(CH2R)2 with pentafluorophenol. (United States)

    Cole, Jacqueline M; Chan, Michael C W; Gibson, Vernon C; Howard, Judith A K


    The synthesis, chemical and structural characterization of a series of pentamethylcyclopentadienyl (Cp*) tantalum imido complexes and aryloxide derivatives are presented. Specifically, the imido complexes Cp*Ta(N(t)Bu)(CH(2)R)(2), where R = Ph [dibenzyl(tert-butylamido) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (1)], Me(2)Ph [tert-butylamido)bis(2-methyl-2-phenylpropyl) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (2)], CMe(3) [(tert-butylamido)bis(2,2-dimethylpropyl) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (3)], are reported. The crystal structure of (3) reveals α-agostic interactions with the Ta atom. The resulting increase in the tantalum core coordination improves electronic stability. As such it does not react with pentafluorophenol, in contrast to the other two reported imido complexes [(1) and (2)]. Addition of C(6)F(5)OH to (1) yields a dimeric aryl-oxide derivative, [Cp*Ta(CH(2)Ph)(OC(6)H(5))(μ-O)](2) [di-μ-oxido-bis[benzyl(pentafluorophenolato) (η(5)-pentamethylcyclopentadienyl)tantalum(V)] (4)]. Its crystal structure reveals long Ta-O(C(6)H(5)) bonds but short oxo-bridging Ta-O bonds. This is explained by accounting for the fierce electronic competition for the vacant d(π) orbitals of the electrophilic Ta(V) centre. Steric congestion around each metal is alleviated by a large twist angle (77.1°) between the benzyl and pentafluorophenyl ligands and the ordering of each of these groups into stacked pairs. The imido complex (2) reacts with C(6)F(5)OH to produce a mixture of Cp*Ta(OC(6)F(5))(4) [tetrakis(pentafluorophenolato)(η(5)-pentamethylcyclopentadienyl)tantalum(V) (5)] and [Cp*Ta(OC(6)F(5))(2)(μ-O)](2) [di-μ-oxido-bis[bis(pentafluorophenolato)(η(5)-pentamethylcyclopentadienyl)tantalum(V)] (6)]. Steric congestion is offset in both cases by the twisting of its pentafluorophenyl ligands. Particularly strong electronic competition for the empty d(π) metal orbitals in (6) is reflected in its bond geometry, and owes itself to the

  2. Base free N-alkylation of anilines with ArCH2OH and transfer hydrogenation of aldehydes/ketones catalyzed by the complexes of η5-Cp*Ir(iii) with chalcogenated Schiff bases of anthracene-9-carbaldehyde. (United States)

    Dubey, Pooja; Gupta, Sonu; Singh, Ajai K


    The condensation of anthracene-9-carbaldehyde with 2-(phenylthio/seleno)ethylamine results in Schiff bases [PhS(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ](L1) and [PhSe(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ] (L2). On their reaction with [(η 5 -Cp*)IrCl(μ-Cl)] 2 and CH 3 COONa at 50 °C followed by treatment with NH 4 PF 6 , iridacycles, [(η 5 -Cp*)Ir(L-H)][PF 6 ] (1: L = L1; 2: L = L2), result. The same reaction in the absence of CH 3 COONa gives complexes [(η 5 -Cp*)Ir(L)Cl][PF 6 ] (3-4) in which L = L1(3)/L2(4) ligates in a bidentate mode. The ligands and complexes were authenticated with HR-MS and NMR spectra [ 1 H, 13 C{ 1 H} and 77 Se{ 1 H} (in the case of L2 and its complexes only)]. Single crystal structures of L2 and half sandwich complexes 1-4 were established with X-ray crystallography. Three coordination sites of Ir in each complex are covered with η 5 -Cp* and on the remaining three, donor atoms present are: N, S/Se and C - /Cl - , resulting in a piano-stool structure. The moisture and air insensitive 1-4 act as efficient catalysts under mild conditions for base free N-alkylation of amines with benzyl alcohols and transfer hydrogenation (TH) of aldehydes/ketones. The optimum loading of 1-4 as a catalyst is 0.1-0.5 mol% for both the activations. The best reaction temperature is 80 °C for transfer hydrogenation and 100 °C for N-alkylation. The mercury poisoning test supports a homogeneous pathway for both the reactions catalyzed by 1-4. The two catalytic processes are most efficient with 3 followed by 4 > 1 > 2. The mechanism proposed on the basis of HR-MS of the reaction mixtures of the two catalytic processes taken after 1-2 h involves the formation of an alkoxy and hydrido species. The real catalytic species proposed in the case of iridacycles results due to the loss of the Cp* ring.

  3. Threshold photoelectron spectroscopy of the methyl radical isotopomers, CH3, CH2D, CHD2 and CD3: synergy between VUV synchrotron radiation experiments and explicitly correlated coupled cluster calculations. (United States)

    Cunha de Miranda, Bárbara K; Alcaraz, Christian; Elhanine, Mohamed; Noller, Bastian; Hemberger, Patrick; Fischer, Ingo; Garcia, Gustavo A; Soldi-Lose, Héloïse; Gans, Bérenger; Mendes, Luiz A Vieira; Boyé-Péronne, Séverine; Douin, Stéphane; Zabka, Jan; Botschwina, Peter


    Threshold photoelectron spectra (TPES) of the isotopomers of the methyl radical (CH(3), CH(2)D, CHD(2), and CD(3)) have been recorded in the 9.5-10.5 eV VUV photon energy range using third generation synchrotron radiation to investigate the vibrational spectroscopy of the corresponding cations at a 7-11 meV resolution. A threshold photoelectron-photoion coincidence (TPEPICO) spectrometer based on velocity map imaging and Wiley-McLaren time-of-flight has been used to simultaneously record the TPES of several radical species produced in a Ar-seeded beam by dc flash-pyrolysis of nitromethane (CH(x)D(y)NO(2), x + y = 3). Vibrational bands belonging to the symmetric stretching and out-of-plane bending modes have been observed and P, Q, and R branches have been identified in the analysis of the rotational profiles. Vibrational configuration interaction (VCI), in conjunction with near-equilibrium potential energy surfaces calculated by the explicitly correlated coupled cluster method CCSD(T*)-F12a, is used to calculate vibrational frequencies for the four radical isotopomers and the corresponding cations. Agreement with data from high-resolution IR spectroscopy is very good and a large number of predictions is made. In particular, the calculated wavenumbers for the out-of-plane bending vibrations, nu(2)(CH(3)(+)) = 1404 cm(-1), nu(4)(CH(2)D(+)) = 1308 cm(-1), nu(4)(CHD(2)(+)) = 1205 cm(-1), and nu(2)(CD(3)(+)) = 1090 cm(-1), should be accurate to ca. 2 cm(-1). Additionally, computed Franck-Condon factors are used to estimate the importance of autoionization relative to direct ionization. The chosen models globally account for the observed transitions, but in contrast to PES spectroscopy, evidence for rotational and vibrational autoionization is found. It is shown that state-selected methyl cations can be produced by TPEPICO spectroscopy for ion-molecule reaction studies, which are very important for the understanding of the planetary ionosphere chemistry.

  4. Decision making about nuclear energy, ch. 2

    International Nuclear Information System (INIS)

    Kramer, R.


    A survey is given of the various influences on the process of making decisions at the governmental level in the Netherlands on nuclear power, covering the last 20 years. The conflicting statements in memoranda, the role of the industry, the lack of public information and the coloured information generated by different ministries as an answer to extra-parliamentary opposition to nuclear power, are in turn put into focus

  5. Formation of doubly and triply bonded unsaturated compounds HCN, HNC and CH2NH via N + CH4 low temperature solid state reaction: from molecular clouds to solar system objects (United States)

    Mencos, Alejandro; Krim, Lahouari


    We show in the current study carried out in solid phase at cryogenic temperatures, that methane (CH4) ice exposed to nitrogen atoms is a source of two acids HCN, HNC and their corresponding hydrogenated unsaturated species CH2NH, in addition to CH3, C2H6, CN- and three nitrogen hydrides NH, NH2 and NH3. The solid state N + CH4 reaction taken in the ground state seems to be strongly temperature dependent. While at temperatures lower than 10 K only CH3, NH, NH2 and NH3 species formation is promoted due to CH bond dissociation and NH bond formation, stable compounds with CN bonds are formed at temperatures ranged between 10 and 40 K. Many of these reaction products, resulting from CH4 + N reaction, have already been observed in N2-rich regions such as the atmospheres of Titan, Kuiper belt objects and molecular clouds of the interstellar medium. Our results show the power of the solid state N-atom chemistry in the transformation of simple astrochemical relevant species such as CH4 molecules and N atoms into complex organic molecules which are also potentially prebiotic species.

  6. Theoretical kinetics study of the reactions CHClBr + HBr ⇄ CH2ClBr + Br, CCl2Br + HBr ⇄ CHCl2Br + Br and CClBr2 + HBr ⇄ CHClBr2 + Br (United States)

    Bracco, Larisa L. B.; Tucceri, María E.; Cobos, Carlos J.


    The kinetics of CHClBr + HBr ⇄ CH2ClBr + Br (1, -1), CCl2Br + HBr ⇄ CHCl2Br + Br (2, -2) and CClBr2 + HBr ⇄ CHClBr2 + Br (3, -3) reactions at 293-787 K has been studied by using the canonical transition state theory with molecular information provided by different quantum chemical methods. The obtained rate constants (in cm3 molecule-1 s-1) are k1 = 5.24 × 10-13 exp[-1.47 kcal mol-1/RT], k-1 = 2.70 × 10-11 exp[-10.21 kcal mol-1/RT], k2 = 4.18 × 10-13 exp[-2.49 kcal mol-1/RT], k-2 = 6.96 × 10-12 exp[-7.36 kcal mol-1/RT], k3 = 3.29 × 10-13 exp[-2.20 kcal mol-1/RT], and k-3 = 8.45 × 10-13 exp[-7.10 kcal mol-1/RT]. Rate constants for (2, -2) and (3, -3) are here reported for the first time.

  7. The influence of the relative thermal expansion and electric permittivity on phase transitions in the perovskite-type bidimensional layered NH3(CH2)3NH3CdBr4 compound (United States)

    Staśkiewicz, Beata; Staśkiewicz, Anna


    Hydrothermal method has been used to synthesized the layered hybrid compound NH3(CH2)3NH3CdBr4 of perovskite architecture. Structural, dielectric and dilatometric properties of the compound have been analyzed. Negative thermal expansion (NTE) effect in the direction perpendicular to the perovskite plane as well as an unusual phase sequence have been reported based on X-ray diffraction analysis. Electric permittivity measurements evidenced the phase transitions at Tc1=326/328 K and Tc2=368/369 K. Relative linear expansion measurements almost confirmed these temperatures of phase transitions. Anomalies of electric permittivity and expansion behavior connected with the phase transitions are detected at practically the same temperatures as those observed earlier in differential scanning calorimetry (DSC), infrared (IR), far infrared (FIR) and Raman spectroscopy studies. Mechanism of the phase transitions is explained. Relative linear expansion study was prototype to estimate critical exponent value β for continuous phase transition at Tc1. It has been inferred that there is a strong interplay between the distortion of the inorganic network, those hydrogen bonds and the intermolecular interactions of the organic component.

  8. The (CH2)2O-H2O hydrogen bonded complex. Ab Initio calculations and Fourier transform infrared spectroscopy from neon matrix and a new supersonic jet experiment coupled to the infrared AILES beamline of synchrotron SOLEIL. (United States)

    Cirtog, M; Asselin, P; Soulard, P; Tremblay, B; Madebène, B; Alikhani, M E; Georges, R; Moudens, A; Goubet, M; Huet, T R; Pirali, O; Roy, P


    A series of hydrogen bonded complexes involving oxirane and water molecules have been studied. In this paper we report on the vibrational study of the oxirane-water complex (CH(2))(2)O-H(2)O. Neon matrix experiments and ab initio anharmonic vibrational calculations have been performed, providing a consistent set of vibrational frequencies and anharmonic coupling constants. The implementation of a new large flow supersonic jet coupled to the Bruker IFS 125 HR spectrometer at the infrared AILES beamline of the French synchrotron SOLEIL (Jet-AILES) enabled us to record first jet-cooled Fourier transform infrared spectra of oxirane-water complexes at different resolutions down to 0.2 cm(-1). Rovibrational parameters and a lower bound of the predissociation lifetime of 25 ps for the v(OH)(b) = 1 state have been derived from the rovibrational analysis of the ν(OH)(b) band contour recorded at respective rotational temperatures of 12 K (Jet-AILES) and 35 K (LADIR jet).

  9. Rational design of organic superconductors through the use of the large, discrete molecular anions M(CF3)4-(M = Cu, Ag, Au) and SO3CF2CH2SF5-

    International Nuclear Information System (INIS)

    Schlueter, J.A.; Geiser, U.; Williams, J.M.


    A new approach to synthesis of organic superconductors has recently been pioneered which involves the use of large discrete molecular anions as the charge-compensating entities in these charge transfer salts. The organic electron-donor molecule bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) has been electrocrystallized with the novel organometallic M(CF 3 ) 4 - (M=Cu, Ag, Au) anions in a variety of 1,1,2-trihaloethane solvents. Over 20 organic superconductors have been synthesized which can be described by (ET) 2 M(CF 3 ) 4 (1,1,2- trihaloethane). These solvated salts are shown to have highly anisotropic physical properties which can be tuned via modifications of each of their three molecular components: ET electron donor molecule, M(CF 3 ) 4 - anion, and neutral 1,1,2- trihaloethane solvent molecule. Superconductivity has also been observed in an ET salt containing the discrete SF 5 CH 2 CF 2 SO 3 - anion with onset temperature near 5.2 K

  10. Synthesis, characterization, and reactivity of nickel hydride complexes containing 2,6-C6H3(CH2PR2)2 (R = tBu, cHex, and iPr) pincer ligands. (United States)

    Boro, Brian J; Duesler, Eileen N; Goldberg, Karen I; Kemp, Richard A


    The syntheses and full characterization of nickel hydrides containing the PCP "pincer"-type ligand, where PCP = 2,6-C(6)H(3)(CH(2)PR(2))(2) (R = tBu, cHex, and iPr), are reported. These Ni-H complexes are prepared by the conversion of ((R)PCP)NiCl precursors into the corresponding nickel hydrides by use of appropriate hydride donors. Surprisingly, although the ((R)PCP)NiCl precursors are quite similar chemically, the conversions to the hydrides were not straightforward and required different hydride reagents to provide analytically pure products. While NaBH(4) was effective in the preparation of pure ((tBu)PCP)NiH, Super-Hydride solution (LiEt(3)BH in THF) was required to prepare either ((cHex)PCP)NiH or ((iPr)PCP)NiH. Attempts to prepare a Ni-H from ((Ph)PCP)NiCl with a variety of hydride reagents yielded only the free ligand as an identifiable product. Two of the derivatives, tBu and cHex, have also been subjected to single crystal X-ray analysis. The solid-state structures each showed a classic, near-square planar arrangement for Ni in which the PCP ligand occupied three meridional ligand points with the Ni-H trans to the Ni-C bond. The resulting Ni-H bond lengths were 1.42(3) and 1.55(2) A for the tBu and cHex derivatives, respectively.

  11. [H3N(CH2)4NH3]2[Al4(C2O4)(H2PO4)2(PO4)4].4[H2O]: A new layered aluminum phosphate-oxalate

    International Nuclear Information System (INIS)

    Peng Li; Li Jiyang; Yu Jihong; Li Guanghua; Fang Qianrong; Xu Ruren


    A new layered inorganic-organic hybrid aluminum phosphate-oxalate [H 3 N(CH 2 ) 4 NH 3 ] 2 [Al 4 (C 2 O 4 )(H 2 PO 4 ) 2 (PO 4 ) 4 ].4[H 2 O](AlPO-CJ25) has been synthesized hydrothermally, by using 1,4-diaminobutane (DAB) as structure-directing agent. The structure has been solved by single-crystal X-ray diffraction analysis and further characterized by IR, 31 P MAS NMR, TG-DTA as well as compositional analyses. Crystal data: the triclinic space group P-1, a=8.0484(7) A, b=8.8608(8) A, c=13.2224(11) A, α=80.830(6) deg. , β=74.965(5) deg. , γ=78.782(6) deg. , Z=2, R 1[ I >2 σ ( I )] =0.0511 and wR 2(alldata) =0.1423. The alternation of AlO 4 tetrahedra and PO 4 tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO 6 octahedra to form the layered structure with 4,6-net sheet. Interestingly, oxalate ions are bis-bidentately bonded by participating in the coordination of AlO 6 , and bridging the adjacent AlO 6 octahedra. The layers are held with each other through strong H-bondings between the terminal oxygens. The organic ammonium cations and water molecules are located in the large cavities between the interlayer regions. -- Graphical abstract: The alternation of AlO 4 tetrahedra and PO 4 tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO 6 octahedra to form the layered structure with 4,6-net sheet. Oxalate ions are bis-bidentately boned by participating in the coordination of AlO 6 , and bridging the adjacent AlO 6 octahedra

  12. Comparison of the effects of [Phe1Ψ(CH2-NH)Gly2]Nociceptin (1-13)NH2 in rat brain, rat vas deferens and CHO cells expressing recombinant human nociceptin receptors (United States)

    Okawa, Hirobumi; Nicol, Beverley; Bigoni, Raffaella; Hirst, Robert A; Calo', Girolamo; Guerrini, Remo; Rowbotham, David J; Smart, Darren; McKnight, Alexander T; Lambert, David G


    Nociceptin(NC) is the endogenous ligand for the opioid receptor like-1 receptor (NC-receptor). [Phe1ΨC(CH2-NH)Gly2]Nociceptin(1-13)NH2 ([F/G]NC(1-13)NH2) has been reported to antagonize NC actions in peripheral guinea-pig and mouse tissues. In this study, we investigated the effects of a range of NC C-terminal truncated fragments and [F/G]NC(1-13)NH2 on NC receptor binding, glutamate release from rat cerebrocortical slices (rCX), inhibition of cyclic AMP accumulation in CHO cells expressing the NC receptor (CHONCR) and electrically evoked contractions of the rat vas deferens (rVD).In radioligand binding assays, a range of ligands inhibited [125I]-Tyr14-NC binding in membranes from rCX and CHONCR cells. As the peptide was truncated there was a general decline in pKi. [F/G]NC(1-13)NH2 was as potent as NC(1-13)NH2.The order of potency for NC fragments to inhibit cyclic AMP accumulation in whole CHONCR cells was NCNH2⩾NC=NC(1-13)NH2>NC(1-12)NH2>>NC(1-11)NH2. [F/G]NC(1-13)NH2 was a full agonist with a pEC50 value of 8.65.NCNH2 and [F/G]NC(1-13)NH2 both inhibited K+ evoked glutamate release from rCX with pEC50 and maximum inhibition of 8.16, 48.5±4.9% and 7.39, 58.9±6.8% respectively.In rVD NC inhibited electrically evoked contractions with a pEC50 of 6.63. Although [F/G]NC(1-13)NH2, displayed a small (instrinsic activity α=0.19) but consistent residual agonist activity, it acted as a competitive antagonist (pA2 6.76) in the rVD.The differences between [F/G]NC(1-13)NH2 action on central and peripheral NC signalling could be explained if [F/G]NC(1-13)NH2 was a partial agonist with high strength of coupling in the CNS and low in the periphery. An alternative explanation could be the existence of central and peripheral receptor isoforms. PMID:10369464

  13. The Third Dimension of a More O'Ferrall-Jencks Diagram for Hydrogen Atom Transfer in the Isoelectronic Hydrogen Exchange Reactions of (PhX)(2)H(•) with X = O, NH, and CH(2). (United States)

    Cembran, Alessandro; Provorse, Makenzie R; Wang, Changwei; Wu, Wei; Gao, Jiali


    A critical element in theoretical characterization of the mechanism of proton-coupled electron transfer (PCET) reactions, including hydrogen atom transfer (HAT), is the formulation of the electron and proton localized diabatic states, based on which a More O'Ferrall-Jencks diagram can be represented to determine the step-wise and concerted nature of the reaction. Although the More O'Ferrall-Jencks diabatic states have often been used empirically to develop theoretical models for PCET reactions, the potential energy surfaces for these states have never been determined directly based on first principles calculations using electronic structure theory. The difficulty is due to a lack of practical method to constrain electron and proton localized diabatic states in wave function or density functional theory calculations. Employing a multistate density functional theory (MSDFT), in which the electron and proton localized diabatic configurations are constructed through block-localization of Kohn-Sham orbitals, we show that distinction between concerted proton-electron transfer (CPET) and HAT, which are not distinguishable experimentally from phenomenological kinetic data, can be made by examining the third dimension of a More O'Ferrall-Jencks diagram that includes both the ground and excited state potential surfaces. In addition, we formulate a pair of effective two-state valence bond models to represent the CPET and HAT mechanisms. We found that the lower energy of the CPET and HAT effective diabatic states at the intersection point can be used as an energetic criterion to distinguish the two mechanisms. In the isoelectronic series of hydrogen exchange reaction in (PhX)(2)H(•), where X = O, NH, and CH(2), there is a continuous transition from a CPET mechanism for the phenoxy radical-phenol pair to a HAT process for benzyl radical and toluene, while the reaction between PhNH(2) and PhNH(•) has a mechanism intermediate of CPET and HAT. The electronically nonadiabatic

  14. Synthesis of binuclear rhodacarboranes from dianions 1,4- and 1,3-C6H4(CH2-9-C2H2B9H9-7,8-nido)22- and (Ph3P)3RhCl

    International Nuclear Information System (INIS)

    Zakharkin, L.I.; Zhigareva, G.G.


    Dianions 1,4 and 1,3-C 6 H 4 (CH 2 -9-C 2 H 2 B 9 H 9 -7,8-nido) 2 2- obtained from nido 7,8-dicarbollide-ion and 1,4-bis(bromomethyl) and 1,3-bis(bromomethyl)benzenes react with (Ph 3 P) 3 RhCl to give binuclear rhodacarboranes, 1,4- and 1,3-[3,3-(Ph 3 P) 2 -3-H-3,1,2-RhC 2 B 9 H 10 -4-CH 2 ] 2 C 6 H 6 with chemical reaction yield 85% and 87% respectively. 7 refs., 1 fig., 1 tab

  15. Formation of closo-rhodacarboranes with the η2,η3-(CH2=CHC5H6) ligand in the reaction of μ-dichloro-bis[(η4-norbornadiene)rhodium] with nido-dicarbaundecaborates [K][nido-7-R1-8-R2-7,8-C2B9H10

    International Nuclear Information System (INIS)

    Safronov, A.V.; Sokolova, M.N.; Vorontsov, E.V.; Petrovskij, P.V.; Barakovskaya, I.G.; Chizhevskij, I.T.


    New closo-(η 2 ,η 3 -(4-vinylcyclopentene-3-yl)rhodacarboranes were prepared by reaction of the complex [(η 4 -C 7 H 8 )RhCl] 2 (C 7 H 8 -norbornadiene) with salts of substituted nido-dicarbaundecaborates [K][nido-7-R 1 -8-R 2 -7,8-C 2 B 9 H 10 ] (R 1 =R 2 =H (a); R = R 2 =Me (b); R 1 , R 2 =1',2'-(CH 2 ) 2 C 6 H 4 (c); R 1 =Me, R 2 =Ph (d) in CH 2 Cl 2 . The structure of the compounds prepared in solution was studied by the method of multinuclear NMR spectroscopy. A probable mechanism of the norbornadiene ligand regrouping was suggested [ru

  16. Insertion and C-H bond activation of unsaturated substrates by bis(benzamidinato)yttrium alkyl, [PhC(NSiMe(3))(2)](2)YR (R=CH(2)Ph center dot THF,CH(SiMe(3))(2)), and hydride, {[PhC(NSiMe(3))(2)]Y-2(mu-H)}(2), compounds

    NARCIS (Netherlands)

    Duchateau, R; vanWee, CT; Teuben, JH


    The reactivity of benzamidinate-stabilized yttrium complexes [PhC(NSiMe(3))(2)](2)YR (R = CH(2)Ph . THF, CH(SiMe(3))(2) and {[PhC(NSiMe(3))(2)]Y-2(mu-H)}(2) have been investigated. The complexes are thermally stable showing no sign of decomposition, ligand or solvent metalation or H/D exchange after

  17. Reaction of (CP(2)asterisk-lnH)(2) (ln=Y, La) and CP(2)asterisk-Y(2-C(6)H(4)CH(2)NMe(2)) with esters and amides and molecular-structure of [CP(2)asterisk-Y(mu- ocme=chc(oet)o)](2)

    NARCIS (Netherlands)

    Deelman, B.J; Wierda, F.; Meetsma, A.; Teuben, J.H


    The activation of esters and amides by (Cp(2)*LnH)(2) [Ln = Y (1a), Ln = La (1b), Cp*=C(5)Me] and Cp(2)*Y(2-C(6)H(4)CH(2)NMe(2)) (2) is described. Compounds 1a and 1b react with ethyl acetate to form Cp(2)*YOEt (3a) and Cp(2)*LaOEt (30). With 1a and ethyl benzoate a 1:1 mixture of 3a and

  18. Fast water exchange on a Pt(II) center: variable temperature and pressure 17O NMR study at 14.1 tesla of the ionic arylplatinum species [Pt{C6H3(CH2NMe2)2-2,6}(OH2)]+(OSO2CF3)

    NARCIS (Netherlands)

    Koten, G. van; Frey, U.; Grove, D.M.


    The water-soluble ionic aryl platinum species [Pt{C{6}H{3}(CH{2}NMe{2})-2, 6} (OH{2})]}+{ undergoes water exchange at a rate 10}7{ times faster than the coordination complex [Pt(OH{2}){4}]}2{}+{; a clear-cut example of the trans effect of the C-bonded organic group. Lineshape analysis of high

  19. Insertion and C-H Bond Activation of Unsaturated Substrates by Bis(benzamidinato)yttrium Alkyl, [PhC(NSiMe3)2]2YR (R = CH2Ph·THF, CH(SiMe3)2), and Hydrido, {[PhC(NSiMe3)2]2Y(μ-H)}2, Compounds

    NARCIS (Netherlands)

    Duchateau, Robbert; Wee, Cornelis T. van; Teuben, Jan H.


    The reactivity of benzamidinate-stabilized yttrium complexes [PhC(NSiMe3)2]2YR (R = CH2Ph·THF, CH(SiMe3)2) and {[PhC(NSiMe3)2]2Y(μ-H)}2 has been investigated. The complexes are thermally stable showing no sign of decomposition, ligand or solvent metalation, or H/D exchange after hours at 100 °C in

  20. Photochemical Properties of CH2═CH-CFCl-CF2Br (4-Bromo-3-chloro-3,4,4-trifluoro-1-butene) and CH3-O-CH(CF3)2(Methyl Hexafluoroisopropyl Ether): OH Reaction Rate Constants and UV and IR Absorption Spectra. (United States)

    Orkin, Vladimir L; Martynova, Larissa E; Kurylo, Michael J


    Rate constants for the reactions of hydroxyl radicals (OH) with 1,1,1,3,3,3-hexafluoroisopropyl methyl ether (CH 3 -O-CH(CF 3 ) 2 ) and 4-bromo-3-chloro-3,4,4-trifluoro-1-butene (CH 2 ═CH-CFCl-CF 2 Br) have been measured over the temperature range 230-370 K to give the following Arrhenius expressions: k CH3OCH(CF3)2 (T) = 7.69 × 10 -14 × (T/298) 2.99 × exp(+342/T), cm 3 molecule -1 s -1 , and k CH2CHCFClCF2Br (T) = (6.45 ± 0.72) × 10 -13 × exp{+(424 ± 32)/T}, cm 3 molecule -1 s -1 . Atmospheric lifetimes of compounds were estimated to be 67 days and 4.5 days, respectively. UV absorption spectrum of CH 2 ═CH-CFCl-CF 2 Br between 164 and 260 nm and IR absorption spectra of both compounds between 450 and 1600 cm -1 were measured at room temperature.

  1. Using a modified Marcus model to analyze the Brønsted correlation of gas-phase reactions of the deprotonation of para-substituted toluenes by CH2Cl-, H(O)C-, CH3O-, H(F)N-, NH2C≡C-, and CH3C≡C- anions (United States)

    Romanskii, I. A.


    Ab initio calculations of the energy parameters for a series of gas-phase reactions of the deprotonation of para-substituted toluenes (OH, CH3, H, Cl, NC, CN, and NO2 substituents) by CH2Cl-, H(O)C-, CH3O-, H(F)N-, NH2C≡C-, and CH3C≡C- anions (the conjugated acids are chloromethane (CH3Cl), formaldehyde (H2CO), methanol (CH3OH), fluoroamine (NH2F), aminoacetylene (NH2C≡CH), and methylacetylene (CH3C≡CH), respectively) is performed using a technique of intramolecular reorganization proposed earlier. The equilibrium ( E a eq) and nonequilibrium ( E a neq ) contributions to energy of activation E a are found for distance Q(C…B) = 3.0 Å (where C and B are the central atoms of the acid and base). At this value of Q, the tunneling mechanism of proton transfer predominates. The results from calculations, together with similar data obtained earlier for reactions of the deprotonation of toluenes by CH2CN- anions, are considered from the viewpoint of the harmonic Marcus model. It is found that in the graph Δ E 0 - E a neq (where Δ E 0 is the internal energy of the reaction (for a collision complex)), the points for five reaction series with C-bases fall on the same quadratic (within the -11 to 12 kcal/mol range of Δ E 0) curve; the second curve, which includes points for the series with N- and O-bases (OCH3 - and H(F)N-) is shifted below the first curve by 1.5 kcal/mol. For most reaction series (except the one with the strongest bases, CH2Cl- and H(O)C-), the curvature and slope of graph Δ E 0 - E a neq are in agreement with the theory. The correlations of energies E a neq , E a eq, E a, and Δ E 0 with the energy of reaction Δ E 00 are satisfactorily described by quadratic equations as well. Differences between the structures of bases are reflected most by energy E a eq and the height of the proton tunneling barrier in the activated complex (AC) E b. For the series of reactions of toluene with a set of bases, graphs Δ E 00 - E a eq and Δ E 0 - E b show

  2. Oxidative alkylation of (η5-C5Me5)2TiR (R = Cl, Me, Et, CH=CH2, Ph, OMe, N=C(H)tBu) to (η5-C5Me5)2Ti(Me)R by group 12 organometallic compounds MMe2

    NARCIS (Netherlands)

    Luinstra, Gerrit A.; Teuben, Jan H.


    Oxidative alkylation of Cp*2TiX (Cp*: η5-C5Me5; X = OMe, Cl, N=C(H)tBu) and Cp* 2TiMe by CdMe2 or ZnMe2 gives diamagnetic Cp*2Ti(Me)X and Cp*2TiMe2 respectively, and cadmium or zinc. The reactions of Cp*2TiR (R = Et, CH=CH2, Ph) with MMe2 (M = Cd, Zn) give statistical mixtures of Cp*2Ti(Me)R,


    NARCIS (Netherlands)



    Oxidative alkylation of Cp*2TiX (Cp*: eta-5-C5Me5; X = OMe, Cl, N = C(H)tBu) and Cp*2TiMe by CdMe2 or ZnMe2 gives diamagnetic Cp*2Ti(Me)X and Cp*2TiMe2 respectively, and cadmium or zinc. The reactions of Cp*2TiR (R = Et, CH = CH2, Ph) with MMe2 (M = Cd, Zn) give statistical mixtures of Cp*2Ti(Me)R,

  4. Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms. (United States)

    Díaz-de-Mera, Yolanda; Aranda, Alfonso; Bravo, Iván; Rodríguez, Diana; Rodríguez, Ana; Moreno, Elena


    The adverse environmental impacts of chlorinated hydrocarbons on the Earth's ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C-F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF(3)CF(2)CF(2)OCH(3)) (1) and its isomer CF(3)CF(2)CF(2)CH(2)OH (2). Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube-mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266-333 and 298-353 K for reactions of HFE-7000 and CF(3)CF(2)CF(2)CH(2)OH, respectively. The measured room temperature rate constants were k(Cl+CF(3)CF(2)CF(2)OCH(3)) = (1.24 +/- 0.28) x 10(-13) cm(3) molecule(-1) s(-1)and k(Cl+CF(3)CF(2)CF(2)CH(2)OH) = (8.35 +/- 1.63) x 10(-13) cm(3) molecule(-1) s(-1) (errors are 2sigma + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k (1)(266-333 K) = (6.1 +/- 3.8) x 10(-13)exp[-(445 +/- 186)/T] cm(3) molecule(-1) s(-1) and k (2)(298-353 K) = (1.9 +/- 0.7) x 10(-12)exp[-(244 +/- 125)/T] cm(3) molecule(-1) s(-1) (errors

  5. Syntheses of the Uranium Complexes [U{N(SiMe(3))(2)}(2){N(SiMe(3))(SiMe(2)CH(2)B(C(6)F(5))(3))}] and [U{C(Ph)(NSiMe(3))(2)}(2){&mgr;(3)-BH(4)}(2)]. Determination of Hydrogen Positions by Single-Crystal X-ray and Neutron Diffraction. (United States)

    Müller, Matthias; Williams, V. Cliff; Doerrer, Linda H.; Leech, Michael A.; Mason, Sax A.; Green, Malcolm L. H.; Prout, Keith


    The complex [U{N(SiMe(3))(2)}(2){N(SiMe(3))(SiMe(2)CH(2)B(C(6)F(5))(3))}] (1) is formed in the reaction between the hydride complex [U{N(SiMe(3))(2)}(3)(H)] and B(C(6)F(5))(3), and H(2) is evolved. The X-ray [C(36)H(53)BF(15)N(3)Si(6)U.3.5C(6)D(6), triclinic, space group P&onemacr;, Z = 2, 90 K, a = 14.065(1) Å, b = 14.496(1) Å, c = 18.759(1) Å, alpha = 82.898(1) degrees, beta = 74.415(1) degrees, gamma = 62.919(1) degrees ] and neutron structure [C(36)H(53)BF(15)N(3)Si(6)U.3.5C(6)D(6), triclinic, space group P&onemacr;, Z = 2, 20 K, a = 13.993(1) Å, b = 14.484(1) Å, c = 18.720(1) Å, alpha = 82.810(1) degrees, beta = 74.200(1) degrees, gamma = 63.054(1)E] of compound 1, which crystallizes with 3.5 molecules of C(6)D(6) per asymmetric unit, show the electron deficiency of the uranium atom to be effectively compensated by the formation of multicenter bonds between U and three Si-CH(2) units of the amido ligands. The reaction of the uranium complex [U{C(Ph)(NSiMe(3))(2)}(2)(Cl)(2)] with [Na(BH(4))] gives the complex [U{C(Ph)(NSiMe(3))(2)}(2){&mgr;(3)-BH(4)}(2)] (2). The X-ray structure of 2 [C(26)H(54)B(2)N(4)Si(4)U, monoclinic, space group C2/c, Z = 4, 90 K, a = 21.613(1) Å, b = 9.233(1) Å, c = 18.132(1) Å, beta = 98.804(1) degrees ] proves unequivocally the &mgr;(3) coordination of the BH(4) moieties. In both single-crystal X-ray structure determinations, all hydrogen and deuterium atoms could be located and isotropically refined, including those which are directly coordinated to the uranium. The reliability of the refined hydrogen and deuterium positions for compound 1 is confirmed by comparison of the X-ray and neutron structure determinations. The ability to locate the hydrogen and deuterium positions in these uranium compounds by single-crystal X-ray diffraction is due to good crystal quality, the measurement of data at low temperature, and the use of image plate technology for data collection.

  6. fac-[Re(CO)(3)L](+) complexes with N-CH(2)-CH(2)-X-CH(2)-CH(2)-N tridentate ligands. synthetic, X-ray crystallographic, and NMR spectroscopic investigations. (United States)

    Christoforou, Anna Maria; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G


    Polyamine ligands (L) have excellent binding characteristics for the formation of fac-99mTc(CO)3-based radiopharmaceuticals. Normally, these L are elaborated so as to leave pendant groups designed to impart useful biodistribution characteristics to the fac-[99mTc(CO)3L] imaging agent. Our goal is to lay a foundation for understanding the features of the bound elaborated ligands by using the fac-[Re(CO)3L]-analogue approach with the minimal prototypical ligands, diethylenetriamine (dien) or simple dien-related derivatives. Treatment of the fac-[Re(CO)3(H2O)3]+ cation with such triamine (NNN) ligands afforded fac-[Re(CO)3L]+ complexes. Ligand variations included having a central amine thioether donor, thus allowing X-ray crystallographic and NMR spectroscopic comparisons of fac-[Re(CO)3L]+ complexes with NNN and NSN ligands. fac-[Re(CO)3L]+ complexes with two terminal exo-NH groups exhibit unusually far upfield exo-NH NMR signals in DMSO-d6. Upon the addition of Cl-, these exo-NH signals move downfield, while the signals of any endo-NH or central NH groups move very little. This behavior is attributed to the formation of 1:1 ion pairs having selective Cl- hydrogen bonding to both exo-NH groups. Base addition to a DMSO-d6 solution of meso-exo-[Re(CO)3(N,N',N''-Me3dien)]PF6 led to isomerization of only one NHMe group, producing the chiral isomer. The meso isomer did not form. The [Re(CO)3(N,N,N',N'',N''-pentamethyldiethylenetriamine)]triflate.[Re(CO)3(mu3-OH)]4.3.35H2O crystal, the first structure with a fac-[Re(CO)3L] complex cocrystallized with this well-known cluster, provided parameters for a bulky NNN ligand and also reveals CO-CO interlocking intermolecular interactions that could stabilize the crystal.

  7. A position dependent particle counter using microchannel plates, ch. 2

    International Nuclear Information System (INIS)

    Wijnaendts van Resandt, R.W.; Harink, H.C. den; Los, J.


    The use of cascaded channel plates as position dependent particle counters is described. A one- and two-dimensional dissection technique, based on the spread of charge between channel plate and collector, is used. The one-dimensional detector is developed for use in atomic scattering experiments. The system is tested by measuring the relative, total differential scattering cross section of electrons by helium between 1deg and 3-4 deg

  8. Crystal structures of two decavanadates(V with pentaaquamanganese(II pendant groups: (NMe42[V10O28{Mn(H2O5}2]·5H2O and [NH3C(CH2OH3]2[V10O28{Mn(H2O5}2]·2H2O

    Directory of Open Access Journals (Sweden)

    Maurício P. Franco


    Full Text Available Two heterometallic decavanadate(V compounds, bis(tetramethylammonium decaaquadi-μ4-oxido-tetra-μ3-oxido-hexadeca-μ2-oxido-hexaoxidodimanganese(IIdecavanadate(V pentahydrate, (Me4N2[V10O28{Mn(H2O5}2]·5H2O, A, and bis{[tris(hydroxymethylmethyl]ammonium} decaaquadi-μ4-oxido-tetra-μ3-oxido-hexadeca-μ2-oxido-hexaoxidodimanganese(IIdecavanadate(V dihydrate, [NH3C(CH2OH3]2[V10O28{Mn(H2O5}2]·2H2O, B, have been synthesized under mild reaction conditions in an aqueous medium. Both polyanions present two [Mn(OH25]2+ complex units bound to the decavanadate cluster through oxide bridges. In A, the decavanadate unit has 2/m symmetry, whereas in B it has twofold symmetry. Apart from this, the main differences between A and B rest on the organic cations, tetramethylammonium and [tris(hydroxymethylmethyl]ammonium, respectively, and on the number and arrangement of the water molecules of crystallization. In both compounds, the H atoms from the coordinating water molecules participate in extensive three-dimensional hydrogen-bonding networks, which link the cluster units both directly and through solvent molecules and, in B, through the `tris' cation hydroxyl groups. The cation in B also participates in N—H...O hydrogen bonds. A number of C—H...O interactions are also observed in both structures.

  9. Anomalous absorption in H2CN and CH2CN molecules

    Indian Academy of Sciences (India)

    Though these molecules have been identified through emission lines, the anomalous absorption of the said lines can be used for confirmation purposes. Acknowledgments. We are grateful to Prof. Jayant V Narlikar and Prof. Dr W H Kegel for their encouragement. Thanks are due to the Indian Space Research Organization, ...

  10. Quantum computing applied to calculations of molecular energies: CH2 benchmark

    Czech Academy of Sciences Publication Activity Database

    Veis, L.; Pittner, Jiří


    Roč. 133, č. 19 (2010), s. 194106 ISSN 0021-9606 R&D Projects: GA ČR GA203/08/0626 Institutional research plan: CEZ:AV0Z40400503 Keywords : computation * algorithm * systems Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.920, year: 2010

  11. Investigations of Chemiluminescence in the CH2 + O Gas Phase Reaction

    National Research Council Canada - National Science Library

    Vaghjiani, Ghanshyam


    ... signatures at high altitudes. A detailed understanding of the pertinent chemical reactions that produce the electronically excited species, and of the competing quenching reactions that remove the internal energy in radiation...

  12. A temperature dependent kinetic study of the reaction of the hydroxyl radical with CH2Br (United States)

    Zhang, Zhengyu; Saini, Rameshwar D.; Kurylo, Michael; Huie, Robert E.


    Rate constants have been measured for the gas phase reaction of the hydroxyl radical (OH) with CH3Br over the temperature range 250 to 400 K. The Arrhenius expression k = (5.79 x 10 exp -12) exp(-1560/T) cu cm/molecule per sec was derived from the kinetic data. From the rate constant at 277 K, the tropospheric lifetime of CH3Br with respect to reaction with OH is estimated to be 2.2 years and the overall atmospheric lifetime to be 2.1 years.

  13. A theoretical study of the carbenoids LiCH2X (X = Cl, Br, I ...

    Indian Academy of Sciences (India)


    Smith. 15. This has motivated a large number of research groups to develop new and wide-range methods to produce cyclopropanated products. Methylene insertion by a carbenoid species into the. C=C bond is one of the most widely used methods since the recognition of the Simmons–Smith reac- tion, which is a reaction ...

  14. Radioimmunological determination of insulin, growth hormone and calcitonin in serum, ch. 2

    International Nuclear Information System (INIS)

    Froelich, M.


    Radioimmunoassay procedures for the determination of insulin, growth hormone and calcitonin in blood serum were developed. The procedure as well as the iodination of antigens and the generation of antibodies are described. Short-term and long-term quality control experiments dealing with specificity, recovery, sensitivity, intrassay variability and interassay variability are reported

  15. Further insights into the reaction 14Be(CH 2,X )10He (United States)

    Jones, M. D.; Kohley, Z.; Baumann, T.; Christian, G.; DeYoung, P. A.; Finck, J. E.; Frank, N.; Haring-Kaye, R. A.; Kuchera, A. N.; Luther, B.; Mosby, S.; Smith, J. K.; Snyder, J.; Spyrou, A.; Stephenson, S. L.; Thoennessen, M.


    A previously published measurement of the reaction of a 59 MeV/nucleon 14Be beam on a deuterated polyethylene target was further analyzed to search for 12He as well as initial state effects in the population of the 10He ground state. No evidence for either was found. A lower limit of about 1 MeV was determined for a possible resonance in 12He . In addition, the three-body decay energy spectrum of 10He could not be described by a reaction mechanism calculation based on the halo structure of the initial 14Be assuming a direct α -particle removal reaction.

  16. Search for 4n contributions in the reaction 14Be(CH2,X)10He (United States)

    Jones, M. D.; Kohley, Z.; Baumann, T.; Christian, G.; DeYoung, P. A.; Finck, J. E.; Frank, N.; Haring-Kaye, R. A.; Kuchera, A. N.; Luther, B.; Mosby, S.; Smith, J. K.; Snyder, J.; Spyrou, A.; Stephenson, S. L.; Thoennessen, M.


    A previously published measurement of the ground state resonance of 10He, populated by a reaction of a 59 MeV/u 14Be beam on a deuterated polyethylene target, was further analyzed to search for 4n emission resulting from 2p removal. No evidence for 4n events was found. A lower limit of about 1 MeV was determined for a possible resonance in 12He.

  17. Search for 4n contributions in the reaction 14Be(CH2,X10He

    Directory of Open Access Journals (Sweden)

    Jones M. D.


    Full Text Available A previously published measurement of the ground state resonance of 10He, populated by a reaction of a 59 MeV/u 14Be beam on a deuterated polyethylene target, was further analyzed to search for 4n emission resulting from 2p removal. No evidence for 4n events was found. A lower limit of about 1 MeV was determined for a possible resonance in 12He.

  18. HO- OJ'r~-CH2-NH-R R --H

    African Journals Online (AJOL)

    The possibility of two types of beta-adrenergic receptors is supported by the results presented. It is shown that the phenylephrine group of compounds have more pro- nounced affinities towards the beta,-(cardiac) adrenergic receptors than towards the beta,-(bronchial) adrenergic receptors. The cardioselective action is the ...

  19. Intramolecular Pnicogen Interactions in PHF(CH2)nPHF (n=26) Systems

    Czech Academy of Sciences Publication Activity Database

    Sanchez-Sanz, Goar; Alkorta, I.; Trujillo, Cristina; Elguero, J.


    Roč. 14, č. 8 (2013), s. 1656-1665 ISSN 1439-4235 Institutional support: RVO:61388963 Keywords : electron density shift * intramolecular interactions * ab initio calculations * pnicogens * electrostatic interactions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.360, year: 2013

  20. Thermodynamic study of (alkyl esters + α,ω-alkyl dihalides) VI. HmE and VmE for 20 binary mixtures {xCu-1H2u-1CO2(CH2)3CH3 + (1 - x)α,ω-BrCH2(CH2)v-2CH2Br}, where u = 1 to 5, α = 1, and v = ω = 2 to 6

    International Nuclear Information System (INIS)

    Navas, A.; Ortega, J.; Nuez, I. de la


    This work shows the experimental values obtained for H m E and V m E at the temperature of 298.15 K and atmospheric pressure, for a set of 20 binary mixtures comprised of the first four butyl esters (methanoate to butanoate) with five α,ω-dibromoalkanes (1,2-dibromoethane to 1,6-dibromohexane). The H m E are endothermic for mixtures with butyl methanoate, while for the other esters the H m E adopt a sigmoidal shape. The V m E are positive for mixtures with low molecular weight dibromoalkanes, becoming negative with contractive effects in the final mixture, as the dihalide chain increases. The results indicate that the mixtures present specific interactions, with simultaneous expansion/contraction and exothermic/endothermic effects, and an explanation is given for the different types of interaction taking place. Experimental data are correlated with a polynomial equation used in previous works with satisfactory results. Modelling of the experimental results of the mixtures is carried out on the H m E values, giving rise to an adequate definition of the different interactions taking place. Two versions of the UNIFAC method were used, and for Dang and Tassios' version different possibilities were considered for the interaction parameters of the ester (G)/dibromide (G'). The best estimations were obtained when the pair of interaction parameters, type a G/G ' , depended on the number of carbon atoms in the compounds constituting the mixture.

  1. Substituent Effects Dehalogenation of Aryl Bromides with NaAlH2(OCH2CH2OCH3)2

    Czech Academy of Sciences Publication Activity Database

    Czakoová, Marie; Hetflejš, Jiří; Včelák, Jaroslav


    Roč. 72, č. 2 (2001), s. 277-287 ISSN 0133-1736 R&D Projects: GA ČR GA203/97/1173 Institutional research plan: CEZ:AV0Z4072921 Keywords : substituent effects * aryl bromides * Co-assisted debromination Subject RIV: CC - Organic Chemistry Impact factor: 0.475, year: 2001

  2. Phosphoinositide binding regulates α-actinin CH2 domain structure: Analysis by hydrogen/deuterium exchange mass spectrometry (United States)

    Full, Stephen J.; Deinzer, Max L.; Ho, P. Shing; Greenwood, Jeffrey A.


    α-Actinin is an actin bundling protein that regulates cell adhesion by directly linking actin filaments to integrin adhesion receptors. Phosphatidylinositol (4,5)-diphosphate (PtdIns (4,5)-P2) and phosphatidylinositol (3,4,5)-triphosphate (PtdIns (3,4,5)-P3) bind to the calponin homology 2 domain of α-actinin, regulating its interactions with actin filaments and integrin receptors. In this study, we examine the mechanism by which phosphoinositide binding regulates α-actinin function using mass spectrometry to monitor hydrogen–deuterium (H/D) exchange within the calponin homology 2 domain. The overall level of H/D exchange for the entire protein showed that PtdIns (3,4,5)-P3 binding alters the structure of the calponin homology 2 domain increasing deuterium incorporation, whereas PtdIns (4,5)-P2 induces changes in the structure decreasing deuterium incorporation. Analysis of peptic fragments from the calponin homology 2 domain showed decreased local H/D exchange within the loop region preceding helix F with both phosphoinositides. However, the binding of PtdIns (3,4,5)-P3 also induced increased exchange within helix E. This suggests that the phosphate groups on the fourth and fifth position of the inositol head group of the phosphoinositides constrict the calponin homology 2 domain, thereby altering the orientation of actin binding sequence 3 and decreasing the affinity of α-actinin for filamentous actin. In contrast, the phosphate group on the third position of the inositol head group of PtdIns (3,4,5)-P3 perturbs the calponin homology 2 domain, altering the interaction between the N and C terminus of the full-length α-actinin antiparallel homodimer, thereby disrupting bundling activity and interaction with integrin receptors. PMID:17965186

  3. Phosphoinositide binding regulates alpha-actinin CH2 domain structure: analysis by hydrogen/deuterium exchange mass spectrometry. (United States)

    Full, Stephen J; Deinzer, Max L; Ho, P Shing; Greenwood, Jeffrey A


    alpha-Actinin is an actin bundling protein that regulates cell adhesion by directly linking actin filaments to integrin adhesion receptors. Phosphatidylinositol (4,5)-diphosphate (PtdIns (4,5)-P(2)) and phosphatidylinositol (3,4,5)-triphosphate (PtdIns (3,4,5)-P(3)) bind to the calponin homology 2 domain of alpha-actinin, regulating its interactions with actin filaments and integrin receptors. In this study, we examine the mechanism by which phosphoinositide binding regulates alpha-actinin function using mass spectrometry to monitor hydrogen-deuterium (H/D) exchange within the calponin homology 2 domain. The overall level of H/D exchange for the entire protein showed that PtdIns (3,4,5)-P(3) binding alters the structure of the calponin homology 2 domain increasing deuterium incorporation, whereas PtdIns (4,5)-P(2) induces changes in the structure decreasing deuterium incorporation. Analysis of peptic fragments from the calponin homology 2 domain showed decreased local H/D exchange within the loop region preceding helix F with both phosphoinositides. However, the binding of PtdIns (3,4,5)-P(3) also induced increased exchange within helix E. This suggests that the phosphate groups on the fourth and fifth position of the inositol head group of the phosphoinositides constrict the calponin homology 2 domain, thereby altering the orientation of actin binding sequence 3 and decreasing the affinity of alpha-actinin for filamentous actin. In contrast, the phosphate group on the third position of the inositol head group of PtdIns (3,4,5)-P(3) perturbs the calponin homology 2 domain, altering the interaction between the N and C terminus of the full-length alpha-actinin antiparallel homodimer, thereby disrupting bundling activity and interaction with integrin receptors.

  4. Isotope effect of glycinium phosphite NH3CH2COOH·H2PO3 studied by neutron diffraction

    International Nuclear Information System (INIS)

    Magome, Eisuke; Komukae, Masaru; Machida, Mitsuo; Tamura, Yuuki


    To study the isotope effect of glycinium phosphite (GPI), temperature dependences of the 5 0 6-bar and 3 0 1 0-bar structure factors of GPI and the 1 1 0 3-bar and 9 0 8-bar structure factors of deuterated GPI (DGPI) were analyzed in the ferroelectric phase by using the quasi-one-dimensional Ising model. The Ising model reproduces well the behavior of all the structure factors in the wide temperature region. The parameters for the intrachain and interchain interactions are determined to be 312 and 7.1 K for GPI, and 477 and 8.4 K for DGPI on average, respectively. (author)

  5. Thermodynamic study of (alkyl esters+α,ω-alkyl dihalides) III. HmEandVmE for 20 binary mixtures {xCu-1H2u-1CO2C4H9+(1-x)α,ω-ClCH2(CH2)v-2CH2Cl}, where u=1 to 4, α=1 and v=ω=2 to 6

    International Nuclear Information System (INIS)

    Ortega, J.; Marrero, E.; Toledo, F.J.


    In this article, the experimental data of excess molar enthalpies H m E and excess molar volumes V m E are presented for a set of 20 binary mixtures comprised of the first four butyl alkanoates (methanoate to butanoate) and five α,ω-dichloroalkanes (1,2-dichloroethane to 1,6-dichlorohexane), obtained at atmospheric pressure and at a temperature of 298.15K. The results indicate the existence of specific interactions between both kinds of compounds resulting in exothermic processes for most mixtures, except for those containing butyl methanoate which give rise to net endo/exothermic effects. The V m E are positive for mixtures of (butyl esters+1,2-dichloroethane or 1,3-dichloropropane) and negative for the remaining ones. The change in H m E with the dichloroethane chain length for a same ester is regular although the V m E presents an irregular variation. It can, therefore, be deuced from this that the mixing process involves both effects, exothermic/endothermic and expansion/contraction, simultaneously. The behaviour of the mixtures is interpreted on the basis of the results observed and attributed to different effects taking place among the molecules studied. To improve application of the UNIFAC model using the version of Dang and Tassios, average values were recalculated again for parameters of the ester/chloride interaction, distinguishing, during its application, the functional group of the acid part of the ester. In spite of this, the model does not adequately reproduce the systems' behaviour.

  6. Thermodynamic study of (alkyl esters+α,ω-alkyl dihalides) II: HmE and VmE for 25 binary mixtures {xCu-1H2u-1CO2C2H5+(1-x)α,ω-BrCH2(CH2)v-2CH2Br}, where u=1 to 5, α=1 and v=ω=2 to 6

    International Nuclear Information System (INIS)

    Ortega, J.; Navas, A.; Placido, J.; Toledo, F.J.


    Excess molar enthalpies H m E , and excess molar volumes V m E , have been determined experimentally at constant conditions of atmospheric pressure and a temperature of T=298.15K, for a set of 25 binary mixtures, composed of ethyl alkanoate (methanoate to pentanoate) with each of the α,ω-dibromoalkanes (1,2-dibromoethane to 1,6-dibromohexane), presenting the values of excess quantities Y m E as a function of the ester composition x. Most of the mixtures presented V m E >0, except those formed by 1,5-dibromopentane and 1,6-dibromohexane with propanoate, butanoate and ethyl pentanoate, for which V m E m E are made using two versions of the UNIFAC group contribution model. The version proposed by Dang and Tassios produces unacceptable estimations, while the version of Gmehling et al. produces results closer to experimentals.

  7. Thermodynamic study of (alkyl esters+α,ω-alkyl dihalides) I: HmE and VmE for 25 binary mixtures {xCu-1H2u-1CO2C2H5+(1-x)α,ω-ClCH2(CH2)v-2CH2Cl}, where u=1 to 5, α=1 and v=ω=2 to 6

    International Nuclear Information System (INIS)

    Ortega, J.; Marrero, E.; Toledo, F.J.; Espiau, F.


    This article presents the experimental data of H m E and V m E , obtained at atmospheric pressure and at a temperature of 298.15K, for a set of 25 binary mixtures composed of the first 5 ethyl alkanoates (methanoate to pentanoate) and five α,ω-dichloroalkanes (1,2-dichloroethane to 1,6-dichlorohexane). Quantitatively, and with only a few exceptions, small values are obtained for the excess properties and the results imply that specific interactions exist between both types of compounds, with exothermic process for most mixtures, but with the exception of some that contain ethyl methanoate and ethanoate. The change in enthalpies with increasing length of the dichloroalkane chain for the same ester is regular, and also the change in H m E with the acid portion of the ethyl ester. However, the change in excess volumes does not present such a regular variation. A behavioural structural model is established to explain the results of the excess properties. Experimental values of H m E and V m E were correlated, as a function of ester concentration, x with a new expression which uses the so-called active fraction as a variable and which, in turn, is a function of this concentration. The application of two versions of the UNIFAC group contribution models produces no good estimations of H m E .

  8. A survey of the 5C2 region with the Westerbork synthesis radio telescope at 1415 MHz (the third Westerbork survey), ch. 2

    International Nuclear Information System (INIS)

    Katgert, P.


    The 5C2 region, observed originally with the Cambridge One-Mile Telescope at 408 MHz, has been reobserved at l4l5 MHz. The resulting source list contains 238 sources with attenuated flux densities exceeding the catalogue limit of 6.25 m.f.u. Out of a total of 190 5C2 sources (i.e. all 5C2 sources within the 10 dB attenuation contour of the present survey), 128 were detected with flux densities above the catalogue limit. Another 22 5C2 sources were detected with flux densities below the catalogue limit. A discussion is given of the procedures used for determining source parameters. Special attention has been given to the determination of flux density and angular size as well as to the question of completeness of the source list as a function of flux density and angular size

  9. Gas-phase synthesis of the rare-gas carbene cation ArCH2+ using doubly ionised bromomethane as a superelectrophilic reagent

    Czech Academy of Sciences Publication Activity Database

    Ascenzi, D.; Tosi, P.; Roithová, Jana; Schröder, Detlef

    -, č. 34 (2008), s. 4055-4057 ISSN 1359-7345 Institutional research plan: CEZ:AV0Z40550506 Keywords : argon * dications * mass spectrometry * rare-gas compounds * superelectrophiles Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.340, year: 2008

  10. High resolution infrared synchrotron study of CH2D81Br: ground state constants and analysis of the ν5, ν6 and ν9 fundamentals

    DEFF Research Database (Denmark)

    Baldacci, A.; Stoppa, P.; Visinoni, R.


    .710 cm-1) and ν9 (930.295 cm-1) fundamental bands. The ground state constants up to sextic centrifugal distortion terms have been obtained for the first time by ground-state combination differences from the three bands and subsequently employed for the evaluation of the excited state parameters. Watson...... and a high-order coupling constant which takes into account the interaction between ν5 and ν9 have been determined....

  11. X-ray diffraction study on Al(NO3)3 and Cr(NO3)3 aqueous solutions, ch. 2

    International Nuclear Information System (INIS)

    Welzen, Th.L.


    Aqueous solutions of the nitrates of aluminium and chromium (both 0.5 M) are investigated with x-ray diffraction at t=25degC in order to obtain information about the hydration of these cations. The experimental intensity is interpreted in terms of an electron product function which is a sum of various pair contributions. The contribution containing the information about cationic (and anionic) hydration has been evaluated by combining the results of separate experiments. For the cations, two hydration shells are found, respectively at 1.90A and 4.10-4.15A for Al 3+ and at 1.98A and 4.20-4.25A for Cr 3+ . For both cations, the sixfold coordination in the first shell is reasonably well established; the second hydration shells contain about 12 watermolecules. A well-resolved hydration shell is not found for the nitrate ion

  12. Evaluación del impacto atmosférico de CF3(CF2)x=0-5 CH=CH2: potenciales sustitutos de CFCS


    González Rubio, Sergio


    Los CFCs (clorofluorocarbonos) son los principales responsables de la destrucción del ozono estratosférico. Por este motivo, el Protocolo de Montreal (1987) implantó una serie de medidas para controlar y reducir las emisiones de CFCs a la atmósfera y sustituirlos por otros gases menos perjudiciales para el medioambiente. La primera generación de sustitutos de CFCs fueron los hidroclorofluorocarbonos (HCFCs), que al poseer átomos de hidrogeno en su estructura reaccionan más rápidamente con...

  13. Ultrafast One-Photon (232 vs 266 nm Bond-Selective Photochemistry of Bromoiodomethane (CH2BrI in Solution

    Directory of Open Access Journals (Sweden)

    Panov M. S.


    Full Text Available Ultrafast broadband transient absorption spectra measured from the deep-ultraviolet to the near-infrared region following single-photon excitation of bromoiodomethane in acetonitrile at different wavelengths manifest chromophore -selective structural rearrangement and carbon-halogen bond dissociation in solution.

  14. Characteristic spin - orbit induced 1H(CH2) chemical shifts upon deprotonation of group 9 polyamine aqua and alcohol complexes

    Czech Academy of Sciences Publication Activity Database

    Hyvärinen, M.; Vaara, J.; Goldammer, A.; Kutzky, B.; Hegetschweiler, K.; Kaupp, M.; Straka, Michal


    Roč. 131, č. 33 (2009), s. 11909-11918 ISSN 0002-7863 R&D Projects: GA ČR GA203/09/2037; GA ČR GA202/07/0732; GA AV ČR IAA400550701; GA AV ČR IAA400550705 Institutional research plan: CEZ:AV0Z40550506 Keywords : relativistic effects * 1H NMR * theoretical calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.580, year: 2009

  15. The diagnostic value of serum hybrid capture 2 (CH2) HPV DNA in cervical cancer: a systematic review and meta-analysis. (United States)

    Yin, Duo; Jiang, Yan; Wang, Ning; Ouyang, Ling; Lu, Yanming; Zhang, Yao; Wei, Heng; Zhang, Shulan


    The diagnostic accuracy of cervical cancer remains a clinical challenge, and a number of studies have used the serum hybrid capture 2 (HC2) human papillomavirus (HPV) DNA in the diagnosis of cervical cancer. The aim of the present meta-analysis was to determine the overall accuracy of HC2 HPV DNA in the diagnosis of cervical cancer. A systematic review of studies from PubMed, Embase, the Cochrane Library, Web of Science, Ovid, Chinese Biomedical Literature Database-disc, Chinese National Knowledge Infrastructure (CNKI), Technology of Chongqing (VIP), and Wan Fang database was conducted, and the data concerning the accuracy of HC2 HPV DNA in the diagnosis of cervical cancer were pooled. The methodological quality of each study was assessed by quality assessment for studies of diagnostic accuracy (QUADAS). Statistical analysis was performed by employing Meta-DiSc (version 1.4) and Stata (version 12.0) software. The overall test performance was summarized using receiver operating characteristic curves. Finally, 12 studies, including 12,492 subjects, met the inclusion criteria and then included in this present meta-analysis. The summary estimates for serum HC2 HPV DNA in the diagnosis of cervical cancer were as follows: sensitivity 0.83 (95 % confidence interval (CI) 0.81-0.85), specificity 0.71 (95 % CI 0.69-0.72), positive likelihood ratio 3.65 (95 % CI 1.77-7.54), negative likelihood ratio 0.32 (95 % CI 0.21-0.48), and diagnostic odds ratio 10.54 (95 % CI 4.95-22.46), and the area under the curve was 0.8922. Our findings suggest that HC2 HPV DNA may improve the accuracy of cervical cancer diagnosis, while the results of HC2 HPV DNA assays should be interpreted in parallel with conventional test results and other clinical findings.

  16. Peripheral modifications of [Ψ[CH2NH]Tpg4]vancomycin with added synergistic mechanisms of action provide durable and potent antibiotics. (United States)

    Okano, Akinori; Isley, Nicholas A; Boger, Dale L


    Subsequent to binding pocket modifications designed to provide dual d-Ala-d-Ala/d-Ala-d-Lac binding that directly overcome the molecular basis of vancomycin resistance, peripheral structural changes have been explored to improve antimicrobial potency and provide additional synergistic mechanisms of action. A C-terminal peripheral modification, introducing a quaternary ammonium salt, is reported and was found to provide a binding pocket-modified vancomycin analog with a second mechanism of action that is independent of d-Ala-d-Ala/d-Ala-d-Lac binding. This modification, which induces cell wall permeability and is complementary to the glycopeptide inhibition of cell wall synthesis, was found to provide improvements in antimicrobial potency (200-fold) against vancomycin-resistant Enterococci (VRE). Furthermore, it is shown that this type of C-terminal modification may be combined with a second peripheral (4-chlorobiphenyl)methyl (CBP) addition to the vancomycin disaccharide to provide even more potent antimicrobial agents [VRE minimum inhibitory concentration (MIC) = 0.01-0.005 μg/mL] with activity that can be attributed to three independent and synergistic mechanisms of action, only one of which requires d-Ala-d-Ala/d-Ala-d-Lac binding. Finally, it is shown that such peripherally and binding pocket-modified vancomycin analogs display little propensity for acquired resistance by VRE and that their durability against such challenges as well as their antimicrobial potency follow now predictable trends (three > two > one mechanisms of action). Such antibiotics are expected to display durable antimicrobial activity not prone to rapidly acquired clinical resistance.

  17. Rate constants for the reactions of OH with HFC-134a (CF3CH2F) and HFC-134 (CHF2CHF2) (United States)

    Demore, W. B.


    Measurements of rate constants for HFC-134 (CF2HCF2H) relative to CH3CCl3, HFC-125, and HFC-134a are reported. The measurements were made in a slow-flow, temperature controlled photochemical reactor, and were based on relative rates of disappearance of the parent compounds as measured by FTIR spectroscopy. Hydroxyl radicals were generated by 254-nm photolysis of O3 in the presence of water vapor. NASA/JPL rate constants for the reference compounds are used to derive temperature-dependent rate constants of both compounds. Rate constants obtained from the different reference compounds are in excellent agreement. The presently recommended rate constant for HFC-134a is about 25 percent too high.

  18. A Study on the Reactivity of WCl6-e--Al-CH2Cl2 with the Silicon-Containing Dienes (United States)

    Düz, Bülent; Aydogdu, Cemil; Karabulut, Solmaz; Imamoglu, Yavuz

    Although until the late 1980s very little information on effective metathesis conversion of organosilicon compounds had been reported, the use of molybdenum (Schrock) catalyst and ruthenium (Grubbs) carbene complexes as catalysts tolerating functional groups in substrates, have opened new synthetic opportunities in organosilicon chemistry. Silicon containing dienes undergo two types of metathetical transformation.

  19. A Ge(Li)-NaI(Tl) Compton-suppression spectrometer for in-beam γ-ray spectroscopy, ch. 2

    International Nuclear Information System (INIS)

    Driel, M.A. van; Hoogenboom, A.M.


    A Compton-suppression spectrometer has been constructed for in-beam γ-ray work. It consists of a closed-end Ge(Li) detector with an efficiency of 21% and a resolution of 2.0 keV for 1.33 MeV γ-rays surrounded by a NaI(Tl) shield (dia. 230 mm, length 280 mm). The overall Compton-suppression factor for a 60 Co spectrum is 10. Details of the construction are discussed and experimental properties are compared with design calculations

  20. Conformational evaluation of labeled C3'-O-P-13CH2-O-C4'' phosphonate internucleotide linkage, a phosphodiester isostere

    Czech Academy of Sciences Publication Activity Database

    Točík, Zdeněk; Buděšínský, Miloš; Barvík Jr., I.; Rosenberg, Ivan


    Roč. 91, č. 7 (2009), s. 514-529 ISSN 0006-3525 R&D Projects: GA AV ČR KAN200520801; GA MŠk(CZ) LC06061; GA MŠk(CZ) LC06077 Institutional research plan: CEZ:AV0Z40550506 Keywords : nucleoside phosphonate * 13C labeling * NMR Subject RIV: CC - Organic Chemistry Impact factor: 2.605, year: 2009

  1. On the stereochemistry of C3'-O-P-CH2-O-C4'' phosphonate internucleotide bond, a phosphate isostere

    Czech Academy of Sciences Publication Activity Database

    Točík, Zdeněk; Buděšínský, Miloš; Barvík Jr., I.; Rosenberg, Ivan

    -, č. 52 (2008), s. 427-428 ISSN 0261-3166. [Joint Symposium of the International Roundtable on Nucleosides, Nucleotides and Nucleic Acids /18./ and the International Symposium on Nucleic Acid Chemistry /35./. Kyoto, 08.09.2008-12.09.2008] R&D Projects: GA MŠk(CZ) LC06061 Institutional research plan: CEZ:AV0Z40550506 Keywords : phosphonate oligonucleotide stereochemistry Subject RIV: CC - Organic Chemistry

  2. Production of H,D(2s, 2p) by electron impact (0 - 2000 eV) on simple hydrogen containing molecules, ch. 2, A2

    International Nuclear Information System (INIS)

    Moehlman, G.R.; Heer, F.J. de


    Absolute emission cross sections of Ly-α (H,D(2p → 1s)) radiation have been determined for 0 - 2000 eV electrons incident on H 2 , HD, HCl, H 2 O, NH 3 and CH 4 . By means of the application of electric quenching, the excitation cross sections of H,D(2s) could be obtained from the increase of the resulting Ly-α radiation for these molecules. Only in the case of electrons on H 2 , D 2 and HD was excitation of H,D(2s) found

  3. Crystal structure, phase transition and conductivity study of two new organic - inorganic hybrids: [(CH2)7(NH3)2]X2, X = Cl/Br (United States)

    Mostafa, Mohga Farid; El-khiyami, Shimaa Said; Abd-Elal, Seham Kamal


    Two hybrids 1,7-heptanediammonium di-halide, [(C7H20N2]X2,X = Cl/Br crystallize in monoclinic P21/c, Z = 4. [(C7H20N2]Cl2: a = 4.7838 (2) Å, b = 16.9879 (8) Å, c = 13.9476 (8) Å, β = 97.773 (2)°, V = 1203.58(10) Å3, D = 1.137 g/cm3, λ = 0.71073 Å, R = 0.052 for 1055 reflections with I > 2σ(I), T = 298(2) K. [(C7H20N2]Br2: a = 4.7952 (10) Å, b = 16.9740 (5) Å, c = 13.9281 (5) Å, β = 97.793 (2)°, V = 1203.83(6) Å3, D = 1.612 g/cm3, λ = 0.71073 Å, R = 0.03 for 1959 reflections with I > 2σ(I) T = 298(2) K. Asymmetric unit cell of [(C7H20N2]X2,X = Cl/Br, each consist of one heptane-1,7-diammonium cation and two halide anions. The organic hydrocarbon layers pack in a stacked herring-bone manner, hydrogen bonded to the halide ions. Lattice potential energy is 1568.59 kJ/mol and 1560.78 kJ/mol, and cation molar volumes are 0.295 nm3 and 0.300 nm3 for chloride and bromide respectively. DTA confirmed chain melting transitions for both hybrids below T ∼ 340 K. Dielectric and ac conductivity measurements (290 340 K. Cross over from Jonscher's universal dielectric response at low temperatures T 340 K is observed. At high temperatures halide ion hopping in accordance with the jump relaxation model prevails.

  4. Syntéza glykosyl donorů obsahujících 2-deoxy-2-{[(2,2,2-trichloroethoxy)-karbonyl]aminovou} skupinu

    Czech Academy of Sciences Publication Activity Database

    Drašar, Lukáš; Ledvina, Miroslav


    Roč. 99, č. 11 (2005), s. 835 ISSN 0009-2770. [Pokroky v organické, bioorganické a farmaceutické chemii /40./. 18.11.2005-20.11.2005, Nymburk] R&D Projects: GA MZe(CZ) QF3115; GA MŠk(CZ) 1P04OCD31.001 Institutional research plan: CEZ:AV0Z40550506 Keywords : glycosyl * donors Subject RIV: CC - Organic Chemistry

  5. Accounting for conformational flexibility and torsional anharmonicity in the H + CH3CH2OH hydrogen abstraction reactions: a multi-path variational transition state theory study. (United States)

    Meana-Pañeda, Rubén; Fernández-Ramos, Antonio


    This work reports a detailed theoretical study of the hydrogen abstraction reactions from ethanol by atomic hydrogen. The calculated thermal rate constants take into account torsional anharmonicity and conformational flexibility, in addition to the variational and tunneling effects. Specifically, the kinetics calculations were performed by using multi-path canonical variational transition state theory with least-action path tunneling corrections, to which we have added the two-dimensional non-separable method to take into account torsional anharmonicity. The multi-path thermal rate constant is expressed as a sum over conformational reaction channels. Each of these channels includes all the transition states that can be reached by internal rotations. The results show that, in the interval of temperatures between 250 and 2500 K, the account for multiple paths leads to higher thermal rate constants with respect to the single path approach, mainly at low and at high temperatures. In addition, torsional anharmonicity enhances the slope of the Arrhenius plot in this range of temperatures. Finally, we show that the incorporation of tunneling into the hydrogen abstraction reactions substantially changes the contribution of each of the transition states to the conformational reaction channel.

  6. High-accuracy estimates for the vinylidene-acetylene isomerization energy and the ground state rotational constants of :C═CH2. (United States)

    Lee, Hyunwoo; Baraban, Joshua H; Field, Robert W; Stanton, John F


    Highly accurate calculations are reported for properties of vinylidene (H2C═C:), specifically the position of its zero-point vibrational level relative to that of acetylene and its equilibrium structure and ground state rotational constants. The isomerization energy of vinylidene calculated at the HEAT-456QP level of theory is 43.53 ± 0.15 kcal mol(-1), in agreement with the previous best estimate, but associated with a much smaller uncertainty. In addition, the thermochemical calculations presented here also allow a determination of the H2CC-H bond energy of the vinyl radical at the HEAT-345(Q) level of theory, which is 77.7 ± 0.3 kcal mol(-1). The equilibrium structure of vinylidene, estimated with an additivity scheme that includes treatment of correlation effects beyond CCSD(T) as well as relativistic and adiabatic (diagonal Born-Oppenheimer correction) contributions, is rCC = 1.2982 ± 0.0003 Å, rCH = 1.0844 ± 0.0003 Å, and θCCH = 120.05 ± 0.05°, with zero-point rotational constants (including vibrational contributions and electronic contributions to the moment of inertia) estimated to be A0 = 9.4925 ± 0.0150 cm(-1), B0 = 1.3217 ± 0.0017 cm(-1), and C0 = 1.1602 ± 0.0016 cm(-1).

  7. Isotope effects in addition reactions of importance in combustion: Theoretical studies of the reactions CH + H2 right-reversible CH3* right-reversible CH2 + H

    International Nuclear Information System (INIS)

    Wagner, A.F.; Harding, L.B.


    Ab initio electronic structure characterizations of the addition reaction path for the title reaction are described. Variational RRKM calculations employing the reaction path properties are then used to compute thermal rate constants for comparison to kinetics measurements on the acetyl radical reaction hydrogen and its isotopic variation

  8. VUV photoionization aerosol mass spectrometric study on the iodine oxide particles formed from O3-initiated photooxidation of diiodomethane (CH2I2)

    Czech Academy of Sciences Publication Activity Database

    Wei, N.; Hu, Ch.; Zhou, S.; Ma, Q.; Mikuška, Pavel; Večeřa, Zbyněk; Gai, Y.; Lin, X.; Gu, X.; Zhao, W.; Fang, B.; Zhang, W.; Chen, J.; Liu, F.; Shan, X.; Sheng, L.


    Roč. 7, č. 89 (2017), s. 56779-56787 ISSN 2046-2069 Institutional support: RVO:68081715 Keywords : iodine oxide particles * photooxidation * aerosol mass spectrometer Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 3.108, year: 2016

  9. Preparation and structural characterization of the intermediate complex [Er{H2C8H16N4(CH2COO)3(CH2(Ph)PO2)}(H2O)2]2Cl2.xH2O in the reaction of Er3+ and the dota-type ligand. An interesting example of two stereoforms of a lanthanide complex

    Czech Academy of Sciences Publication Activity Database

    Vojtíšek, P.; Rohovec, Jan


    Roč. 71, č. 2 (2006), s. 264-278 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z30130516 Keywords : x-ray diffraction * lanthanoids * lanthanide complexes * erbium * stereochemistry Subject RIV: DD - Geochemistry Impact factor: 0.881, year: 2006

  10. Unusual electronic features and reactivity of the dipyridylazaallyl ligand: characterizations of (smif)2M [M = Fe, Co, Co+, Ni; smif = {(2-py)CH}2N] and [(TMS)2NFe]2(smif)2. (United States)

    Frazier, Brenda A; Wolczanski, Peter T; Lobkovsky, Emil B; Cundari, Thomas R


    Application of the dipyridylazaallyl ligand (2-py)CHNCH(2-py) (smif) to a series of first-row transition metals afforded (smif)(2)M(n) [n = 0, M = Fe (1), Co (2), Ni (3); n = +1, M = Co (2+)] and {(TMS)(2)NFe}(2)(smif)(2) (4(2)) via metathetical procedures. The Mossbauer spectrum of 1 (S = 0) and TDDFT calculations, including a UV-vis spectral simulation, reveal it to be a covalent, strong-field system with Delta(o) estimated as approximately 18,000 cm(-1) and B approximately 470 cm(-1). (smif)(2)Co (2) has S = 1/2 according to SQUID data at 10 K. DFT calculations suggest that the odd electron is localized in a smif pi* orbital, i.e., smif is redox-active. EPR-silent (smif)(2)Ni (3) has S = 1 (SQUID), and calculations show that the unpaired spins reside in the d(z(2)) and d(x(2))(-y(2)) orbitals. X-ray structural parameters suggest that low-spin d(6) 1 and 2+ are relatively symmetric D(2d) species, but 2 and 3 manifest a distortion in which one smif is canted in the plane perpendicular to the other. (smif)FeN(TMS)(2) (4) is principally monomeric in solution, but reversibly dimerizes (K(eq) approximately 10(-4) M(-1)) via C-C bond formation in the azaallyl backbone to crystallize as {(TMS)(2)NFe}(2)(smif)(2) (4(2)). The azaallyl compounds possess extraordinary UV-vis absorptivities (epsilon approximately 18,000-52,000) at 580 +/- 15 nm and 406(25) nm that have been identified as intraligand bands with C(nb) --> smif pi* character.

  11. Macropolyhedral borane reaction chemistry: Reductive oligomerisation of (BuNC)-Bu-ter by anti-B18H22 to give the boron-coordinated {((BuNHCH)-Bu-ter) {(BuNHC)-Bu-ter)CN)}CH2:} carbene residue

    Czech Academy of Sciences Publication Activity Database

    Jelínek, Tomáš; Kilner, C. A.; Barrett, S. A.; Štíbr, Bohumil; Thornton-Pett, M.; Kennedy, J.D.


    Roč. 8, č. 5 (2005), s. 491-494 ISSN 1387-7003 R&D Projects: GA ČR GA203/05/2646; GA ČR GA203/00/1042; GA MŠk LC523; GA AV ČR IAA4032701 Grant - others:EPSRC(GB) J/56929; EPSRC(GB) K/05818; EPSRC(GB) M/83360 Institutional research plan: CEZ:AV0Z40320502 Keywords : borane cluster * X-ray structure * NMR spectroscopy Subject RIV: CA - Inorganic Chemistry Impact factor: 1.826, year: 2005

  12. Ten-vertex rhodadithiaborane chemistry:[8-{I(CH2)5}-3-(.eta.5-C5Me5)-arachno-3,7,8,-RhS2B8H9

    Czech Academy of Sciences Publication Activity Database

    Marcías, R.; Barrett, S. A.; Bould, J.; Dörfler, U.; Holub, Josef; Kennedy, J. D.; Thornton-Pett, M.; Štíbr, Bohumil


    Roč. 57, č. 5 (2001), s. 520-522 ISSN 0108-2701 R&D Projects: GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : boranes * heteroboranes * metalladithiaboranes Subject RIV: CA - Inorganic Chemistry Impact factor: 0.570, year: 2001

  13. MSU Ch 2/3 Daily Lower Troposphere Temps with Limb93 Correction L3 1 day 2.5 degree x 2.5 degree V001 (MSULTT) at GES DISC (United States)

    National Aeronautics and Space Administration — The Microwave Sounding Unit (MSU) Lower Troposphere Deep Layer Temperature product (MSULTT) provides gridded lower tropospheric temperatures derived from MSU...

  14. Kinetics and mechanisms for the isomerization of internucleosidic 3'-O-P-CH2-5' and 3'-O-P-CH(OH)-5' linkages to their 2',5'-counterparts

    Czech Academy of Sciences Publication Activity Database

    Lönnberg, T.; Králíková, Šárka; Rosenberg, Ivan; Lönnberg, H.


    Roč. 71, č. 6 (2006), s. 859-870 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40550506 Keywords : nucleosides * nucleotides * RNA Subject RIV: CC - Organic Chemistry Impact factor: 0.881, year: 2006

  15. Threshold Photoelectron Spectroscopy of the Methyl Radical Isotopomers, CH3, CH2D, CHD2 and CD3: Synergy between VUV Synchrotron Radiation Experiments and Explicitly Correlated Coupled Cluster Calculations

    Czech Academy of Sciences Publication Activity Database

    Cunha de Miranda, B. K.; Alcaraz, Ch.; Elhanine, M.; Noller, B.; Hemberger, P.; Fischer, I.; Garcia, G. A.; Soldi-Lose, H.; Gans, B.; Mendes, L. A. V.; Boyé-Péronne, S.; Douin, S.; Žabka, Ján; Botschwina, P.


    Roč. 114, č. 14 (2010), s. 4818-4830 ISSN 1089-5639 Grant - others:CNRS-AVCR(FR) 20201 Institutional research plan: CEZ:AV0Z40400503 Keywords : Threshold photoelectron spectroscopy * isotopomers * clusters Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.732, year: 2010

  16. Activation of ethers and sulfides by organolanthanide hydrides - molecular-structures of (cp-asterisk(2)y)(2)(mu- och(2)ch(2)0)(thf)(2) and (cp-asterisk-ce-2)(2)(mu-o)(thf)(2)

    NARCIS (Netherlands)

    Deelman, B.J; Booij, M.; Meetsma, A.; Teuben, J.H; Kooijman, H.; Spek, A.L.

    Dialkyl ethers, ROR', are cleaved by hydrides (Cp*(2)LnH)(2) (Ln = Y 1a, La 1b, Ce 1c) to form alkoxides Cp*(2)LnOR (2), Cp*(2)LnOR', R'H, and RH. The extent to which either of the C-O bonds of asymmetric substituted dialkyl ethers ROR' is attacked strongly depends on the alkyl substituents but is

  17. Detailed structural characterization of the grafting of [Ta(=CHtBu)(CH2tBu)3] and [Cp*TaMe4] on silica partially dehydroxylated at 700 C and the activity of the grafted complexes toward alkane metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Le Roux, Erwan; Chabanas, Mathieu; Baudouin, Anne; de Mallmann, Aimery; Coperet, Christophe; Quadrelli, E. Allesandra; Thivolle-Cazat, Jean; Basset, Jean-Marie; Lukens, Wayne; Lesage, Anne; Emsley, Lyndon; Sunley, Glenn J.


    The reaction of [Ta({double_bond}CHtBu)(CH{sub 2}tBu){sub 3}] or [Cp*Ta(CH{sub 3}){sub 4}] with a silica partially dehydroxylated at 700 C gives the corresponding monosiloxy surface complexes [({triple_bond}SiO)Ta({double_bond}CHtBu)(CH{sub 2}tBu){sub 2}] and [({triple_bond}SiO)Ta(CH{sub 3}){sub 3}Cp*] by eliminating a {sigma}-bonded ligand as the corresponding alkane (H-CH{sub 2}tBu or H-CH{sub 3}). EXAFS data show that an adjacent siloxane bridge of the surface plays the role of an extra surface ligand, which most likely stabilizes these complexes as in [({triple_bond}SiO)Ta({double_bond}CHtBu)(CH{sub 2}tBu){sub 2}({triple_bond}SiOSi{triple_bond})] (1a') and [({triple_bond}SiO)Ta(CH{sub 3}){sub 3}Cp*({triple_bond}SiOSi{triple_bond})] (2a'). In the case of [({triple_bond}SiO)Ta({double_bond}CHtBu)(CH{sub 2}tBu){sub 2}({triple_bond}SiOSi{triple_bond})], the structure is further stabilized by an additional interaction: a C-H agostic bond as evidenced by the small J coupling constant for the carbenic C-H (H{sub C-H} = 80 Hz), which was measured by J-resolved 2D solid-state NMR spectroscopy. The product selectivity in propane metathesis in the presence of [({triple_bond}SiO)Ta({double_bond}CHtBu)-(CH{sub 2}tBu){sub 2}({triple_bond}SiOSi{triple_bond})] (1a') as a catalyst precursor and the inactivity of the surface complex [({triple_bond}SiO)Ta-(CH{sub 3}){sub 3}Cp*({triple_bond}SiOSi{triple_bond})] (2a') show that the active site is required to be highly electrophilic and probably involves a metallacyclobutane intermediate.

  18. Synthesis, solvatochromism and crystal structure of trans-[Cu(Et2NCH2CH2NH2)2.H2O](NO3)2 complex: Experimental with DFT combination (United States)

    Warad, Ismail; Musameh, Sharif; Badran, Ismail; Nassar, Nashaat N.; Brandao, Paula; Tavares, Carlos Jose; Barakat, Assem


    In this study, two dicationic asymmetrical diamine/copper(II) nitrate salt complexes of the general formula trans-[CuII(NN‧)2.H2O](NO3)2 were successfully synthesized using N,N-dimethylethylenediamine and N,N-diethylethylenediamine as asymmetrical diamine ligands. The structure of complex 2 was identified by X-ray single crystal diffraction analysis confirming that the bidentate ligand N,N-dimethylethylenediamine forms a penta-coordinated complex with an H2O molecule located around the copper(II) ion in a trans configuration. It was found that the metal centre is coordinated in a distorted square pyramidal fashion with a τ value of 0.274. The desired complexes were fully characterized using, MS, UV-Vis, CV, FTIR, TG/DTA, and Hirshfeld surface computational analysis. High level theoretical calculations were also performed in order to investigate the complexes structure, conformers, vibrational frequencies, and their excited states.

  19. Structural Basis for Unusually Long-Wavelenght Charge Transfer Transitions in Complexes [MCl(ECH2CH2NME2)(PR3)] (E=Te, Se; M=Pt, Pd): Experimental Results and TD-DFT Calculations

    Czech Academy of Sciences Publication Activity Database

    Dey, S.; Jain, V. K.; Knödler, A.; Klein, A.; Kaim, W.; Záliš, Stanislav


    Roč. 41, č. 11 (2002), s. 2864-2870 ISSN 0020-1669 R&D Projects: GA MŠk ME 439; GA MŠk OC D15.10 Institutional research plan: CEZ:AV0Z4040901 Keywords : platinum (II( complexes * palladium (II) * spectroelectrochemistry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.950, year: 2002

  20. NATURAL-SCIENCE EDUCATION: SCIENTIFIC AND RELIGIOUS KNOWLEDGE CORRELATION IN THE VIEW OF A SYMMETRY PRINCIPLE. Ch. 2. Examples of religious content selection in general natural science courses based on the principle of symmetry

    Directory of Open Access Journals (Sweden)

    Vitalii L. Gapontsev


    Full Text Available This work is aimed at demonstrating the possibility of the inclusion of religious elements contained in Holy Scripture and Holy Tradition in the general natural scientific courses based on the principle of symmetry.The method used in the work is confined to a comparison of perceptions formed in modern science and is closely related to the forms of symmetry and invariance principles (symmetry principles and, in particular, space-time concepts with those of the Book of Genesis. Such a comparison reveals the following unexpected feature: most profound presentation of modern natural sciences is closer to the provisions of Holy Scripture and Holy Tradition than a look at the same things existed in the earlier stages of the development of science. This allows the authors to formulate the hypothesis that in the process of development of scientific knowledge, it gradually becomes closer to the religious worldview. This process is slow, so its results have become visible only within 3500 years after the establishment of the truth of the Old Testament and 2000 years after the New Testament.Results and scientific novelty. The «firmament of heaven» and «water under the firmament» concepts are explained in the terms of the model of the Kleinert – Planck World crystal and understanding of the properties of matter and fields which are related with the conservation law of the wave-function parity. The relational nature of phenomena such as «life» and «death» in the course of universe evolution as a general trend is considered as the process of lowering the degree of symmetry of matter after the Big Bang wherein the Universe was created. The concepts used by E. Wigner for the description of the structure of the scientific knowledge are analysed. Its structure is determined by shapes and specific principles of the symmetry of exact sciences. The analysis of the concept «natural phenomenon» has shown that they are different in the degree of space-time localization. As the nonlocality of nature phenomenon becomes intensive, the limits of the scientific knowledge are approached. Understanding of creatures with the utmost degree of nonlocality is beyond the scientific knowledge. There is a tendency in modern science to study the behavior of objects in frames of nonlocal spacetime description. This trend is reflected, for example, in a study of the phenomenon of quantum entanglement. It can be stated that in this respect the position of science closes in the positions of the religious worldview.Practical significance. In this paper the authors present a few examples of selection of content of the course based on the Principle of symmetry.

  1. Molecular structures of arachno-decaborane derivatives 6,9-X2B8H10 (X = CH2, NH, Se) including a gas-phase electron-diffraction study of 6,9-C2B8H14

    Czech Academy of Sciences Publication Activity Database

    Hnyk, Drahomír; Bühl, M.; Holub, Josef; Hayes, S. A.; Wann, D. A.; Mackie, I.D.; Borisenko, K.B.; Robertson, H. E.; Rankin, D. W. H.


    Roč. 45, č. 15 (2006), s. 6014-6019 ISSN 0020-1669 R&D Projects: GA MŠk LC523 Grant - others:EPSRC(GB) GR/R17768; EPSRC(GB) EP/C513649 Institutional research plan: CEZ:AV0Z40320502 Keywords : nuclear-magnetic-resonance * chemical-shift calculation * density-functional theory Subject RIV: CA - Inorganic Chemistry Impact factor: 3.911, year: 2006

  2. A Kumada Coupling Catalyst, [Ni{(Ph2P)2N(CH2)3Si(OCH3)3-P,P }Cl2], Bearing a Ligand for Direct Immobilization Onto Siliceous Mesoporous Molecular Sieves

    Czech Academy of Sciences Publication Activity Database

    Stamatopoulos, I.; Giannitsios, D.; Psycharis, V.; Raptopoulou, C. P.; Balcar, Hynek; Zukal, Arnošt; Svoboda, J.; Kyritsis, P.; Vohlídal, J.


    Roč. 2015, č. 18 (2015), s. 3038-3044 ISSN 1434-1948 R&D Projects: GA ČR GAP108/12/1143 Institutional support: RVO:61388955 Keywords : homogenous catalysis * heterogeneous catalysis * cross coupling Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.686, year: 2015

  3. Selective Generation of the Radical Cation Isomers [CH3CN](center dot+) and [CH2CNH](center dot+) via VUV Photoionization of Different Neutral Precursors and Their Reactivity with C2H4

    Czech Academy of Sciences Publication Activity Database

    Polášek, Miroslav; Zins, E. L.; Alcaraz, Ch.; Žabka, Ján; Křížová, Věra; Giacomozzi, L.; Tosi, P.; Ascenzi, D.


    Roč. 120, č. 27 (2016), s. 5041-5052 ISSN 1089-5639 R&D Projects: GA MŠk(CZ) LD14024; GA ČR(CZ) GA14-19693S Institutional support: RVO:61388955 Keywords : COMPLEX ORGANIC-MOLECULES * MILLIMETER EMISSION-LINES * TITANS UPPER-ATMOSPHERE Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.847, year: 2016

  4. Preliminary crystallographic study of native HIV-1 protease inhibited by hydroxyethylamine modified tetrapeptides of Boc-Phe-.psi.[(R/S)-CH(OH)CH2NH]-Phe-Ile-Phe-NH2 type

    Czech Academy of Sciences Publication Activity Database

    Buchtelová, Eva; Hašek, Jindřich; Dohnálek, Jan; Tykarska, E.; Jaskolski, M.; Olivi, L.


    Roč. 6, č. 1 (1999), s. 6-7 ISSN 1211-5894 R&D Projects: GA AV ČR IAA4050811; GA ČR GV203/98/K023 Institutional research plan: CEZ:AV0Z4050913 Keywords : HIV protease * hydroxyethylamine inhibitors * crystallization Subject RIV: CD - Macromolecular Chemistry

  5. In vivo carbon-edited detection with proton echo-planar spectroscopic imaging (ICED PEPSI) : [3,4-(CH2)-C-13] glutamate/glutamine tomography in rat brain

    NARCIS (Netherlands)

    Hyder, F; Renken, R; Rothman, DL


    A method for in vivo carbon-edited detection with proton echo-planar spectroscopic imaging (ICED PEPSI) is described. This method is composed of an echo-planar based acquisition implemented with C-13-H-1 J editing spectroscopy and is intended for high temporal and spatial resolution in vivo

  6. An effective route to fluorine containing asymmetric alpha-aminophosphonates using chiral Bronsted acid catalyst. (United States)

    Bhadury, Pinaki S; Zhang, Yuping; Zhang, Sha; Song, Baoan; Yang, Song; Hu, Deyu; Chen, Zhuo; Xue, Wei; Jin, Linhong


    Asymmetric addition of dialkyl phosphites (--CH2CH3, --CH2CH2CH3, --CH(CH3)2, --CH2(CH2)3CH3, --CH2CH2OCH3 and --CH2CH2OC2H5) induced by chiral organocatalyst e.g. (R)- and (S)-3,3'-[3,5-bis(trifluoromethyl)phenyl]2-1,1'-binaphthyl phosphate on fluorinated aldimines derived from cinnamaldehyde has been found effective to give new bioactive alpha-aminophosphonates in good yields (58-73%) and high enantiomeric excess (64.6%-90.6%) under mild conditions.

  7. Synthesis of functionalized cobaltacarboranes based on the closo-[(1,2-C2B9H11)(2)-3,3 '-Co](-) ion bearing polydentate ligands for separation of M3+ cations from nuclear waste solutions. Electrochemical and liquid-liquid extraction study of selective transfer of M3+ metal cations to an organic phase. Molecular structure of the closo-[(8-(2-CH3O-C5H4-O)-(CH2CH2O)(2)-1,2-C2B9H10)-(1 ',2 '-C2B9H11)-3,3 '-Co]Na determined by X-ray diffraction analysis

    Czech Academy of Sciences Publication Activity Database

    Plešek, Jaromír; Grüner, Bohumír; Heřmánek, Stanislav; Báča, Jiří; Mareček, Vladimír; Jänchenová, Hana; Lhotský, Alexandr; Holub, Karel; Selucký, P.; Rais, J.; Císařová, I.; Čáslavský, Josef


    Roč. 21, 9-10 (2002), s. 975-986 ISSN 0277-5387 R&D Projects: GA MŠk LN00A028; GA MŠk LB98233; GA ČR GA104/01/0142; GA ČR GA203/99/M037; GA ČR GA104/99/1096 Institutional research plan: CEZ:AV0Z4032918 Keywords : carboranes * carba metallaboranes * dicarbollides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.414, year: 2002

  8. Microstructure alterations in the base material, heat affected zone and weld metal of a 440-VVER-reactor pressure vessel caused by high fluence irradiation during long term operation: material: 15 Ch2MFA {approx} 0, 15 C-2,5 Cr-0, 7Mo-0,3 V; Veraenderungen der Mikrostruktur in Grundwerkstoff, WEZ und Schweissgut eines 440-VVER-Reaktordruckbehaelters, verursacht durch Neutronenbestrahlung im langzeitigen Betrieb; Werkstoff: 15 Ch2MFA {approx} 0,15 C-2,5 Cr-0, 7Mo-0,3 V

    Energy Technology Data Exchange (ETDEWEB)

    Maussner, G.; Scharf, L.; Langer, R. [Siemens AG Energieerzeugung KWU, Erlangen (Germany); Gurovich, B. [Russian Research Centre Kurchatov Inst., Moscow (Russian Federation)


    Within the scope of the Tacis `91/1.1 project of the European Community, ``Reactor Vessel Embrittlement``, specimens were taken from the heavily irradiated circumferential welds of a VVER pressure vessel. The cumulated fast neutron fluence in the specimens amounts to up to 6.5 x 10{sup 19} cm{sup -}2 (E > 0.5 MeV). For the multi-laboratory, coordinated study, the specimens were cutted for mechanical testing as well as analytical, microstructural and microanalytical examinations in the base metal, HAZ and weld metal with respect to the effects of reactor operatio and post-irradiation annealing as well as thermal treatment (475 C, 560 C). The analytical transmission electron microscopy (200 kV) revealed the alterations found in the mechanical properties to be due to the formation of black dots and irradiation-induced segregations and accumulations of copper and carbides. These effects, caused by operation, (neutron radiation, temperature), are much more significant in the HAZ than in the base metal. (orig./CB) [Deutsch] Im Rahmen des von der Europaeischen Union beauftragten Tacis `91/1.1 Programms `Reactor Vessel Embrittlement` wurden Bohrkerne aus dem hochbestrahlten Rundnahtbereich eines VVER-Reaktordruckbehaelters entnommen. Die kumulierte schnelle Neutronenfluenz in diesen Proben betraegt bis zu 6,5 x 10{sup 19} cm{sup -2} (E>0,5 MeV). In einer gemeinschaftlichen Untersuchung wurden mechanisch-technologische, chemische sowie mirkostrukturelle Untersuchungen an Grundwerkstoff-, WEZ- und Schweissgutproben im vergleichbaren Ausgangs-, bestrahlten und anschliessend waermebehandelten (475 C, 560 C) Werkstoffzustand durchgefuehrt. Die analytische Durchstrahlelektronenmikroskopie (200 kV) laesst als Ursache fuer die festgestellten Veraenderungen der mechanischen Eigenschaften die Bildung von Versetzungsringen (black dots) sowie von bestrahlungsinduzierten Ausscheidungen und Anreicherungen von Kupfer in den Karbiden erkennen. Diese Effekte, als Folge der betrieblichen Beanspruchung (Neutronenstrahlung, Temperatur) entstanden, treten in der WEZ deutlicher in Erscheinung als im Grundwerkstoff. (orig.)

  9. In situ visualization and quantitative investigation of the distribution of polycyclic aromatic hydrocarbons in the micro-zones of mangrove sediment. (United States)

    Li, Ruilong; Zhu, Yaxian; Zhang, Yong


    The distribution of polycyclic aromatic hydrocarbons (PAHs) in the micro-zones of mangrove sediment is a predominant factors determining PAH bioavailability. In this study, a novel method for the in situ visualization (via microscope) and quantitative investigation of the PAH distribution in the micro-zones of mangrove sediment was established using microscopic fluorescence spectral analysis combined with derivative synchronous fluorescence spectroscopy (MFSA-DSFS). The MFSA-DSFS method significantly suppressed the background fluorescence signal of the sediment (the S/N values increased by over two orders of magnitude). The proportion of the nonpolar organic carbon content in the particulate organic matter (POM) rather than its content in the total organic matter (TOM) showed a significantly positive correlation with the uneven PAH distribution (Relative DC-M values) evaluated using the established method (p micro-zones of aged sediment was higher than that in the spiked sediment. Moreover, the distribution pattern of the PAHs within the mangrove sediment changed to become more homogeneous in the presence of low-molecular-weight organic acids (LMWOAs), which primarily contribute to increasing the POM content. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. The Zwitterion [8,8′-μ-CH2O(CH3)-(1,2-C2B9H10)2-3,3′-Co]0 as a Versatile Building Block To Introduce Cobalt Bis(Dicarbollide) Ion into Organic Molecules

    Czech Academy of Sciences Publication Activity Database

    Plešek, Jaromír; Grüner, Bohumír; Šícha, Václav; Böhmer, V.; Císařová, I.


    Roč. 31, č. 5 (2012), s. 1703-1715 ISSN 0276-7333 R&D Projects: GA MŠk LC523; GA AV ČR IAAX00320901 Institutional research plan: CEZ:AV0Z40320502 Keywords : boranes * carboranes * dicarbollides * X-ray diffraction * NMR Subject RIV: CA - Inorganic Chemistry Impact factor: 4.145, year: 2012

  11. Structures of, and Related Consequences of Deprotonation on, Two C-s-Symmetric Arachno Nine-Vertex Heteroboranes, 4,6-X2B7H9 (X = CH2; S) Studied by Gas Electron Diffraction/Quantum Chemical Calculations and GIAO/NMR

    Czech Academy of Sciences Publication Activity Database

    Wann, D. A.; Lane, P. D.; Robertson, H. E.; Holub, Josef; Hnyk, Drahomír


    Roč. 52, č. 8 (2013), s. 4502-4508 ISSN 0020-1669 R&D Projects: GA ČR GAP208/10/2269 Institutional support: RVO:61388980 Keywords : GAUSSIAN-BASIS SETS * CORRELATED MOLECULAR CALCULATIONS * AB-INITIO CALCULATIONS Subject RIV: CA - Inorganic Chemistry Impact factor: 4.794, year: 2013

  12. Total Syntheses and Initial Evaluation of [Ψ[C(=S)NH]Tpg4]vancomycin, [Ψ[C(=NH)NH]Tpg4]vancomycin, [Ψ[CH2NH]Tpg4]vancomycin and their (4-Chlorobiphenyl)methyl Derivatives: Synergistic Binding Pocket and Peripheral Modifications for the Glycopeptide Antibiotics (United States)

    Okano, Akinori; Nakayama, Atsushi; Wu, Kejia; Lindsey, Erick A.; Schammel, Alex W.; Feng, Yiqing; Collins, Karen C.


    Full details of studies are disclosed on the total synthesis of binding pocket analogues of vancomycin, bearing the peripheral L-vancosaminyl-1,2-D-glucosyl disaccharide, that contain changes to a key single atom in the residue 4 amide (residue 4 carbonyl O → S, NH, H2) designed to directly address the underlying molecular basis of resistance to vancomycin. Also disclosed are studies piloting the late stage transformations conducted on the synthetically more accessible C-terminus hydroxymethyl aglycon derivatives and full details of the peripheral chlorobiphenyl functionalization of all the binding pocket modified vancomycin analogues designed for dual D-Ala-D-Ala/D-Ala-D-Lac binding are reported. Their collective assessment indicate that combined binding pocket and chlorobiphenyl peripherally modified analogues exhibit a remarkable spectrum of antimicrobial activity (VSSA, MRSA, VanA and VanB VRE) and impressive potencies against both vancomycin-sensitive and vancomycin-resistant bacteria (MICs = 0.06–0.005 μg/mL and 0.5–0.06 μg/mL for the amidine and methylene analogues, respectively) and likely benefit from two independent and synergistic mechanisms of action, only one of which is dependent on D-Ala-D-Ala/D-Ala-D-Lac binding. Such analogues are likely to display especially durable antibiotic activity not prone to rapidly acquired clinical resistance. PMID:25750995

  13. The Synthesis and Crystal Structure of a Remarkable Binuclear, Double Pd–Cl–H–O–Pd Bridged Palladium Alcohol Complex. Catalytic Oxidations with Molecular Oxygen mediated by [{[Me2C(OH)CH2CONMe2]Pd(Cl)NO2}2

    NARCIS (Netherlands)

    Kiers, Niklaas H.; Kooijman, Huub; Spek, Anthony L.; Leeuwen, Piet W.N.M. van; Feringa, Bernard


    The Pd(Cl)NO2 complex of N,N-3-trimethyl-3-hydroxybutyramide is dimeric in the solid state with two Pd–Cl–H–O–Pd hydrogen-bond bridges; however, in solution the complex is monomeric and catalytically active in the oxidation of alkenes.

  14. A crystallizable f-element tuck-in complex: the tuck-in tuck-over uranium metallocene [(C{sub 5}Me{sub 5})U{μ-η"5:η"1:η"1-C_5Me_3(CH_2)_2}(μ-H){sub 2}U(C{sub 5}Me{sub 5}){sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Evans, William J.; Miller, Kevin A. [Department of Chemistry, University of California, Irvine, CA (United States); DiPasquale, Antonio G.; Rheingold, Arnold L. [Department of Chemistry and Biochemistry, University of California, San Diego, CA (United States); Stewart, Timothy J.; Bau, Robert [Department of Chemistry, University of Southern California, Los Angeles, CA (United States)


    Long sought structural data on an f-element tuck-in complex have been obtained for the title compound that contains the first example of both tuck-in and tuck-over bonding in a ligand derived from C{sub 5}Me{sub 5}{sup -} by metalation. (Abstract Copyright [2008], Wiley Periodicals, Inc.)

  15. Free energies for degradation reactions of 1,2,3-trichloropropane from ab initio electronic structure theory. (United States)

    Bylaska, Eric J; Glaesemann, Kurt R; Felmy, Andrew R; Vasiliu, Monica; Dixon, David A; Tratnyek, Paul G


    Electronic structure methods were used to calculate the gas and aqueous phase reaction energies for reductive dechlorination (i.e., hydrogenolysis), reductive β-elimination, dehydrochlorination, and nucleophilic substitution by OH− of 1,2,3-trichloropropane. The thermochemical properties ΔH(f)°(298.15 K), S°(298.15 K, 1 bar), and ΔG(S)(298.15 K, 1 bar) were calculated by using ab initio electronic structure calculations, isodesmic reactions schemes, gas-phase entropy estimates, and continuum solvation models for 1,2,3-trichloropropane and several likely degradation products: CH3−CHCl−CH2Cl, CH2Cl−CH2CH2Cl, C•H2−CHCl−CH2Cl, CH2Cl−C•H−CH2Cl, CH2═CCl−CH2Cl, cis-CHCl═CH−CH2Cl, trans-CHCl═CH−CH2Cl, CH2═CH−CH2Cl, CH2Cl−CHCl−CH2OH, CH2Cl−CHOH−CH2Cl, CH2═CCl−CH2OH, CH2═COH−CH2Cl, cis-CHOH═CH−CH2Cl, trans-CHOH═CH−CH2Cl, CH(═O)−CH2CH2Cl, and CH3−C(═O)−CH2Cl. On the basis of these thermochemical estimates, together with a Fe(II)/Fe(III) chemical equilibrium model for natural reducing environments, all of the reactions studied were predicted to be very favorable in the standard state and under a wide range of pH conditions. The most favorable reaction was reductive β-elimination (ΔG(rxn)° ≈ −32 kcal/mol), followed closely by reductive dechlorination (ΔG(rxn)° ≈ −27 kcal/mol), dehydrochlorination (ΔG(rxn)° ≈ −27 kcal/mol), and nucleophilic substitution by OH− (ΔG(rxn)° ≈ −25 kcal/mol). For both reduction reactions studied, it was found that the first electron-transfer step, yielding the intermediate C•H2−CHCl−CH2Cl and the CH2Cl−C•H−CH2Cl species, was not favorable in the standard state (ΔG(rxn)° ≈ +15 kcal/mol) and was predicted to occur only at relatively high pH values. This result suggests that reduction by natural attenuation is unlikely.

  16. Role of the metal oxidation state in the SNS-Cr catalyst for ethylene trimerization: isolation of di- and trivalent cationic intermediates. (United States)

    Jabri, Amir; Temple, Claire; Crewdson, Patrick; Gambarotta, Sandro; Korobkov, Ilia; Duchateau, Robbert


    The reaction of the highly selective [CySCH2CH2N(H)CH2CH2SCy]CrCl3 catalyst precursor with alkyl aluminum activators was examined with the aim of isolating reactive intermediates. Reaction with Me3Al afforded a cationic trivalent chromium alkyl species {[CySCH2CH2N(H)CH2CH2SCy]CrMe(mu-Cl)}2{(AlMe3)2(m-Cl}2.(C7H8)2 (1a). Although it was not possible to obtain crystalline samples of sufficient quality from the reaction with MAO (the most preferred activator), the near-to-identical EPR spectra indicated a very close structural similarity with 1a. Ethylene oligomerization tests clearly revealed that 1 and other cationic trivalent dimeric complexes {[CySCH2CH2N(H)CH2CH2SCy] CrCl(mu-Cl)}2{AlCl4}2.(C7H8)1.5 (2), monomeric [(CySCH2CH2N(H)CH2CH2SCy)CrCl2 (THF)][AlCl4] (3), and {[CySCH2CH2N(H)CH2CH2SCy]Cr(eta2-AlCl4)}{Al2Cl7} (4) adducts display the same catalyst selectivity as the [CySCH2CH2N(H)CH2CH2SCy]CrCl3 complex and, therefore, are probably all precursors to the same catalytically active species. 2, 3, and 4 were obtained upon treatment of [CySCH2CH2N(H)CH2CH2SCy] CrCl3 with different stoichiometric ratios of AlCl3.. When i-BAO activator was used, reduction of the metal center occurred readily, affording {([CySCH2CH2N(H)CH2CH2S Cy]Cr)(mu-Cl)]2}{(i-Bu)2AlCl2}2 (5). 5 is also a selective catalyst, thus indicating that trivalent species are most probably precursors to a divalent catalytically active complex. Reaction of CrCl2(THF)2 with the ligand afforded the labile divalent adduct [CySCH2CH2N(H)CH2CH2SCy]CrCl2(THF) (6), also catalytically active and selective. Instead, deprotonation of the ligand with n-BuLi followed by reaction with CrCl2(THF)2 gave the dinuclear complex [(mu-CySCH2CH2NCH2CH2SCy)CrCl]2 (7), which did not produce oligomers.

  17. α, ω-Cholesterol-Functionalized Low Molecular Weight Polyethylene Glycol as a Novel Modifier of Cationic Liposomes for Gene Delivery

    Directory of Open Access Journals (Sweden)

    Cui-Cui Ma


    Full Text Available Here, three novel cholesterol (Ch/low molecular weight polyethylene glycol (PEG conjugates, termed α, ω-cholesterol-functionalized PEG (Ch2-PEGn, were successfully synthesized using three kinds of PEG with different average molecular weight (PEG600, PEG1000 and PEG2000. The purpose of the study was to investigate the potential application of novel cationic liposomes (Ch2-PEGn-CLs containing Ch2-PEGn in gene delivery. The introduction of Ch2-PEGn affected both the particle size and zeta potential of cationic liposomes. Ch2-PEG2000 effectively compressed liposomal particles and Ch2-PEG2000-CLs were of the smallest size. Ch2-PEG1000 and Ch2-PEG2000 significantly decreased zeta potentials of Ch2-PEGn-CLs, while Ch2-PEG600 did not alter the zeta potential due to the short PEG chain. Moreover, the in vitro gene transfection efficiencies mediated by different Ch2-PEGn-CLs also differed, in which Ch2-PEG600-CLs achieved the strongest GFP expression than Ch2-PEG1000-CLs and Ch2-PEG2000-CLs in SKOV-3 cells. The gene delivery efficacy of Ch2-PEGn-CLs was further examined by addition of a targeting moiety (folate ligand in both folate-receptor (FR overexpressing SKOV-3 cells and A549 cells with low expression of FR. For Ch2-PEG1000-CLs and Ch2-PEG2000-CLs, higher molar ratios of folate ligand resulted in enhanced transfection efficacies, but Ch2-PEG600-CLs had no similar in contrast. Additionally, MTT assay proved the reduced cytotoxicities of cationic liposomes after modification by Ch2-PEGn. These findings provide important insights into the effects of Ch2-PEGn on cationic liposomes for delivering genes, which would be beneficial for the development of Ch2-PEGn-CLs-based gene delivery system.

  18. The family of N -adenine: New entry for adenine–benzamide ...

    Indian Academy of Sciences (India)

    sisting linker, reactive functionality and adenine nucleo- base 1, 2 and 3 were synthesized as described below. Adenine derivatives 7 and 12 were synthesized accord- ing to slightly modified literature procedures and char- acterized spectroscopically.28,29 Boc-NH(CH2CH2O)2-. CH2CH2NH2 4 was synthesized according ...

  19. High-pressure oxidation of ethane

    DEFF Research Database (Denmark)

    Hashemi, Hamid; G. Jacobsen, Jon; Rasmussen, Christian T.


    constants for reactions on the C2H5O2 potential energy surface were adopted from the recent theoretical work of Klippenstein. In the present work, the internal H-abstraction in CH3CH2OO to form CH2CH2OOH was treated in detail. Modeling predictions were in good agreement with data from the present work......, the chain branching sequence CH3CH2OO⟶CH2CH2OOH⟶+O2OOCH2CH2OOH→branching is not competitive, because the internal H-atom transfer in CH3CH2OO to CH2CH2OOH is too slow compared to thermal dissociation to C2H4 and HO2....

  20. Phosphorus–nitrogen compounds: Part 15. Synthesis ...

    Indian Academy of Sciences (India)


    a number of interesting papers have appeared in the literature about the symmetrical. 34 and unsym- metrical. 35,36 spiro- and ansa-. 37 phosphazene archi- tectures. We report here, (i) the synthesis of spiro-crypta phosphazenes, N3P3Cl4{Ph2[OR1O][CH2NR2N CH2]}. [R1 = (CH2)3, R2 = (CH2)4. (5) and R1 = (CH2)4,.

  1. Kinetic and Mechanistic Study of the Reactions of Atomic Chlorine with C2H5Br, n- C3H7Br, and 1,2-C2H4Br2 (United States)

    Laine, P. L.; Nicovich, J. M.; Wine, P. H.


    Halogenated alkanes are present in our atmosphere as a result of both natural and anthropogenic sources. The bromoalkanes ethyl bromide (CH3CH2Br), n-propylbromide (CH3CH2CH2Br), and 1,2-dibromoethane (CH2BrCH2Br) are emitted into the atmosphere from anthropogenic sources, and are thought to play a role in stratospheric ozone depletion. While the primary tropospheric sink for the above bromocarbons is reaction with OH radicals, reaction with chlorine atoms may also represent a non-negligible sink. We have coupled production of Cl by laser flash photolysis with time-resolved monitoring of Br atom appearance by atomic resonance fluorescence spectroscopy to study the kinetics of the title reactions over a wide range of temperature and pressure. Atomic Br is generated by rapid dissociation of the CH2CH2Br product of Cl + CH3CH2Br, the CH3CHCH2Br product of Cl + CH3CH2CH2Br, and the only possible H-abstraction product of Cl + CH2BrCH2Br. By comparing product Br signal strengths with those obtained when Cl removal is dominated by reaction with Br2, temperature-dependent branching ratios for abstraction of the â hydrogen are obtained for the Cl + CH3CH2Br and Cl + CH3CH2CH2Br reactions.

  2. Oxygenates for Advanced Petroleum-Based Diesel Fuels (United States)


    CH3OCH2OCH2CH2OCH2OCH3 42.6 1.0050 68 13.8 P Diglyme CH3OCH2CH2OCH2CH2OCH3 35.8 0.9451 67 17.4 P Diethylene glycol monoethyl ether CH3CH2OCH2CH2OCH2CH2OH...Vol.% Water D Diethylene glycol monoethyl ether 25 NA ------ ------ ------ ------ ------ D Dimethyl Succinate 27 NA...7 13 / 0 9.5 / 1.5 6.5 / 3.5, b D Diethylene glycol monoethyl ether 25 NA ------ ------ ------ ------ ------ A 2-Ethoxy ethyl acetate 0 0 0.125

  3. Polyamines (United States)

    Marton, Laurence J.

    The polyamines spermidine [NH2(CH2)3NH(CH2)4NH2] and spermine [NH2(CH2)3NH(CH2)4NH(CH2)3NH2] and their diamine precursor, putrescine [NH2(CH2)4NH2], have been the subject of intense study relative to their potential as tumor markers during the past decade (1). These compounds have been implicated in numerous biochemical reactions and have been clearly associated with cellular growth processes. A number of publications have reviewed our present knowledge regarding these compounds, including their relationship to human disease (2-6).

  4. Experimental study of thermodynamic and transport properties of binary mixtures of poly(ethylene glycol diacrylate and alcohols at different temperatures

    Directory of Open Access Journals (Sweden)

    Vuksanović Jelena M.


    Full Text Available Experimental density r, refractive index nD and viscosity h data of three binary systems of poly(ethylene glycol diacrylate (PEGDA + ethanol, + 1-propanol, and + 1-butanol were measured at eight temperatures from (288.15 to 323.15 K, with temperature step of 5 K, and at atmospheric pressure. The experimental data were correlated as a function of PEGDA mole fraction and temperature. Densities and refractive indices of the investigated mixtures could be fitted well with exponential function vs. composition, including temperature dependence of parameters, while in the case of viscosities polynomial function fits well over a mixture’s composition. In the case of temperature correlation, all three properties (ρ, lnη and nD exhibit linear trend. The viscosity modeling was performed using four models: UNIFAC-VISCO, ASOG-VISCO, Mc-Allister and Teja-Rice. For application of UNIFAC-VISCO model interaction parameters of following groups were determined: CH2=CH/CH3, CH2=CH/CH2, CH2=CH/OH, CH2=CH/CH2O and CH2=CH/COO. Also, in the same way binary interaction parameters used in ASOG-VISCO of the following groups were determined: CH2=CH/CH2, CH2=CH/OH, CH2=CH/CH2O and CH2=CH/COO. [Projekat Ministarstva nauke Republike Srbije, br. 172063

  5. Periphery-palladated carbosilane dendrimers : Synthesis and reactivity of model organopalladium(II) and (IV) complexes : Crystal structure of [PdMe(C6H4(OCH2Ph)-4)(bpy)] (bpy=2,2'-bipyridine

    NARCIS (Netherlands)

    Koten, G. van; Hovestad, N.J.; Hoare, J.L.; Jastrzebski, J.T.B.H.; Canty, A.J.; Smeets, W.J.J.; Spek, A.L.


    A carbosilane dendrimer with 12 peripheral iodoarene groups, [Si{(CH2)3Si((CH2)3SiMe2(C6H4CH2OC6H4I-4))3}4] (G1-ArI, 9), and the corresponding G0 model compound [Si{(CH2)3SiMe2(C6H4CH2OC6H4I-4)}4] (G0-ArI, 8) have been prepared from [Si{(CH2)3Si((CH2)3SiMe2(C6H4CH2Br))3}4] (G1-Br, 7) and the

  6. CCSD(T) study of the infrared spectrum of ethyl-methyl-ether isotopic varieties

    International Nuclear Information System (INIS)

    Senent, M.L.; Ruiz, R.; Villa, M.; Dominguez-Gomez, R.


    Band positions for the infrared bands of various ethyl-methyl-ether isotopomers (CH 3 CH 2 OCH 2 D, CH 2 DCH 2 OCH 3 , CH 3 CH 2 OCD 3 , CD 3 CH 2 OCH 3 , CH 3 CD 2 OCH 3 , CH 3 CH 2 O 13 CH 3 , 13 CH 3 CH 2 OCH 3 , and CH 3 13 CH 2 OCH 3 ) are determined using second order perturbation theory. For species showing G 18 symmetry, band position are calculated variationally from a CCSD(T)/cc-pVTZ three-dimensional potential energy surface corrected vibrationally. Potential energy barriers, fundamental frequencies, and rotational constants for excited vibrational levels, are also provided. Calculated frequencies for CH 3 CH 2 OCD 3 confirm experimental assignments and our predictions for the most abundant isotopomer .

  7. Centrifugal washing and recovery as an improved method for obtaining lignin precipitated from South African kraft mill black liquor

    CSIR Research Space (South Africa)

    Namane, M


    Full Text Available 2-methoxy-3methyl-phenol * 17 24.44 154.1 OCH3 OCH3 Phenol, 2,6-dimethoxy 18 24,63 164.1 CH2CH=CH2 OCH3 Eugenol 19 24.77 151.1 O=CCH3 OCH3 Apocynin 20 24.95 137.1 CH2CH2(CH3 or OH) OCH3 Phenol, 2-methoxy-4-propyl or Homovanillyl alcohol 21...

  8. Rate Constants for the Reactions of OH with CH(sub 3)Cl, CH(sub 2) C1(sub 2), CHC1(sub 3)and CH(sub 3)Br (United States)

    Hsu, H-J.; DeMore, W.


    Rate constants for the reactions of OH with CH3C1, CH2Cl2, CHCl3 and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2)and for CH2Cl2, HFC-161 (CH3CH2F).

  9. Ruthenium(II) piano stool coordination compounds with aminomethylphosphanes: Synthesis, characterisation and preliminary biological study in vitro. (United States)

    Płotek, Michał; Starosta, Radosław; Komarnicka, Urszula K; Skórska-Stania, Agnieszka; Kołoczek, Przemysław; Kyzioł, Agnieszka


    Reaction of {[Ru(η 6 -p-cymene)Cl] 2 (μ-Cl) 2 } (1) with aminomethylphosphane derived from morpholine (P{CH 2 N(CH 2 CH 2 ) 2 O} 3 (A), PPh 2 {CH 2 N(CH 2 CH 2 ) 2 O} (B)) or piperazine (P{CH 2 N(CH 2 CH 2 ) 2 NCH 2 CH 3 } 3 (C), PPh 2 {CH 2 N(CH 2 CH 2 ) 2 NCH 2 CH 3 } (D)) results in four new piano stool ruthenium(II) coordination compounds: [Ru(η 6 -p-cymene)Cl 2 (A)] (2A), [Ru(η 6 -p-cymene)Cl 2 (B)] (2B), [Ru(η 6 -p-cymene)Cl 2 (C)] (2C) and [Ru(η 6 -p-cymene)Cl 2 (D)] (2D). Every complex was fully characterized using spectroscopic methods ( 1 H, 13 C{ 1 H}, 31 P{ 1 H} NMR and ESI-MS), elemental analysis, X-ray single crystal diffraction and DFT calculations. Preliminary studies of in vitro cytotoxicity on the A549 (human lung adenocarcinoma) and MCF7 (human breast adenocarcinoma) cell lines revealed 2A-2D activity in the same order of magnitude as in the case of cisplatin. Additionally, the study confirmed the ability of 2A-2D to interact with DNA helix and transferrin. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Vapor Phase Self-assembled Monolayers for Anti-stiction Applications in MEMS

    DEFF Research Database (Denmark)

    Zhuang, Yanxin; Hansen, Ole; Knieling, Thomas


    (CF2)7(CH2)2SiCl3 (FDTS), and CH3(CH2)17(CH2)2SiCl3 (OTS). The SAM coatings that were grown on silicon substrates were characterized with respect to static contact angle, surface energy, roughness, nanoscale adhesive force, nanoscale friction force, and thermal stability. The best overall anti...

  11. Synthesis and characterization of a heptadentate (N 4 O 3 ) schiff ...

    African Journals Online (AJOL)

    CH2CH2N=CH(2-OH-5-BrC6H3)]3} (H3L6) and associated neutral Gd(III), La(III) and Sm(III) complexes, were synthesized. The new compounds were characterized by IR spectroscopy, elemental analysis and mass spectrometry in all cases and ...

  12. Synthesis and characterization of technetium(III) complexes containing 2,2'-bipyridine and 1,10-phenanthroline. X-ray crystal structures of cis (Cl),trans(P)-[TcCl2(P(CH3)2C6H5)2(bpy)]B(C6H5)4, cis (Cl),trans(P)-[TcCl2(P(CH3)2C6H5)2(phen)]B(C6H5)4, and cis (Cl),trans(P)-[TcCl2(P(CH3CH2)(C6H5)2)2(bpy)]SO3CF3

    International Nuclear Information System (INIS)

    Wilcox, B.E.; Ho, D.M.; Deutsch, E.


    Technetium(III) complexes of the general formula cis(Cl),trans(P)-[TcCl 2 (P) 2 L] + , where (P) is dimethylphenylphosphine (PMe 2 Ph) or ethyldiphenylphosphine (PEtPh 2 ) and L is 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (Me 2 bpy), or 1,10-phenanthroline (phen), have been synthesized and characterized. They are prepared by L substitution onto, with concomitant displacement of one chloride and one phosphine ligand from, the mer-TcCl 3 (P) 3 starting material in refluxing ethanol. Analysis of these complexes by fast atom bombardment mass spectrometry (in the positive ion mode) provides fingerprint mass spectra that exhibit peaks assigned to the molecular ion M + as well as peaks assigned to M + minus one or more monodentate ligands. Results of single-crystal x-ray structure determinations of cis(Cl),trans(P)-[TcCl 2 (PMe 2 Ph) 2 (bpy)]BPh 4 (A), cis(Cl),trans(P)-[TcCl 2- (PMe 2 Ph) 2 (phen)]BPh 4 (B), and cis(Cl),trans(P)-[TcCl 2 (PEtPh 2 ) 2 (bpy)]SO 3 CF 3 (C), with formula weights of 921.62, 945.64, and 903.65, respectively are reported. 26 refs., 5 figs., 5 tabs

  13. Synthesis of fluorinated ReCl(4,4'-R2-2,2'-bipyridine)(CO)3 complexes and their photophysical characterization in CH3CN and supercritical CO2. (United States)

    Doherty, Mark D; Grills, David C; Fujita, Etsuko


    Two new CO(2)-soluble rhenium(I) bipyridine complexes bearing the fluorinated alkyl ligands 4,4'-(C(6)F(13)CH(2)CH(2)CH(2))(2)-2,2'-bipyridine (1a), and 4,4'-(C(8)F(17)CH(2)CH(2)CH(2))(2)-2,2'-bipyridine (1b) have been prepared and their photophysical properties investigated in CH(3)CN and supercritical CO(2). Electrochemical and spectroscopic characterization of these complexes in CH(3)CN suggests that the three methylene units effectively insulate the bipyridyl rings and the rhenium center from the electron-withdrawing effect of the fluorinated alkyl chains. Reductive quenching of the metal-to-ligand charge-transfer excited states with triethylamine reveals quenching rate constants in supercritical CO(2) that are only 6 times slower than those in CH(3)CN.

  14. Absolute rate constants for the reaction of NO with a series of peroxy radicals in the gas at 295 K

    DEFF Research Database (Denmark)

    Sehested, J.; Nielsen, O.J.; Wallington, T.J.


    The rate constants for the reaction of NO with a series of peroxy radicals: CH3O2, C2H5O2, (CH3)3CCH2O2, (CH3)3CC(CH3)2CH2O2, CH2FO2, CH2ClO2, CH2BrO2, CHF2O2, CF2ClO2, CHF2CF2O2, CF3CF2O2, CFCl2CH2O2 and CF2ClCH2O2 were measured at 298 K and a total pressure of 1 atm. The rate constants were...

  15. Stability constants of glutarate complexes of copper(II), zinc(II), cobalt(II) and uranyl(II) by paper electrophoresis

    International Nuclear Information System (INIS)

    Singh, R.K.P.; Yadava, J.R.; Yadava, K.L.


    Stability constants of Copper(II), Zinc(II), Cobalt(II) and Uranyl(II) glutarates have been determined by paper electrophoresis. Glutaric acid (0.005 mol dmsup(-3)) was added to the background electrolyte : 0.1 mol dmsup(-3) HClO 4 . The proportions of (CH 2 ) 3 COOH COO - and (CH 2 ) 3 C 2 O 4 2- were varied by changing the pH of the electrolyte. These anions yielded the complexes Cu(CH 2 ) 3 C 2 O 4 , [Zn(CH 2 ) 3 COOH COO] + [Co(CH 2 ) 3 COOH COO] + and UO 2 (CH 2 ) 3 C 2 O 4 whose stability constants are found to be 10sup(3.9), 10sup(2.9), 10sup(2.7) and 10sup(13.5) respectively. (author)

  16. Investigation of the interfacial bonding in composite propellants. 1,3,5-Trisubstituted isocyanurates as universal bonding agents

    Directory of Open Access Journals (Sweden)



    Full Text Available A series of 1,3,5-trisubstituted isocyanurates (substituents: CH2CH2OH, CH2CH=CH2 and CH2CH2COOH was synthesized according to a modified literature procedure. Experimental investigations included modification of the synthetic procedure in terms of the starting materials, solvents, temperature, isolation techniques, as well as purification and identification of the products. All the synthesized isocyanurates were identified by their melting point and FTIR, 1H NMR and UV spectroscopic data. Fourier transform infrared spectrophotometry was also used to study the interaction between ammonium perchlorate, hydroxyl terminated poly(butadiene, carboxyl terminated poly(butadiene, poly(butadiene-co-acrylonitrile, poly(propylene ether, cyclotrimethylenetrinitramine and the compounds synthesized in this work, which can serve as bonding agents. The results show that tris(2-hydroxyethylisocyanurate is a universal bonding agent for the ammonium perchlorate/carboxyl terminated poly(butadiene/cyclotrimethylenetrinitramine composite propellant system.

  17. Assessment of diagnostic methods for determining degradation of check valves

    International Nuclear Information System (INIS)

    Haynes, H.D.; Farmer, W.S.


    The Oak Ridge National Laboratory (ORNL) has carried out a comprehensive aging assessment of check valves in support of the Nuclear Plant Aging Research (NPAR) program. This paper provides a summary of the ORNL check valve aging assessment with emphasis on the identification, evaluation, and application of check valve monitoring methods and techniques. Several check valve monitoring methods are described and compared. These methods include: acoustic emission monitoring, ultrasonic inspection, magnetic flux signature analysis (MFSA), external magnetics. These diagnostic technologies were shown to be useful in determining check valve condition (e.g., disc position, disc motion, and seat leakage), although none of the methods was by itself, successful in monitoring all three condition indicators. The combination of acoustic emission with either ultrasonics or one of the magnetic technologies, however, yields a monitoring system that succeeds in providing the sensitivity to detect all major check valve operating conditions. Other areas covered in the paper include descriptions of relevant regulatory issues, utility group activities, and interactions ORNL has had with outside organizations for the purpose of disseminating research results

  18. Recent improvements in check valve monitoring methods

    International Nuclear Information System (INIS)

    Haynes, H.D.


    In support of the NRC Nuclear Plant Aging Research (NPAR) program, ORNL has carried out an evaluation of three check valve monitoring methods: acoustic emission, ultrasonic inspection, and magnetic flux signature analysis (MFSA). This work has focussed on determining the capabilities of each method to provide diagnostic information useful in determining check valve aging and service wear effects (degradation) and undesirable operating modes. In addition, as part of the ORNL Advanced Diagnostic Engineering Research and Development Center (ADEC), two novel nonintrusive monitoring methods were developed (external ac- and dc-magnetic monitoring) that provide several improvements over the other methods. None of the examined methods could, by themselves, monitor the instantaneous position and motion of check valve internals and valve leakage; however, the combination of acoustic emission monitoring with one of the other methods provides the means to determine vital check valve operational information. This paper describes the benefits and limitations associated with each method and includes recent laboratory and field test data to illustrate the capabilities of these methods to detect simulated check valve degradation. 3 refs., 22 figs., 4 tabs

  19. Recent improvements in check valve monitoring methods

    International Nuclear Information System (INIS)

    Haynes, H.D.


    In support of the NRC Nuclear Plant Aging Research (NPAR) program, ORNL has carried out an evaluation of three check valve monitoring methods: acoustic emission, ultrasonic inspection, and magnetic flux signature analysis (MFSA). This work has focused on determining the capabilities of each method to provide diagnostic information useful in determining check valve aging and service wear effects (degradation) and undesirable operating modes. In addition, as part of the ORNL Advanced Diagnostic Engineering Research and Development Center (ADEC), two noval nonintrusive monitoring methods were developed (external ac- and dc-magnetic monitoring) that provide several improvements over the other methods. None of the examined methods could, by themselves, monitor the instantaneous position and motion of check valve internals and valve leakage; however, the combination of acoustic emission monitoring with one of the other methods provides the means to determine vital check valve operational information. This paper describes the benefits and limitations associated with each method and includes recent laboratory and field test data to illustrate the capabilities of these methods to detect simulated check valve degradation. 3 refs., 22 figs., 4 tabs

  20. Response to the Comment on Paper 'Water vapor Enhancement of Rates of Peroxy Radical Reactions', Int. J. Chem. Kinetics, 47, 395, 2015

    Energy Technology Data Exchange (ETDEWEB)

    Kumbhani, Sambhav R.; Cline, Taylor S.; Killian, Marie C.; Clark, Jared M.; Keeton, William J.; Hansen, Lee D.; Shirts, Randall B.; Robichaud, David J.; Hansen, Jaron C.


    Comments provided here aid in understanding the effect of water vapor on the rate of the self-reaction of HOCH2CH2O2 recently reported by Kumbhani et al. [1] Kumbhani et al. asserts that water vapor increases the rate of the HOCH2CH2O2 self-reaction by formation of an HOCH2CH2O2-H2O complex.

  1. Syntheses, structures, thermal stabilities and luminescence of two new lead sulfonates with phosphonate, carboxylate and pyridine

    International Nuclear Information System (INIS)

    Fu, Ruibiao; Hu, Shengmin; Wu, Xintao


    Hydrothermal reactions of Pb 2+ ion with disodium 4,4'-bis(2-sulfonatostyryl)biphenyl (Na 2 L1), 4-pyridyl-CH 2 N(CH 2 COOH)(CH 2 PO 3 H 2 ) (H 3 L2) and 4,4'-bipyridine (4,4'-bipy) afforded two new lead sulfonates, namely, [Pb 4 (L1) 2 (HL2) 2 (H 2 O)

  2. Thermal behavior of novel hybrid inorganic-organic phosphazene polymers

    NARCIS (Netherlands)

    Bosscher, G; Wieringa, RH; Jekel, AP; vandeGrampel, JC

    The thermal behavior of the following systems have been investigated by TGA and XPS: the homopolymer of N3P3Cl4(CH3)(CH2C6H4CH=CH2) (1), copolymers of 1 with MMA and styrene, and copolymers of N3P3Cl4(i-C3H7) {C[OC(O)CH3]=CH2} (2) with MMA and styrene. Upon heating under TGA conditions the highest

  3. Kinetics of the degradation of sulfur mustard on ambient and moist concrete

    International Nuclear Information System (INIS)

    Brevett, Carol A.S.; Sumpter, Kenneth B.; Nickol, Robert G.


    The rate of degradation of the chemical warfare agent sulfur mustard, bis(2-chloroethyl) sulfide, was measured on ambient and moist concrete using 13 C Solid State Magic Angle Spinning Nuclear Magnetic Resonance (SSMAS NMR). Three samples of concrete made by the same formulation, but differing in age and alkalinity were used. The sulfur mustard eventually degraded to thiodiglycol and 1,4-oxathiane via the intermediate sulfonium ions CH-TG, H-TG, H-2TG and O(CH 2 CH 2 ) 2 S + CH 2 CH 2 OH on all of the concrete samples, and in addition formed 8-31% vinyl moieties on the newer, more alkaline concrete samples. This is the first observation of the formation of O(CH 2 CH 2 ) 2 S + CH 2 CH 2 OH on a solid substrate. The addition of 2-chloroethanol to concrete on which mustard had fully degraded to thiodiglycol and 1,4-oxathiane resulted in the formation of O(CH 2 CH 2 ) 2 S + CH 2 CH 2 OH, thus demonstrating the reversibility of sulfur mustard degradation pathways. The sulfur mustard degradation half-lives on ambient concrete at 22 deg. C ranged from 3.5 to 54 weeks. When the substrates were moistened, the degradation half-lives at 22 deg. C ranged from 75 to 350 h. The degradation of sulfur mustard occurred more quickly at elevated temperatures and with added water. The non-volatile toxic sulfonium ions persisted for months to years on concrete at 22 deg. C and weeks to months on concrete at 35 deg. C, before decomposing to the relatively non-toxic compounds thiodiglycol and 1,4-oxathiane

  4. 593 The Spirit of Adventure and the Art of Creation

    Indian Academy of Sciences (India)

    H. H. H. O. H. N. H. N. N. N. Et. H. O. MeO2C. O. O. Mg. 645. Cephalosporin- C. N. S. O. CH2OAc. C. H. HN. COCH2CH2CH2 CH. O. OH. H. CO2. -. NH3. +. 649. Crystallized Cyanocobalamin. (Vitamin B12). Credit: Stefan Eberhard, The. University of Georgia, Complex. Carbohydrate Research Center,. Athens, Georgia USA ...

  5. 4,4´-(Hexane-1,6-diyldioxy)dianiline


    Khan, Muhammad Saif Ullah; Akhter, Zareen; Bolte, Michael; Siraj, Amna; Siddiqi, Humaira Masood


    The complete molecule of the title compound, C18H24N2O2, is generated by a crystallographic inversion centre. The torsion angles in the hexa­methyl­ene chain are consistent with an anti­periplanar conformation, whereas the conformation of the O—CH2CH2CH2 unit is gauche. The three-dimensional crystal packing is stabilized by N—H⋯O and N—H⋯N hydrogen bonding.

  6. 4,4′-(Hexane-1,6-diyldioxydianiline

    Directory of Open Access Journals (Sweden)

    Humaira M. Siddiqi


    Full Text Available The complete molecule of the title compound, C18H24N2O2, is generated by a crystallographic inversion centre. The torsion angles in the hexamethylene chain are consistent with an antiperiplanar conformation, whereas the conformation of the O—CH2CH2CH2 unit is gauche. The three-dimensional crystal packing is stabilized by N—H...O and N—H...N hydrogen bonding.

  7. Synthesis of methyltrioxorhenium(VII) arylamine complexes and mono- and bis(ortho)-chelated arylaminorhenium(VII) trioxides

    NARCIS (Netherlands)

    Koten, G. van; Rietveld, M.H.P.; Nagelholt, L.; Grove, D.M.; Veldman, N.; Spek, A.L.; Rauch, M.U.; Hermann, W.


    From the reaction of MeReO{3} with the neutral arylamine C{6}H{5}CH{2}NMe{2} and the aryldiamine C{6}H{4}(CH{2}NMe{2}){2}-1, 3, have been isolated in good yields the 1/1 adduct complex [MeReO{3}.C{6}H{5}CH{2}NMe{2}], 1, and the21 adduct complex [(MeReO{3}){2} . C{6}H{4}(CH{2}NMe{2}){2}-1,3], 2,

  8. Structural aspects of lithium arenethiolate complexes with intramolecular coordinating amine donors

    NARCIS (Netherlands)

    Koten, G. van; Janssen, M.D.; Rijnberg, E.; Wolf, C.A. de; Hogerheide, M.P.; Kruis, D.; Kooijman, H.; Spek, A.L.


    Reaction of aryllithium reagents LiR (R = C6H4((R)-CH(Me)NMe2)-2 (1a), C6H3(CH2NMe2)2-2,6 (1b), C6H4(CH2N(Me)CH2CH2OMe)-2 (1c)) with 1 equiv of sulfur (1/8 S8) results in the quantitative formation of the corresponding lithium arenethiolates [Li{SC6H4((R)-CH(Me)NMe2)-2}]6 (3),

  9. Preparation of “Constrained Geometry” Titanium Complexes of [1,2]Azasilinane Framework for Ethylene/1-Octene Copolymerization

    Directory of Open Access Journals (Sweden)

    Seul Lee


    Full Text Available The Me2Si-bridged ansa-Cp/amido half-metallocene, [Me2Si(η5-Me4C5(NtBu]TiCl2, termed a “constrained-geometry catalyst (CGC”, is a representative homogeneous Ziegler catalyst. CGC derivatives with the [1,2]azasilinane framework, in which the amide alkyl substituent is joined by the Si-bridge, were prepared, and the catalytic performances of these species was studied. Me4C5HSi(Me(CH2CH=CH2-NH(C(R(R’CH=CH2 (R, R’ = H or methyl; Me4C5H = tetramethylcyclopentadienyl was susceptible to ring closure metathesis (RCM when treated with Schrock’s Mo-catalyst to afford -Si(Me4C5H(MeCH2CH=CHC(R(R’NH- containing a six-membered ring framework. Using the precursors and the products of RCM, various CGC derivatives, i.e., [-Si(η5-Me4C5(MeCH2CH=CHC(R(HN-]TiMe2 (13, R = H; 15, R = Me, [-Si(η5-Me4C5(MeCH2CH2CH2CH2N]TiMe2 (14, [(η5-Me4C5Si(Me(CH2CH=CH2NCH2CH=CH2]TiMe2 (16, [(η5-Me4C5Si (Me(CH=CH2NCH2CH=CH2]TiMe2 (17, and [(η5-Me4C5Si(Me(CH2CH3NCH2CH2CH3]TiMe2 (18, were prepared. The catalytic activity of the newly prepared complexes was lower than that of CGC when activated with [Ph3C][B(C6F54]/iBu3Al. However, the catalytic activity of these species was improved by using tetrabutylaluminoxane ([iBu2Al]2O instead of iBu3Al and the activity of 14/[Ph3C][B(C6F54]/[iBu2Al]2O was comparable to that of CGC/[Ph3C][B(C6F54]/iBu3Al (4.7 and 5.0 × 106 g/mol-Ti, respectively. Advantageously, the newly prepared complexes produced higher molecular weight poly(ethylene-co-1-octenes than CGC.

  10. Oxidation of heteroleptic diarylpalladium compounds with tert-butyl hydroperoxide. Substituent effects in aromatic oxidation reactions

    NARCIS (Netherlands)

    Koten, G. van; Valk, J.-M.; Boersma, J.


    A series of heteroleptic diarylpalladium compounds, containing both a naphthyl (1-C10H6CH2NMe2-2 or 1-C10H5CH2NMe2-2-Me-3) and a phenyl (1-C6H4CH2NMe2-2 or 1-C6H3CH2NMe2-2-Me-x, x = 3, 5, 6) monoanionic C,N-bidentate ligand, was reacted with tert-butyl hydroperoxide (TBHP) to give selective oxygen

  11. Acetylcholinesterase and Acetylcholine Receptor (United States)


    formaldehyde in the active site. tert-Butyl peracetate, (CH3 ) 3 COOCOCH3 , acted as both a substrate, -10% as reactive as AcCh, and as an...BrPin had K, = 0.7 mM for Torpedo AcChE, 0.2 mM for eel enzyme. 4- Oxo -N,N,N-trimethylpentaminium, (CH 3 ) 3 N+CH2 - CH2 CH2 COCH. , had K, = 0.2 mM...This compound, examined as a substrate, appeared to hydrolyze slowly. Chloromethyl acetate, CHCO2 CH2 C1, was synthesized from formaldehyde and

  12. Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S{sub 2}CN(iPr)CH{sub 2}CH{sub 2}OH]{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Yee Seng; Halim, Siti Nadiah Abdul [Malaya Univ., Kuala Lumpur (Malaysia). Dept. of Chemistry; Tiekink, Edward R.T. [Malaya Univ., Kuala Lumpur (Malaysia). Dept. of Chemistry; Sunway Univ., Bandar Sunway (Malaysia). Centre for Chemical Crystallography


    Crystallization of Cd[S{sub 2}CN(iPr)CH{sub 2}CH{sub 2}OH]{sub 2} from ethanol yields the coordination polymer [{Cd[S_2CN(iPr)CH_2CH_2OH]_2}.EtOH]{sub ∞} (1) within 3 h. When the solution is allowed to stand for another hour, the needles begin to dissolve and prisms emerge of the supramolecular isomer (SI), binuclear {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2}.2EtOH (2). These have been fully characterized spectroscopically and by X-ray crystallography. Polymeric 1 has 2-fold symmetry and features dithiocarbamate ligands coordinating two octahedral Cd atoms in a μ{sub 2}κ{sup 2}-tridentate mode. Binuclear 2 is centrosymmetric with two ligands being μ{sub 2}κ{sup 2}-tridentate as for 1 but the other two being κ{sup 2}-chelating leading to square pyramidal geometries. The conversion of the kinetic crystallization product, 1, to thermodynamic 2 is irreversible but transformations mediated by recrystallization (ethanol and acetonitrile) to related literature SI species, namely coordination polymer [{Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 3}.MeCN]{sub ∞} and binuclear {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2}.2H{sub 2}O.2MeCN, are demonstrated, some of which are reversible. Three other crystallization outcomes are described whereby crystal structures were obtained for the 1:2 co-crystal {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2}:2[3-(propan-2-yl)-1,3-oxazolidine-2-thione] (3), the salt co-crystal [iPrNH{sub 2}(CH{sub 2}CH{sub 2}OH)]{sub 4}[SO{sub 4}]{sub 2}{Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2} (4) and the salt [iPrNH{sub 2}(CH{sub 2}CH{sub 2}OH)]{Cd[S_2CN(iPr)CH_2CH_2OH]_3} (5). These arise as a result of decomposition/oxidation of the dithiocarbamate ligands. In each of 3 and 4 the binuclear {Cd[S_2CN(iPr)CH_2CH_2OH]_2}{sub 2} SI, as in 2, is observed strongly suggesting a thermodynamic preference for this form.

  13. A study of formaldehyde sources in air (United States)

    Shen, Haiwei

    Formaldehyde (CH2O) is a central component of photooxidation chemistry. The atmospheric sources of CH2O involve a complex mixture of biogenic and anthropogenic volatile organic compounds (VOCs). This study explores the geographical and altitudinal variations of CH2O production from its precursors over the Eastern U.S. and assesses the contributions from biogenic and anthropogenic VOC emissions to atmospheric CH2O. Measurements of airborne CH2O and hydrocarbons over North America and model results were used to evaluate CH2O production from its precursors. Source attribution results from a photochemical box model indicate 95% of the CH2O arose in various proportions from a mixture of methane, isoprene, methyl hydroperoxide, methanol, and a peroxyacetyl group. Methane on average contributed 32% at altitudes below 2 km to CH2O production, 43% in 2-6 km, and 52% in 6-12 km. It was the predominant CH 2O source in 1-12 km. Isoprene served as a major source of CH2 O (range 0-72%, average 17%) over the southeastern U.S. region within 0-1-km layer. Methyl hydroperoxide was one of the predominant contributors over the ocean and averaged from 6 to 33% in all layers. Production from the peroxyacetyl group and methanol were 7-17% and 10-14% on average in the layers in 0-12 km, respectively. A compound specific radiocarbon analysis technique was developed for atmospheric CH2O to examine its biogenic and anthropogenic carbon fraction. The method used filter collection, a preparative capillary gas chromatography isolation technique, and AMS detection. Ambient samples were collected on the roof of the CACS building at the Bay Campus of the University of RI, Narragansett, RI. The 14CH2O data, 48-hour back trajectories, and VOC observations from the RI Department of Environmental Management were used to assess the relative contributions of biogenic and fossil precursors to CH2O. The results show a large fraction of fossil/industrial carbon in collected CH2O samples and imply the

  14. Theoretical study of isomerization and decomposition of propenal

    International Nuclear Information System (INIS)

    Chin, Chih-Hao; Lee, Shih-Huang


    We investigated the dynamics of isomerization and multi-channel dissociation of propenal (CH 2 CHCHO), methyl ketene (CH 3 CHCO), hydroxyl propadiene (CH 2 CH 2 CHOH), and hydroxyl cyclopropene (cyclic-C 3 H 3 -OH) in the ground potential-energy surface using quantum-chemical calculations. Optimized structures and vibrational frequencies of molecular species were computed with method B3LYP/6-311G(d,p). Total energies of molecules at optimized structures were computed at the CCSD(T)/6-311+G(3df,2p) level of theory. We established the potential-energy surface for decomposition to CH 2 CHCO + H, CH 2 CH + HCO, CH 2 CH 2 /CH 3 CH + CO, CHCH/CH 2 C + H 2 CO, CHCCHO/CH 2 CCO + H 2 , CHCH + CO + H 2 , CH 3 + HCCO, CH 2 CCH + OH, and CH 2 CC/cyclic-C 3 H 2 + H 2 O. Microcanonical rate coefficients of various reactions of trans-propenal with internal energies 148 and 182 kcal mol -1 were calculated using Rice-Ramsperger-Kassel-Marcus and Variational transition state theories. Product branching ratios were derivable using numerical integration of kinetic master equations and the steady-state approximation. The concerted three-body dissociation of trans-propenal to fragments C 2 H 2 + CO + H 2 is the prevailing channel in present calculations. In contrast, C 3 H 3 O + H, C 2 H 3 + HCO and C 2 H 4 + CO were identified as major channels in the photolysis of trans-propenal. The discrepancy between calculations and experiments in product branching ratios indicates that the three major photodissociation channels occur mainly on an excited potential-energy surface whereas the other channels occur mainly on the ground potential-energy surface. This work provides profound insight in the mechanisms of isomerization and multichannel dissociation of the system C 3 H 4 O.

  15. Borata-Wittig olefination reactions of ketones, carboxylic esters and amides with bis(pentafluorophenyl)borata-alkene reagents. (United States)

    Wang, Tongdao; Kohrt, Sonja; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard


    The strongly electrophilic borane derivative amino-CH 2 CH 2 CH 2 -B(C 6 F 5 ) 2 6 was α-CH deprotonated with LiTMP to give the borata-alkene {[amino-(CH 2 ) 2 -CH[double bond, length as m-dash]B(C 6 F 5 ) 2 - ][Li + ]} 2 9 which underwent facile [2 + 2] cycloaddition reactions with benzophenone or fluorenone to yield the respective 1,2-oxaboretanides 11a,b. Compounds 9 and 11 were characterized by the X-ray diffraction. Thermolysis or hydrolysis of compounds 11a,b gave the corresponding borata-Wittig olefination products 12a,b. A variety of R-CH 2 -CH 2 -B(C 6 F 5 ) 2 boranes (conveniently generated by hydroboration of terminal alkenes R-CH[double bond, length as m-dash]CH 2 with Piers' borane [HB(C 6 F 5 ) 2 ]) were analogously deprotonated to give the respective borata-alkenes 16a-e (R: Ph-CH 2 -, n C 4 H 9 , t Bu, Cy, PhCH 2 CH 2 -). They underwent "non-classical" borata-Wittig olefination reactions with ethylformate to give the respective enolether carbonylation products, or their C 1 -elongated aldehydes (after hydrolysis). The borata-alkene [Ph-(CH 2 ) 2 -CH[double bond, length as m-dash]B(C 6 F 5 ) 2 - ] [Li + HTMP] (16a) gave the respective "non-classical" borata-Wittig olefination products, the enolethers 25a,b and 27, respectively, upon treatment with methyl- or ethyl acetate or γ-butyrolactone.

  16. Formation of ethylene glycol and other complex organic molecules in star-forming regions (United States)

    Rivilla, V. M.; Beltrán, M. T.; Cesaroni, R.; Fontani, F.; Codella, C.; Zhang, Q.


    Context. The detection of complex organic molecules related with prebiotic chemistry in star-forming regions allows us to investigate how the basic building blocks of life are formed. Aims: Ethylene glycol (CH2OH)2 is the simplest sugar alcohol and the reduced alcohol of the simplest sugar glycoladehyde (CH2OHCHO). We study the molecular abundance and spatial distribution of (CH2OH)2, CH2OHCHO and other chemically related complex organic species (CH3OCHO, CH3OCH3, and C2H5OH) towards the chemically rich massive star-forming region G31.41+0.31. Methods: We analyzed multiple single-dish (Green Bank Telescope and IRAM 30 m) and interferometric (Submillimeter Array) spectra towards G31.41+0.31, covering a range of frequencies from 45 to 258 GHz. We fitted the observed spectra with a local thermodynamic equilibrium (LTE) synthetic spectra, and obtained excitation temperatures and column densities. We compared our findings in G31.41+0.31 with the results found in other environments, including low- and high-mass star-forming regions, quiescent clouds and comets. Results: We report for the first time the presence of the aGg' conformer of (CH2OH)2 towards G31.41+0.31, detecting more than 30 unblended lines. We also detected multiple transitions of other complex organic molecules such as CH2OHCHO, CH3OCHO, CH3OCH3, and C2H5OH. The high angular resolution images show that the (CH2OH)2 emission is very compact, peaking towards the maximum of the 1.3 mm continuum. These observations suggest that low abundance complex organic molecules, like (CH2OH)2 or CH2OHCHO, are good probes of the gas located closer to the forming stars. Our analysis confirms that (CH2OH)2 is more abundant than CH2OHCHO in G31.41+0.31, as previously observed in other interstellar regions. Comparing different star-forming regions we find evidence of an increase of the (CH2OH)2/CH2OHCHO abundance ratio with the luminosity of the source. The CH3OCH3/CH3OCHO and (CH2OH)2/C2H5OH ratios are nearly constant with

  17. Molecular modification of coumarin dyes for more efficient dye sensitized solar cells

    International Nuclear Information System (INIS)

    Sanchez-de-Armas, Rocio; San-Miguel, Miguel A.; Oviedo, Jaime; Sanz, Javier Fdez.


    In this work, new coumarin based dyes for dye sensitized solar cells (DSSC) have been designed by introducing several substituent groups in different positions of the NKX-2311 structure. Two types of substitutions have been considered: the introduction of three electron-donating groups (-OH, -NH 2 , and -OCH 3 ) and two different substituents with steric effect: -CH 2 -CH 2 -CH 2 - and -CH 2 -HC=CH-. The electronic absorption spectra (position and width of the first band and absorption threshold) and the position of the LUMO level related to the conduction band have been used as theoretical criteria to evaluate the efficiency of the new dyes. The introduction of a -NH 2 group produces a redshift of the absorption maximum position and the absorption threshold, which could improve the cell efficiency. In contrast, the introduction of -CH 2 -CH 2 -CH 2 - does not modify significantly the electronic structure of NKX-2311, but it might prevent aggregation. Finally, -CH 2 -HC=CH- produces important changes both in the electronic spectrum and in the electronic structure of the dye, and it would be expected as an improvement of cell efficiency for these dyes.

  18. Nido-Carborane building-block reagents. 3. Cyclic and open-chain oligomers incorporating -CB4H6C - units. Crown carboranes

    International Nuclear Information System (INIS)

    Boyter, H.A. Jr.; Grimes, R.N.


    The open-chain dialkynes EtC≡C(CH 2 ) n C≡CEt (n = 4, 6), the trialkyne HC≡C(CH 2 ) 5 C≡CH, and the cyclic dialkynes CH 2 (CH 2 ) 4 C≡C(CH 2 ) n C≡C (n = 4-6) were treated with B 5 H 9 and (C 2 H 5 ) 3 to give the corresponding nido-carborane oligomers, in which the original -C≡C- units are converted to -CB 4 H 6 C- nido-carborane cages. In each case, all available -C≡C- groups were transformed to carborane moieties. No partially converted products (having both carborane and -C≡C- groups in the chain) were found; when the B 5 H 9 /-C≡C- ratio employed was 2+ and oxidative fusion, forming products incorporating C 4 B 8 cages. The cyclic bis(carborane) CH 2 (CH 2 ) 4 CB 4 H 6 C(CH 2 ) 5 CB 4 H 6 C is an air-stable oil that can be deprotonated but does not under metal-promoted oxidative fusion. All products were characterized by 11 B and 1 H NMR, infrared, visible-uv, and mass spectroscopy, and the 13 C NMR spectra of linear bis(carboranes) are reported. 9 references, 7 figures, 4 tables

  19. Synthesis, electrochemical properties, and charge-transfer band of binuclear 1,10-phenanthroline/bis(2,2'-bipyridine) complexes of ruthenium

    International Nuclear Information System (INIS)

    Tinnemans, A.H.A.; Timmer, K.; Reinten, M.; Kraaijkamp, J.G.; Alberts, A.H.; van der Linden, J.G.M.; Schmitz, J.E.J.; Saaman, A.A.


    The preparation of the mononuclear [Ru(bpy) 2 L] 2+ (L = bpy, phenOCH 3 , phenC(==O)NH-n-C 3 H 7 ), the binuclear [(bpy) 2 RuLRu(bpy) 2 ] 4+ (L = phenO(CH 2 CH 2 O)/sub n/phen (n = 2-4), phenC(==O)NHCH 2 CH 2 O)/sub n/(CH 2 CH 2 NH(O==)Cphen (n = 1,2), phenC(==O)NH(CH 2 )/sub n/NH(O==)Cphen (n = 3,6)), and the trinuclear [N[CH 2 CH 2 OphenRu(bpy) 2 ] 3 ] 6+ is described. Both the mononuclear and the binuclear complexes exhibit at a platinum electrode one oxidation wave and three reduction waves at potentials close to those observed for Ru(bpy) 3 2+ . The oxidation and the reductions of the binuclear complexes are two-electron-transfer reactions. From the reduction of the peak width of the differential pulse polarograms it is concluded that K/sub con/less than or equal to 1 for the conproportionation equilibrium [2,2] + [3,3] in equilibrium 2[2,3]. The mixed-valence 5+ ion has an intervalence-transfer band in the solid state (KBr) in the near-infrared spectral region. Given the saturated character of the bridge, this represents a clear example of an intramolecular outer-sphere electron-transfer transition

  20. Thermal decomposition of vinyl- and allylsilane platinum(II ...

    African Journals Online (AJOL)

    CHCH2SiMe3)], K[(acac)PtCl(CH2=CHSiMe3)] and [PtCl(CH2=CHCH2SiMe3)]2, were examined. All complexes were found to be stable at room temperature but they decomposed without melting above about 90 oC. The allylsilane complex ...

  1. Aluminiumverbindung für einen Kleber sowie Verwendungszwecke


    Glaubitt, W.; Wittstadt, K.; Ulm, G.


    Aluminum compound (I), is new. Aluminum compound of formula (Al(OH) 3 - x[(O(CH 2) n)-N-((CH 2) nOH) 2] x) (I), is new. n : 1-18; and x : 1 or 2. Independent claims are also included for: (1) an adhesive comprising (I); and (2) the preparation of (I).

  2. Highly Efficient Method for Solvent-Free Synthesis of Diarylmethane ...

    African Journals Online (AJOL)



    Feb 25, 2011 ... methane and triarylmethane was studied at room temperature, under solvent-free conditions, for five successive runs. In each run, the reaction was stopped after 120 min, cooled and sus- pended in anhydrous CH2Cl2. The suspension was then filtered and the reagent washed with anhydrous CH2Cl2 (2 ...

  3. Grafting of polypeptides on solid substrates by initiation of N-carboxyanhydride polymerization by amino-terminated self-assembled monolayers

    NARCIS (Netherlands)

    Heise, Andreas; Menzel, Henning; Yim, Hyun; Foster, Mark D.; Wieringa, Reinier Hendrik; Schouten, Arend Jan; Erb, Volker; Stamm, Manfred


    A series of mixed self-assembled monolayers of functionalized (Br(CH2)(11)SiCl3) and unfunctionalized (CH3(CH2)(10)SiCl3) alkyltrichlorosilanes of different compositions have been prepared on bulk silicon substrates. By in situ modification of these monolayers the bromo end groups were transformed

  4. Pulse radiolysis of 9,10-anthraquinone in methanol

    International Nuclear Information System (INIS)

    Mayer, J.; Krasiukianis, R.


    The reactions of anthraquinone with intermediates in methanol (e 2 - , . CH 2 O - , . CH 2 OH) were investigated using γ-radiolysis and pulse radiolysis method. The anthraquinone radical anions are reactive towards O 2 (ca 3 x 10 8 mol -1 dm 3 s -1 ) and can disproportionate giving corresponding dianion. (author)

  5. Small-angle neutron scattering studies of nonionic surfactant: Effect

    Indian Academy of Sciences (India)

    Micellar solution of nonionic surfactant -dodecyloligo ethyleneoxide surfactant, decaoxyethylene monododecyl ether [CH3(CH2)11(OCH2CH2)10OH], C12E10 in D2O solution have been analysed by small-angle neutron scattering (SANS) at different temperatures (30, 45 and 60°C) both in the presence and absence of ...

  6. Biological Potential of Halfsandwich Ruthenium(II) and Iridium (III) Complexes. (United States)

    Ludwig, Gerd; Mojić, Marija; Bulatović, Mirna; Mijatović, Sanja; Maksimović-Ivanić, Danijela; Steinborn, Dirk; Kaluđerović, Goran N


    In vitro studies with the ruthenium(II) and analogous iridium(III) complexes [Ru(η6- p-cymene)Cl2{Ph2PCH2CH2CH2S(O)xPh-κP}], [Ru(η6-p-cymene)Cl{Ph2PCH2CH2CH2S(O)xPh- κP,κS}][PF6] (1-4), [Ir(η5-C5Me5)Cl2{Ph2PCH2CH2CH2S(O)xPh-κP}] and [Ir(η5-C5Me5)Cl{Ph2 PCH2CH2CH2S(O)xPh-κP,κS}][PF6] (5-8; x = 0, 1) revealed the high selectivity toward the 8505C, A253, MCF-7, SW480 and 518A2 cancer cell lines. Thus, the cationic ruthenium complex 4 proved to be the most selective one. In case of the neutral and cationic ruthenium complexes 1-4 the caspase-dependent apoptotic cell death was proven as the main cause of the drug's tumoricidal action on 8505C cell line.

  7. Dependence of the cone angles of phosphorus-containing ligands ...

    Indian Academy of Sciences (India)


    )(L)][BF4], dppe = Ph2CH2CH2Ph2, L = P(OMe)3, P(OEt)3, PMe2Ph,. P(OiPr)3 have been prepared and characterized using a procedure similar to the one reported earlier. It was found that the binding ability of the ligand decreases in the order.

  8. Cross-protection or enhanced symptom display in greenhouse tomato co-infected with different Pepino mosaic virus isolates

    NARCIS (Netherlands)

    Hanssen, I.M.; Gutiérrez-Aguirre, I.; Paeleman, A.; Goen, K.; Wittemans, L.; Lievens, B.; Vanachter, A.C.R.C.; Ravnikar, M.; Thomma, B.P.H.J.


    The potential of three mild Pepino mosaic virus (PepMV) isolates, belonging to the CH2, EU and LP genotypes, to protect a tomato (Solanum lycopersicum) crop against an aggressive challenge isolate of the CH2 genotype was assessed in greenhouse trials and PepMV symptoms were rated at regular time

  9. Analytical product study of germanium-containing medicine by different ICP-MS applications

    NARCIS (Netherlands)

    Krystek, Petra; Ritsema, Rob


    For several years organo-germanium containing medicine has been used for special treatments of e.g. cancer and AIDS. The active substances contain germanium as beta-carboxyethylgermanium sesquioxide ((GeCH2CH 2COO-H)2O3/"Ge-132"), spirogermanium, germanium-lactate-citrate or unspecified forms. For

  10. Formation of C7F15COOH (PFOA) and other perfluorocarboxylic acids during the atmospheric oxidation of 8:2 fluorotelomer alcohol

    DEFF Research Database (Denmark)

    Wallington, T. J.; Hurley, M. D.; Xia, J.


    Calculations using a three-dimensional global atmospheric chemistry model (IMPACT) indicate that n-C8F17CH2CH2-OH (widely used in industrial and consumer products) degrades in the atmosphere to give perfluorooctanoic acid (PFOA) and other perfluorocarboxylic acids (PFCAs). PFOA is persistent, bio...

  11. Charge Transport Across Insulating Self-Assembled Monolayers: Non-equilibrium Approaches and Modeling To Relate Current and Molecular Structure

    NARCIS (Netherlands)

    Mirjani, F.; Thijssen, J.M.; Whitesides, G.M.; Ratner, M.A.


    This paper examines charge transport by tunneling across a series of electrically insulating molecules with the structure HS(CH2)4CONH(CH2)2R) in the form of self-assembled monolayers (SAMs), supported on silver. The molecules examined were studied experimentally by Yoon et al. (Angew. Chem. Int.

  12. C-H activation with elemental sulfur: synthesis of cyclic thioureas from formaldehyde aminals and S8. (United States)

    Denk, M K; Gupta, S; Brownie, J; Tajammul, S; Lough, A J


    The C-H activation of cyclic formaldehyde aminals LCH2 (L = RN-CH2CH2CH2-NR and RNCH2CH2-NR, R = Me, Et, iPr, tBu, or Ph) with S8 proceeds at unusually low temperatures (TS8 was investigated. 1,3-Dithiolane is cleanly converted into 1,3-dithiolane-2-thione (S8, 14 d, 190 degrees C) and resembles the cyclic formaldehyde aminals in this respect. 1,3-Dioxolane (L = OCH2CH2O) is completely inert towards sulfur even under forceful reaction conditions (190 degrees C, 14 d). The formation of thioureas from aminals was investigated at the CBS-4 and B3LYP/6-31G(d) levels of theory.

  13. Convenient synthesis of volatile streptomyces lactones

    Digital Repository Service at National Institute of Oceanography (India)

    Amonkar, C.P.; Tilve, S.G.; Parameswaran, P.S.

    Compound R Yield (%) 671 a H50 a 87 – b CH 3 50 a 85 92 c b CH 2 CH 2 CH 3 57 92 77 d CH 2 (CH 2 ) 3 CH 3 60 89 93 e CH 2 CH(CH 3 ) 2 65 90 94 a Yield based on phosphorane consumed. b Yield: 49%, obtained using IBX. 11 PAPER Convenient Synthesis... + + 1), 95 (17), 67 (100), 65 (20), 43 (13). 5-Methyl-3-[(E)-ethylidene]dihydrofuran-2(5H)-one (7b) Yield: 85%. IR (neat): 1756 (C=O), 1680 (C=C) cm –1 . 1 H NMR (300 MHz, CDCl 3 ): d = 1.35 (d, J = 6.3 Hz, 3 H, CHCH 3 ), 1.84 (dt, J = 6.9, 2.1, 1.8 Hz...

  14. Applying a Computational Fluid Dynamics model to understand flow structures in a large river: the Rio Paraná (United States)

    Sandbach, S. D.; Hardy, R. J.; Lane, S. N.; Ashworth, P. J.; Parsons, D. R.


    Our understanding of large rivers is limited due to the difficulties in obtaining field data at these large scales. Data rich results may be obtained using computational fluid dynamic (CFD) models permitting the investigation of detailed flow patterns that would otherwise not be available. However, the application of these models to large rivers is not without its own complications and has yet to be fully developed. This is the result of two limiting factors, our inability; i) to design numerically stable meshes for complex topographies at these spatial resolutions; and; ii) to collect high resolution data appropriate for the boundary conditions of the numerical scheme. Here, we demonstrate a five-term mass-flux scaling algorithm (MFSA) for including bed topography in a very large river, where the discretised form of the mass and momentum equations are modified using a numerical blockage. Converged solutions were obtained using the Reynolds-averaged Navier stokes (RANS) equations modelling turbulence with a κ-ɛ RNG turbulence model. The boundary conditions were supplied from a field investigation of the Rio Paraná upstream of the Paraguay-Paraná confluence. A 38 km long reach was investigated where topographic and velocity data was collected using an acoustic Doppler current profiler (aDcp) and a single beam echo sounder. The model was validated against the aDcp data and in general showed good agreement. The model was then used to explore the impacts of roughness height upon key characteristics of the 3D flow field in large rivers. The results demonstrate the importance of topographic forcing on determining flow structures including the detection of large helical flow structures.

  15. Synthesis and characterization of mixed monolayer protected gold nanorods and their Raman activities

    International Nuclear Information System (INIS)

    Mlambo, Mbuso; Mdluli, Phumlani S.; Shumbula, Poslet; Mpelane, Siyasanga; Moloto, Nosipho; Skepu, Amanda; Tshikhudo, Robert


    Graphical abstract: Gold nanorods surface functionalization. - Highlights: • Mixed monolayer protected gold nanorods. • Surface enhanced Raman spectroscopy. • HS-(CH 2 ) 11 -NHCO-coumarin as a Raman active compound. - Abstract: The cetyltrimethylammonium bromide (CTAB) gold nanorods (AuNRs) were prepared by seed-mediated route followed by the addition of a Raman active compound (HS-(CH 2 ) 11 -NHCO-coumarin) on the gold nanorods surfaces. Different stoichiometric mixtures of HS-(CH 2 ) 11 -NHCO-coumarin and HS-PEG-(CH 2 ) 11 COOH were evaluated for their Raman activities. The lowest stoichiometric ratio HS-(CH 2 ) 11 -NHCO-coumarin adsorbed on gold nanorods surface was detected and enhanced by Raman spectroscopy. The produced mixed monolayer protected gold nanorods were characterized by UV-vis spectrometer for optical properties, transmission electron microscope (TEM) for structural properties (shape and aspect ratio) and their zeta potentials (charges) were obtained from ZetaSizer to determine the stability of the produced mixed monolayer protected gold nanorods. The Raman results showed a surface enhanced Raman scattering (SERS) enhancement at the lowest stoichiometric ratio of 1% HS-(CH 2 ) 11 -NHCO-coumarin compared to high ratio of 50% HS-(CH 2 ) 11 -NHCO-coumarin on the surface of gold nanorods

  16. Organic iodine in Antarctic sea ice: A comparison between winter in the Weddell Sea and summer in the Amundsen Sea (United States)

    Granfors, Anna; Ahnoff, Martin; Mills, Matthew M.; Abrahamsson, Katarina


    Recent studies have recognized sea ice as a source of reactive iodine to the Antarctic boundary layer. Volatile iodinated compounds (iodocarbons) are released from sea ice, and they have been suggested to contribute to the formation of iodine oxide (IO), which takes part in tropospheric ozone destruction in the polar spring. We measured iodocarbons (CH3I, CH2ClI, CH2BrI, and CH2I2) in sea ice, snow, brine, and air during two expeditions to Antarctica, OSO 10/11 to the Amundsen Sea during austral summer and ANT XXIX/6 to the Weddell Sea in austral winter. These are the first reported measurements of iodocarbons from the Antarctic winter. Iodocarbons were enriched in sea ice in relation to seawater in both summer and winter. During summer, the positive relationship to chlorophyll a biomass indicated a biological origin. We suggest that CH3I is formed biotically in sea ice during both summer and winter. For CH2ClI, CH2BrI, and CH2I2, an additional abiotic source at the snow/ice interface in winter is suggested. Elevated air concentrations of CH3I and CH2ClI during winter indicate that they are enriched in lower troposphere and may take part in the formation of IO at polar sunrise.

  17. Environmental Requirements Management

    Energy Technology Data Exchange (ETDEWEB)

    Cusack, Laura J.; Bramson, Jeffrey E.; Archuleta, Jose A.; Frey, Jeffrey A.


    CH2M HILL Plateau Remediation Company (CH2M HILL) is the U.S. Department of Energy (DOE) prime contractor responsible for the environmental cleanup of the Hanford Site Central Plateau. As part of this responsibility, the CH2M HILL is faced with the task of complying with thousands of environmental requirements which originate from over 200 federal, state, and local laws and regulations, DOE Orders, waste management and effluent discharge permits, Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) response and Resource Conservation and Recovery Act (RCRA) corrective action documents, and official regulatory agency correspondence. The challenge is to manage this vast number of requirements to ensure they are appropriately and effectively integrated into CH2M HILL operations. Ensuring compliance with a large number of environmental requirements relies on an organization’s ability to identify, evaluate, communicate, and verify those requirements. To ensure that compliance is maintained, all changes need to be tracked. The CH2M HILL identified that the existing system used to manage environmental requirements was difficult to maintain and that improvements should be made to increase functionality. CH2M HILL established an environmental requirements management procedure and tools to assure that all environmental requirements are effectively and efficiently managed. Having a complete and accurate set of environmental requirements applicable to CH2M HILL operations will promote a more efficient approach to: • Communicating requirements • Planning work • Maintaining work controls • Maintaining compliance

  18. Indoor air quality in the Karns research houses: baseline measurements and impact of indoor environmental parameters on formaldehyde concentrations

    International Nuclear Information System (INIS)

    Matthews, T.G.; Fung, K.W.; Tromberg, B.J.; Hawthorne, A.R.


    Baseline indoor air quality measurements, a nine-month radon study, and an environmental parameters study examining the impact of indoor temperature (T) and relative humidity (RH) levels on formaldehyde (CH 2 O) concentrations have been performed in three unoccupied research homes located in Karns, Tennessee. Inter-house comparison measurements of (1) CH 2 O concentration, (2) CH 2 O emission rates from primary CH 2 O emission sources, (3) radon and radon daughter concentrations, and (4) air exchange rates indicate that the three homes are similar. The results of the nine-month radon study indicate indoor concentrations consistently below the EPA recommended level of 4 pCi/L. Evidence was found that crawl-space concentrations may be reduced using heat pump systems whose outdoor units circulate fresh air through the crawl-space. The modeled results of the environmental parameters study indicate approximate fourfold increases in CH 2 O concentrations from 0.07 to 0.27 ppM for seasonal T and RH conditions of 20 0 C, 30% RH and 29 0 C, 80% RH, respectively. Evaluation of these environmental parameters study data with steady-state CH 2 O concentration models developed from laboratory studies of the environmental dependence of CH 2 O emissions from particleboard underlayment indicate good correlations between the laboratory and field studies

  19. Formation of C2 oxygenates and ethanol from syngas on an Fe-decorated Cu-based catalyst: insight into the role of Fe as a promoter. (United States)

    Ling, Lixia; Wang, Qiang; Zhang, Riguang; Li, Debao; Wang, Baojun


    In this study, the formation mechanism of C 2 oxygenates and ethanol from syngas on Fe-decorated Cu bimetallic catalyst was investigated using density functional theory (DFT) calculations together with microkinetic modeling. The results showed that CH 2 was the most favored monomer among all the CH x (x = 1-3) species over the FeCu bimetallic catalyst, which was more favorable than CH 3 OH formation. Namely, the FeCu catalyst exhibited a good selectivity toward CH 2 formation instead of CH 3 OH formation in syngas conversion. Starting from the CH 2 monomer, CH 2 CO and CH 3 CO via CO insertion into CH 2 and CH 2 CO hydrogenation were the major products instead of C 2 hydrocarbons or methane, CH 3 CO was successively hydrogenated to ethanol via CH 3 CHO and CH 3 CH 2 O intermediates. Moreover, the microkinetic modeling showed that the FeCu bimetallic catalyst had a high selectivity toward ethanol rather than methanol and methane. Further, the addition of Fe into the Cu catalyst promoted CH x formation by accelerating C-O bond cleavage, suppressed methanol formation, and facilitated C 2 oxygenate formation rather than methane formation, suggesting that the synergetic effect between Fe and Cu played an important role in the formation of C 2 oxygenates and ethanol. In addition, it is believed that the insights derived from this study can provide clues for the catalyst design of oxygenate synthesis and other bimetallic catalytic systems.

  20. Deoxygenation of Palmitic Acid on Unsupported Transition-Metal Phosphides

    Energy Technology Data Exchange (ETDEWEB)

    Peroni, Marco [Technische Universität München, Department; Lee, Insu [Technische Universität München, Department; Huang, Xiaoyang [Technische Universität München, Department; Baráth, Eszter [Technische Universität München, Department; Gutiérrez, Oliver Y. [Technische Universität München, Department; Lercher, Johannes A. [Technische Universität München, Department; Institute


    Abstract Highly active bulk transition metal phosphides (WP, MoP, and Ni2P) were synthesized for the catalytic hydrodeoxygenation of palmitic acid, hexadecanol, hexadecanal, and microalgae oil. The specific activities positively correlated with the concentration of exposed metal sites, although the relative rates changed with temperature due to activation energies varying from 57 kJ·mol-1 for MoP to 142 kJ·mol-1 for WP. The reduction of the fatty acid to the aldehyde occurs through a Langmuir-Hinshelwood mechanism, where the rate-determining step is the addition of the second H to the hydrocarbon. On WP, the conversion of palmitic acid proceeds via R-CH2COOH R-CH2CHO R-CH2CH2OH R-CHCH2 R-CH2CH3 (hydrodeoxygenation). Decarbonylation of the intermittently formed aldehyde (R-CH2COOH R-CH2CHO R-CH3) was an important pathway on MoP and Ni2P. Conversion via dehydration to a ketene, followed by its decarbonylation occurred only on Ni2P. The rates of alcohol dehydration (R-CH2CH2OH R-CHCH2) correlate with the concentration of Lewis acid sites of the phosphides. Acknowledgements The authors would like to thank Roel Prins for the critical discussion of the results. We are also grateful to Xaver Hecht for technical support. Funding by the German Federal Ministry of Food and Agriculture in the framework of the Advanced Biomass Value project (03SF0446A) is gratefully acknowledged. J.A.L. acknowledges support for his contribution by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for exploring non-oxidic supports for deoxygenation reactions.

  1. Analgesic and anticonvulsant effects of extracts from the leaves of Kalanchoe crenata (Andrews) Haworth (Crassulaceae). (United States)

    Nguelefack, T B; Nana, P; Atsamo, A D; Dimo, T; Watcho, P; Dongmo, A B; Tapondjou, L A; Njamen, D; Wansi, S L; Kamanyi, A


    Kalanchoe crenata Andr. (Crassulaceae) is a fleshy herbaceous plant used in the African traditional medicine as remedies against otitis, headache, inflammations, convulsions and general debility. In the present work, the analgesic effects of methylene chloride/methanol (1:1) (CH(2)Cl(2)/CH(3)OH) extract and its hexane, methylene chloride (CH(2)Cl(2)), ethyl acetate, n-butanol fractions and aqueous residue have been evaluated using acetic acid, formalin and pressure test. The anticonvulsant effects of the CH(2)Cl(2)/CH(3)OH extract were also investigated on seizures induced by pentylenetetrazol (PTZ 70 mg/kg), strychnine sulphate (STN 2.5 mg/kg) and thiosemicarbazide (TSC 50 mg/kg). CH(2)Cl(2)/CH(3)OH extract and its fractions, administered orally at the doses of 150 and 300 mg/kg, exhibited protective effect of at least 30% on the pain induced by acetic acid. The CH(2)Cl(2) fraction at 300 mg/kg showed a maximal effect of 78.49%. The CH(2)Cl(2)/CH(3)OH extract and its CH(2)Cl(2) fraction at the doses of 150 and 300 mg/kg significantly reduced the first phase of pain induced by formalin while the second phase was completely inhibited. The CH(2)Cl(2) fraction produced more than 45% reduction in the sensitivity to pain induced by pressure. The CH(2)Cl(2)/CH(3)OH extract of Kalanchoe crenata significantly increased the latency period in seizures induced by PTZ and significantly reduced the duration of seizures induced by the three convulsant agents. The extract protected 20% of animals against death in seizures induced by TSC and STN. These results suggest a peripheral and central analgesic activities as well as an anticonvulsant effect of the leaves of Kalanchoe crenata.

  2. The preparation, characterisation and in vitro cytotoxicity of potentially chemotherapeutic heterobimetallic complexes containing early and late transition metals. (United States)

    Wedgwood, Janet L; Kresinski, Roman A; Merry, Stephen; Platt, Andrew W G


    The reactions of phosphine Ph(2)P(CH(2))(2)SO(3)Na with Cp(2)M'Cl(2) (M'=Ti, Zr) in aqueous solution give the metallophosphines, Cp(2)Ti(OSO(2)(CH(2))(2)PPh(2))(2) (Cp=cyclopentadienyl) and CpZr(OH)(OSO(2)(CH(2))(2)PPh(2))(2). These react with CODM"Cl(2) (M"=Pd, Pt) (COD=1,5-cyclooctadiene) in dichloromethane to give heterobimetallic complexes Cp(2)Ti(OSO(2)(CH(2))(2)PPh(2))(2)M"Cl(2) and CpZr(OH)(OSO(2)(CH(2))(2) PPh(2))(2)M"Cl(2) respectively. The compounds are characterised by infrared and NMR spectroscopies and elemental analysis. Electrospray mass spectra of the complexes are reported and compared to those of Cp(2)M'Cl(2) in water and dimethylsulfoxide (DMSO). For zirconocene dichloride and its product heterobimetallic complexes, the addition of ethylenediamine tetraacetic acid disodium salt (Na(2)H(2)EDTA) was found to be an effective ionisation enhancement agent for the electrospray mass spectral studies. Cytotoxicity studies for the previously reported Cl(2)Pt(PPh(2)(CH(2))(2)SO(3)H)(2).3.5H(2)O (Wedgwood et al., Inorg. Chim. Acta 290 (1999) 189), and the compounds Cp(2)Ti(OSO(2)(CH(2))(2) PPh(2))(2).1.5H(2)O and Cp(2)Ti(OSO(2)(CH(2))(2)PPh(2))(2)PtCl(2).4H(2)O reported here, have been evaluated by colony formation assay against cisplatin-sensitive and -resistant cell lines L929 and L929/R to highlight potential chemotherapeutic activity. The compound Cl(2)Pt(PPh(2)(CH(2))(2)SO(3)H)(2).3.5H(2)O overcomes cisplatin resistance.

  3. Epoxy Pipelining Composition and Method of Manufacture. (United States)


    decanoic acid (capric acid , 5 CH3(CH 2),CO2H), dodecanoic acid ( lauric acid , CH3(CH 2)10C0 2H), tetradecanoic acid 6 (myristic acid , CH 3(CH 2)12C0 2H...hydrochloric acid , hydrogen sulfide, sulfuric acid , and other corrosive 21 products of bacterial activity. Excessively high flow rates also erode the impact test). There is a need for a pipelining network polymer which resists attack 14 from fuels, chemicals, acids , bases, sewage and other

  4. New monodentate amidine superbasic ligands with a single configuration in fac-[Re(CO)3(5,5'- or 6,6'-Me2bipyridine)(amidine)]BF4 complexes. (United States)

    Abhayawardhana, Pramuditha; Marzilli, Patricia A; Perera, Theshini; Fronczek, Frank R; Marzilli, Luigi G


    Treatment of two precursors, fac-[Re(CO)(3)(L)(CH(3)CN)]BF(4) [L = 5,5'-dimethyl-2,2'-bipyridine (5,5'-Me(2)bipy) (1) and 6,6'-dimethyl-2,2'-bipyridine (6,6'-Me(2)bipy) (2)], with five C(2)-symmetrical saturated heterocyclic amines yielded 10 new amidine complexes, fac-[Re(CO)(3)(L)(HNC(CH(3))N(CH(2)CH(2))(2)Y)]BF(4) [Y = CH(2), (CH(2))(2), (CH(2))(3), NH, or O]. All 10 complexes possess the novel feature of having only one isomer (amidine E configuration), as established by crystallographic and (1)H NMR spectroscopic methods. We are confident that NMR signals of the other possible isomer (amidine Z configuration) would have been detected, if it were present. Isomers are readily detected in closely related amidine complexes because the double-bond character of the amidine C-N3 bond (N3 is bound to Re) leads to slow E to Z isomer interchange. The new fac-[Re(CO)(3)(L)(HNC(CH(3))N(CH(2)CH(2))(2)Y)]BF(4) complexes have C-N3 bonds with essentially identical double-bond character. However, the reason that the Z isomer is so unstable as to be undetectable in the new complexes is undoubtedly because of unfavorable clashes between the equatorial ligands and the bulky N(CH(2)CH(2))(2)Y ring moiety of the axial amidine ligand. The amidine formation reactions in acetonitrile (25 °C) proceeded more easily with 2 than with 1, indicating that the distortion in 6,6'-Me(2)bipy resulting from the proximity of the methyl substituents to the inner coordination sphere enhanced the reactivity of the coordinated CH(3)CN. Reaction times for 1 and 2 exhibited a similar dependence on the basicity and ring size of the heterocyclic amine reactants. Moreover, when the product of the reaction of 1 with piperidine, fac-[Re(CO)(3)(5,5'-Me(2)bipy)(HNC(CH(3))N(CH(2)CH(2))(2)CH(2))]BF(4), was challenged in acetonitrile-d(3) or CDCl(3) with a 5-fold excess of the strong 4-dimethylaminopyridine ligand, there was no evidence for replacement of the amidine ligand after two months, thus establishing

  5. Radiation-chemical hydroxypropylation of methanol

    International Nuclear Information System (INIS)

    Silaev, M.M.; AFanus'ev, A.N.; Bugaenko, L.T.; Kalyazin, E.P.


    A new method has been developed for the synthesis of 1.4-butanediol based on the possibility discovered by the authors for radiationchemical hydroxypropylation of methanol in the alpha position by means of 2-propen-l-ol, i.e., addition of a CH 2 CH 2 CH 2 OH fragment to methanol. Cylindrical molybdenum-glass ampuls containing 0.8 cm 3 of a solution of 2-propen-l-ol in cp methanol were evacuated and then irradiated by 60 CO gamma-rays. The results show that 2-propen-l-ol can be used as a potentially new telogen for radiation telomerization

  6. Isocyanates useful for forming synthetic antigens receptive to radiolabelling

    International Nuclear Information System (INIS)

    Eisenhardt, W.A. Jr.; Hedaya, E.; Theodoropulos, S.


    This patent claim on behalf of Union Carbide Corporation, relates to synthesizing isocyantes useful for forming synthetic antigens receptive to radio labelling. The claim is for an isocyanate having the structural formula (R) 3 SiO-R' -N=C=O, wherein each R is independently selected from alkyl, alicyclic, aryl, alkaryl and aralkyl groups, each having no more than 10 carbon atoms and being optionally substituted by one or more halogen atoms, and R' is selected from -C 6 H 4 -CH 2 -CH 2 - and -C 6 H 4 -CH 2 -CH-COOCH 3 . (U.K.)

  7. Column Extraction and Separation of Some Metal Ions by Diethylenetriamine Polysiloxane Immobilized Ligand System


    El-Ashgar, Nizam M.


    An extraction chromatographic solid porous polysiloxane functionalized by chelating diethylenetriamine ligand of the general formula P-(CH2)3-NH(CH2)2NH(CH2)2NH2, (Where P represents [Si-O]n siloxane network) has been evaluated for the separation of Co(II), Ni(II) and Cu(II) from aqueous solutions. The chromatographic parameters of the separation method have been optimized. The ligand system retained Co(II), Cu(II) and Zn(II) effectively when used as a metal ion extractant by controlling the...

  8. Selective catalytic dehydration of furfuryl alcohol to 2, 2'-difurfuryl ether using a polyoxometalate catalyst. (United States)

    Yang, Shaoxiang; Hao, Yanfeng; Wang, Jialin; Wang, Hao; Zheng, Yimeng; Tian, Hongyu; Liu, Yongguo; Sun, Baoguo


    The spice flavour compound 2, 2'-difurfuryl ether (DFE) is widely utilised in the food industry as it has a coffee-like, nutty, earthy, mushroom-like odour. However, despite intensive research efforts, to date, an environmentally friendly and practical synthetic preparation technique for 2, 2'-difurfuryl ether is still unavailable. Here, we investigate a new approach using polyoxometalate catalysts to selectively catalytically dehydrate furfuryl alcohol to 2, 2'-difurfuryl ether. We have successfully applied this methodology using the polyoxometalate (POMs) catalyst {[(CH 3 CH 2 CH 2 CH 2 ) 4 N] 2 [SMo 12 O 40 ]} to produce 2,2'-difurfuryl ether in a 30.86% isolated yield.

  9. Excess enthalpies of the ternary mixtures: {tetrahydrofuran + 3-methylpentane + (octane or decane)} at the temperature 298.15 K

    International Nuclear Information System (INIS)

    Wang Zhaohui; Benson, George C.; Lu, Benjamin C.-Y.


    Measurements of excess molar enthalpies at the temperature 298.15 K in a flow microcalorimeter, are reported for the two ternary mixtures {X 1 C 4 H 8 O + X 2 CH 3 CH 2 CH(CH 3 )CH 2 CH 3 + (1-X 1 -X 2 )CH 3 (CH 2 ) v-2 CH 3 } with v=8 and 10. Smooth representations of the results are described and used to construct constant-enthalpy contours on Roozeboom diagrams. It is shown that useful estimates of the ternary enthalpies can be obtained from the Liebermann-Fried model, using only the physical properties of the components and their binary mixtures

  10. Solid-phase synthesis of isoxazoles using vinyl ethers as chameleon catches. (United States)

    Barrett, A G; Procopiou, P A; Voigtmann, U


    [reaction: see text] Regioselective 1,3-dipolar cycloadditions of supported vinyl ethers R(1)C(=CH(2))O-CH(2)-polymer, prepared by the Tebbe olefination of R(1)CO(2)-CH(2)-polymer, with ethyl cyanoformate N-oxide gave supported isoxazoline derivatives. Release from the support under mild acidic conditions gave the isoxazoles ethyl 5-R(1)-isoxazole-3-carboxylates. Alternatively, further on-resin functionalization of the R(1) substituent using Suzuki coupling reactions and release from the support under acidic conditions gave more structurally diverse isoxazoles.

  11. Alkylating Derivatives of Vitamin D Hormone for Prostate Cancer (United States)


    For example aspirin contains a hydrolysable ester bond, yet acetyl salicylate is the active principle of this drug, and not salicylic acid , its... Acetic Anhydride / Pyridine/ 40C 1. UV / Toluene 2. EtOH - Reflux TBDMSCl / Imidazole /DMF BrCH2COOH / DCC / DMAP / CH2Cl2 1,25(OH)2D3-3-BE Figure 1...G) (8 mg), DCC (2.5 X, 8.12 mg), DMAP (catalytic), bromoacetic acid (1.5 X, 3.3 mg) in one ml of anhydrous CH2Cl2 was stirred for 20 hours followed

  12. Interactions of Verkade's Superbase with Strong Lewis Acids: From Labile Mono- and Binuclear Lewis Acid-Base Complexes to Phosphenium Cations. (United States)

    Mummadi, Suresh; Kenefake, Dustin; Diaz, Rony; Unruh, Daniel K; Krempner, Clemens


    A series of mono- and binuclear Lewis acid-base complexes of the formulas N[CH 2 CH 2 N(Pr i )] 3 P→LA [LA = BH 3 (8), Ga(C 6 F 5 ) 3 (10), GaCl 3 (11)], LA←N[CH 2 CH 2 N(Pr i )] 3 P [LA = Al(C 6 F 5 ) 3 (6a), AlMe 3 (6b), AlEt 3 (6c), AlBu i 3 (6d), BF 3 (13)], and LA←N[CH 2 CH 2 N(Pr i )] 3 P→LA [Lewis acid (LA) = Al(C 6 F 5 ) 3 (7a), AlMe 3 (7b), AlEt 3 (7c), AlBu i 3 (7d), AlCl 3 (7e), BH 3 (9)] were generated from reactions of Verkade's base, N[CH 2 CH 2 N(Pr i )] 3 P (1), with various boron-, aluminum-, and gallium-containing Lewis acids, and characterized by multinuclear NMR spectroscopy. {N[CH 2 CH 2 N(Pr i )] 3 P→C 7 H 7 }[BF 4 ] (5) was synthesized via the treatment of 1 with [C 7 H 7 ][BF 4 ]. The reaction of 1 with B(C 6 F 5 ) 3 , followed by the addition of [Ph 3 C] 2 [B 12 Cl 12 ], gave rise to the rearranged borate salt [PN 4 C 9 H 17 (Pr i ) 2 ][B 12 Cl 12 ] (3), while treating 1 with [Ph 3 C] 2 [B 12 Cl 12 ] exclusively afforded {N[CH 2 CH 2 N(Pr i )] 3 PH} 2 [B 12 Cl 12 ] (4). Reactions of 1 with 2 equiv of GaCl 3 and BF 3 , respectively, afforded the novel phosphenium gallate and borate salts 12a, 12b, and 15. The solid-state structures of 1, 3-5, 6b, 7a, 7b, 7e, 8, 10, 11, 12b, 13, and 15 were determined by X-ray crystallography.

  13. Unanticipated guest motion during a phase transition in a ferroelastic inclusion compound. (United States)

    Hollingsworth, Mark D; Peterson, Matthew L; Pate, Kevin L; Dinkelmeyer, Brian D; Brown, Michael E


    Urea inclusion compounds (UICs) have been used as tools to understand ferroelastic domain switching and molecular recognition during crystal growth. Although the vast majority of UICs contain helical arrangements of host H-bonds, those containing guests with the formula X(CH(2))(6)Y (X, Y = Br, Cl, CN, NC) adopt an alternative P2(1)/n packing mode in which the host molecules exist as stacked loops of urea hexamers. Such structures may be further separated into two classes, ones distorted away from hexagonal symmetry along [100] (Br(CH(2))(6)Br, Br(CH(2))(6)Cl, and Cl(CH(2))(6)Cl) and those distorted along [001] (e.g. NC(CH(2))(6)CN). In each of these systems, guests exist as equilibrium mixtures of gauche conformers whose populations control the direction and magnitude of the observed distortion. Such UICs are potentially ferroelastic, but the n-glide requires that domains are not related by a simple rotation-translation mechanism as in the helical systems. Ferroelastic (degenerate) domain reorientation would necessitate a large-scale reorganization of the urea framework and rupture of numerous H-bonds. Coupled with distortions of 2 to 10%, this mechanism-based barrier to domain switching has precluded observation of this phenomenon. To prepare ferroelastic UICs with minimal distortions from hexagonal symmetry, attempts were made to form solid solutions of UICs containing guests from the two classes. This failed, however: solid solution formation of the stacked loop form is usually possible within a series (e.g. with Cl(CH(2))(6)Cl and Br(CH(2))(6)Br), but not between series (e.g. Cl(CH(2))(6)Cl and NC(CH(2))(6)CN). Crystals of Cl(CH(2))(6)CN/urea, in which a single guest contains substituents from each class, are distorted along [001] by only 0.5% from hexagonal symmetry at 298 K and exhibit ferroelastic domain reorientation at high forces. At -66 degrees C, Cl(CH(2))(6)CN/urea undergoes a topotactic phase transition that is unexpectedly nontopochemical. The

  14. Design, synthesis and bioevalucation of novel 2,3-dihydro-1H-inden-1-amine derivatives as potent and selective human monoamine oxidase B inhibitors based on rasagiline. (United States)

    Xiao, Xuan; Zhang, Xing-Xing; Zhan, Mei-Miao; Cheng, Kai; Li, Shiyu; Xie, Zhouling; Liao, Chenzhong


    Parkinson's disease (PD) is associated with elevated levels of hMAO-B in the brain, and MAO-B has been recognized a successful target for developing anti-PD drugs. Herein we report rasagiline derivatives as novel potent and selective hMAO-B inhibitors. They were designed by employing fragment-based drug design strategy to link rasagiline and hydrophobic fragments, which may target a hydrophobic pocket in the entrance cavity of hMAO-B. Different linkers such as -OCH 2 -, -SCH 2 -, -OCH 2 CH 2 -, -OCH 2 CH 2 O-, -OCH 2 CH 2 CH 2 O- were tried. A promising selective hMAO-B inhibitor D14 with similar inhibitory activity as rasagiline and improved isoform selectivity was yielded. The selectivity profile of compounds reported herein suggests that we can further develop more potent hMAO-B inhibitors with high isoform selectivity through this strategy. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

  15. The arsonomethyl analogue of adenosine 5'-phosphate. An uncoupler of adenylate kinase. (United States)

    Adams, S R; Sparkes, M J; Dixon, H B


    Adenosine was converted into the arsonomethyl analogue of AMP. The reactions used provide a general route for converting an alcohol, R-CH2-OH, into the arsonomethyl analogue, R-CH2-CH2-AsO3H2, of its phosphate, R-CH2-O-PO3H2. The analogue of AMP proves to be a substrate for rabbit adenylate kinase, which shows a limiting velocity with it of 1/17 that with AMP, a Michaelis constant raised 70-fold to about 10 mM, and hence a specificity constant lowered about 1200-fold. The product of transfer of a phospho group from ATP to the analogue is, like all anhydrides of arsonic acids, unstable to hydrolysis, and so breaks down to yield orthophosphate and regenerate the analogue. Hence adenylate kinase is converted into an ATPase by the presence of the analogue. PMID:6089748

  16. Synthesis and characterization of a heptadentate (N4O3 Schiff base ligand and associated La(III, Sm(III and Gd(III complexes, and a theoretical study

    Directory of Open Access Journals (Sweden)

    Sadegh Salehzadeh


    Full Text Available A new symmetrical potentially heptadentate (N4O3 Schiff base ligand {N[CH2CH2CH2N=CH(2-OH-5-BrC6H3]3} (H3L6 and associated neutral Gd(III, La(III and Sm(III complexes, were synthesized. The new compounds were characterized by IR spectroscopy, elemental analysis and mass spectrometry in all cases and in the case of ligand also with NMR spectroscopy. The relative capability of H3L6 to encapsulate a lanthanide ion, herein La(III, has been theoretically studied by ab initio restricted Hartree-Fock (RHF and DFT (B3LYP methods. The calculation confirmed that the H3L6 ligand can effectively encapsulate a lanthanide ion and enforce a seven-coordinate geometry.

  17. 15-00544_SI.doc

    Indian Academy of Sciences (India)

    31P{1H} NMR spectrum [C5H4N(BH3)-CH2NHP(BH3)Ph2] of (1a). S3. 11B{1H} NMR spectrum of [C5H4N(BH3)-CH2NHP(BH3)Ph2] of (1a). S4. 13C{1H} NMR spectrum of [C5H4N(BH3)-CH2NHP(BH3)Ph2] (1a). S5. 1H{1H} NMR spectrum of [C5H4N(BH3)-CH2NHP(Se)Ph2] (2a). S6. 31P{1H} NMR spectrum of ...

  18. Advanced TCCS for Spacesuit Applications, Phase I (United States)

    National Aeronautics and Space Administration — A recent trade study showed that active removal of ammonia (NH3) and formaldehyde (CH2O) is crticial to meeting the 24-hr SMAC limits in the advanced space suit...

  19. Elastic scattering of light neutron rich exotic beams on a proton target

    International Nuclear Information System (INIS)

    Cortina-Gil, M.D.; Roussel-Chomaz, P.; Mittig, W.; Casandjian, J.M.; Chartier, M.; Alamanos, N.; Auger, F.; Fekou-Youmbi, V.; Barrette, J.; Blumenfeld, Y.; and others.


    The elastic scattering of 6 He, 10,11 Be secondary beams on a (CH 2 ) 3 target has been measured. A microscopic optical potential was used to reproduce the proton-nucleus elastic scattering data. (author)

  20. Radiation induced solid-state polymerization of long-chain acrylates containing fluorocarbon chain

    International Nuclear Information System (INIS)

    Shibasaki, Y.; Zhu, Zhi-Qin


    γ-Ray irradiation post-polymerizations of long-chain acrylates containing fluorocarbon chain, H(CF 2 ) 10 CH 2 OCOCH=CH 2 and H(CF 2 ) 8 CH 2 OCOCH=CH 2 , were investigated and also the structures and thermal properties of comb-like polymers obtained were studied. It was found that these monomers exhibited very high polymerizability at wide temperature ranges around the melting points. Because the fluorocarbon chains are less flexible and thicker than the hydrocarbon chains, it can be expected that the aggregation force among the monomer molecules is strong and the conformational freedom of functional group for polymerization is large. According to the DSC and the X-ray diffraction measurements of the comb-like polymers obtained, the fluorocarbon chains are aggregated in a mode of hexagonal packing in the lamellar crystals. This situation can be considered as an optimum condition for the γ-ray irradiation post-polymerization. (author)

  1. Analgesic effects of the methylene chloride/methanol extract of the ...

    African Journals Online (AJOL)

    CH2Cl2/CH3OH) extract of Laportea ovalifolia (Urticaceae) were evaluated using acetic acid and formalin test. The anticonvulsant effects of the same extract were also investigated on seizures induced by pentylenetetrazol (PTZ) and picrotoxin.

  2. Drug: D00123 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D00123 Drug Cyanamide (JP17); Cyanamide (TN) ... CH2N2 D00123.gif ... Other ... DG01718 ... Drugs... for addictive disorder ... DG01716 ... Drugs for alcohol dependence Same as: C01566 Therapeutic category: 3

  3. Kinetics and mechanism of the reactions of chloromethyl radical with acetylene and decomposition of 1-chloroallyl and 2-chloromethyl vinyl radicals (United States)

    Knyazev, Vadim D.


    Three reactions occurring on the C3H4Cl potential energy surface (PES) were studied computationally using quantum chemistry and master equation/RRKM: CH2Cl + C2H2 → Products (1), CH2CHCHCl → Products (2), and CH2ClCHCH → Products (3). The results indicate low importance of the 1,3-Cl shift channel linking the PESs of reactions 1 and 2 despite a relatively low energy barrier. Addition and chemically activated H elimination are the two major products of reaction 1, with branching dependent on pressure and temperature. Cl and cyclopropene are the major products of reaction 2, and CH2Cl + C2H2 - of reaction 3.

  4. Atmospheric chemistry of C4F9O(CH2)3OC4F9 and CF3CFHCF2O (CH2)3OCF3CFHCF2

    DEFF Research Database (Denmark)

    Toft, A. M.; Hurley, M. D.; Wallington, T. J.


    FTIR smog chamber techniques were used to measure k(Cl + CF3CFHCF2O(CH2)(3)OCF2CFHCF3) = (2.97 +/- 0.17) x 10(-12) k(OH + CF3CFHCF2O(CH2)(3)OCF2CFHCF3) = (2.45 +/- 0.14) x 10(-13), k(Cl + C4F9O(CH2)(3)OC4F9) = (1.45 +/- 0.16) x 10(-12), and k(OH + C4F9O(CH2)(3)OC4F9) = (1.44 +/- 0.10) x 10(-13) c...

  5. Rational Design of Coordination Polymers with Flexible Oxyethylene Side Chains

    International Nuclear Information System (INIS)

    Choi, Eun Young; Gao, Chunji; Lee, Suck Hyun; Kwon, O Pil


    We rationally designed and synthesized metallopolymers with organic 1,4-benzenedicarboxylic acid (BDC) linkers with different lengths of oxyethylene side chains in order to examine the influence of side chains on the coordination characteristics. While in a previous report the BDC linkers with alkyl side chains were found to form three-dimensional (3D) isoreticular metal-organic framework (IRMOF) structures or one-dimensional (1D) coordination polymeric structures with short -O(CH 2 ) 6 CH 3 or long -O(CH 2 ) 9 CH 3 side chains, respectively, new BDC linkers with oxyethylene side chains of the same lengths, -(OCH 2 CH 2 ) 2 CH 3 and -(OCH 2 CH 2 ) 3 CH 3 , form only 3D IRMOF structures. This result is attributed to the higher flexibility and smaller volume of oxyethylene side chains compared to alkyl side chains

  6. Thermal decomposition of vinyl- and allylsilane platinum(II complexes and platinum(II catalysed synthesis of (E,(E-1,4-diphenyl-1,3-butadiene

    Directory of Open Access Journals (Sweden)

    Paul P. Mebe


    Full Text Available Thermal stabilities of Pt(II complexes: K[PtCl3(CH2=CHSiMe3], K[PtCl3(CH2=CHCH2SiMe3], K[(acacPtCl(CH2=CHSiMe3] and [PtCl(CH2=CHCH2SiMe3]2, were examined. All complexes were found to be stable at room temperature but they decomposed without melting above about 90 oC. The allylsilane complex decomposed above about 125 oE,(E-1,4-diphenyl-1,3-butadiene was stereoselectively synthesised in good yield from (E-β-styrylsilane in the presence of Zeise’s salt.

  7. Molecular structures of various alkyldichlorosilanes in the solid state. (United States)

    Wagler, Jörg; Gericke, Robert


    A series of organodichlorosilanes RR'SiCl 2 (R,R' = (CH 2 ) 3 ; (CH 2 ) 4 ; (CH 2 ) 5 ; Me,Me; Me,H; Me,Cl) was studied by single-crystal X-ray diffraction analyses. At ambient temperature liquid chlorosilanes (melting points in the range of 180-220 K) were transferred into glass capillaries and crystallized in situ on a diffractometer. In the solid state structure these chlorosilanes are monomeric, even in the case of the sterically less demanding 1,1-dichlorosilacyclobutane (CH 2 ) 3 SiCl 2 . Interestingly, regardless the steric demand of the alkyl substituents, the dialkyldichlorosilanes exhibit essentially the same Cl-Si-Cl angle (for (CH 2 ) 3 SiCl 2 , (CH 2 ) 4 SiCl 2 , (CH 2 ) 5 SiCl 2 , Me 2 SiCl 2 : 106.08(3)°, 106.07(4)°/105.86(4)°, 106.91(2)° and 105.59(6)°, respectively). Replacement of one alkyl group by hydrogen has only a marginal influence on the Cl-Si-Cl angle (MeHSiCl 2 106.31(3)°), whereas in MeSiCl 3 slightly wider Cl-Si-Cl angles are found (ranging between 107.04(11)° and 107.86(11)°), in accordance with VSEPR. Computational analyses, i.e., potential energy surface scans of the Cl-Si-Cl angle variation, of (CH 2 ) 3 SiCl 2 , Me 2 SiCl 2 , MeHSiCl 2 and H 2 SiCl 2 reveal essentially identical energy profiles for the Cl-Si-Cl deformation in these four dichlorosilanes with basically superimposed curves for (CH 2 ) 3 SiCl 2 and Me 2 SiCl 2 , whereas with increasing H-substitution the energetic minimum is shifted to a slightly wider Cl-Si-Cl angle. In the crystal packing only MeHSiCl 2 exhibits weak intermolecular SiCl van der Waals contacts, whereas the Si-Cl moieties of the other five chlorosilanes engage in intermolecular ClH and (for (CH 2 ) 3 SiCl 2 , (CH 2 ) 4 SiCl 2 and MeSiCl 3 ) ClCl contacts.

  8. Synthesis, characterization and in vitro antibacterial activity of novel ...

    Indian Academy of Sciences (India)


    dried and activated in vacuum at 100. ◦. C. Activated diatomite. (2 g) was dispersed in dry CH2Cl2 and chlorosulfonic acid. (1 mL) was added to the solution at room temperature. After. 2 h, the white solid was filtered, washed repeatedly by dry. CH2Cl2, and dried at 120. ◦. C for 12 h. 2.3 General procedure for the synthesis of.

  9. 1,2-Bis(2-methoxy-6-formylphenoxyethane

    Directory of Open Access Journals (Sweden)

    Hongqi Li


    Full Text Available In the title compound [systematic name: 3,3′-dimethoxy-2,2′-(ethane-1,2-diyldioxydibenzaldehyde], C18H18O6, prepared from 1,2-dibromoethane and ortho-vanillin in the presence of sodium carbonate, the two vanillin units are linked via a CH2CH2 bridge. The two benzene rings are inclined at a dihedral angle of 41.6 (5°.

  10. Ni(II) complexes of dithiophosphonic acids

    Indian Academy of Sciences (India)

    bacterial properties. ∗. For correspondence. Three novel dithiophosphinates with the formula HS2P. (p-C6H4OMe)(OCH2CH(CH3)2) (I), [S2P(C6H11NH)(p-. C6H4OMe)H3N. +. C6H11] (II) and [S2P(phCH2CH2NH). (p-C6H4OMe)H3N. +.

  11. Fulltext PDF

    Indian Academy of Sciences (India)


    Abstract. Synthesis, structures and stability (thermal and air) of allenylphosphonates of the type. (OCH2CMe2CH2O)P(O)C(R)=C=CR′R″ and [R″R′C=C=C(R)P(O)(OCH2)2]2C are discussed. Thermally activated dimerization (cycloaddition) of (OCH2CMe2CH2O)P(O)C(H)=C=CMe2 leads to the phos-.

  12. A Structural Investigation of the D 2 O Solvated, Acetone Solvated ...

    African Journals Online (AJOL)

    ... to –19.31(12) ° and 15.3(2) –15.7(2) ° in 1 and 2, respectively, whereas in 3, the CH2 groups of each NCH2CH2N moiety are almost eclipsed, the torsion angles ranging from –2.89(18) to –1.50(16) °. KEYWORDS Cyclopentadienyliron dicarbonyl complex, 1,4-diazabicyclo[2.2.2]octane (DABCO), X-ray crystallography.

  13. Characterization of alkanethiol/ZnO structures by X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Ogata, K.; Hama, T.; Hama, K.; Koike, K.; Sasa, S.; Inoue, M.; Yano, M.


    1-Propanethiol (CH 3 CH 2 CH 2 SH) was connected with O-polar zinc oxide (ZnO) surfaces toward biofunctional devices. X-ray photoelectron spectroscopy (XPS) measurement revealed that the S-O bonds were formed between 1-propanethiol and ZnO layers. Although the surface coverage of the molecule is less than a few percent, 1-propanethiol/ZnO structures were stable even at thermal treatment of 400 deg. C

  14. supp4.doc

    Indian Academy of Sciences (India)

    1H NMR Spectrum of CAR-THIOX in CDCl3. , ppm. SI-3. 1H NMR Spectrum of CAR-TPA in CDCl3. SI-4. Cyclic Voltammogramme of CAR-THIOHX in CH2Cl2. SI-5. Emission Spectra of CAR-THIOHX in Different Solvents. SI-6. Emission Spectra of CAR-TPA in Different Solvents. SI-7. Singlet State Decay in CH2Cl2 Solvent.

  15. New insights into structural and electrochemical properties of anisotropic polymer electrolytes

    International Nuclear Information System (INIS)

    Livshits, E.; Kovarsky, R.; Lavie, N.; Hayashi, Y.; Golodnitsky, D.; Peled, E.


    The inter-relationship between the orthogonal alignment of polymer helices and improvement of lithium-transport properties of polymer electrolytes has been determined by scanning electron microscopy, differential-scanning calorimetry and dielectric spectroscopy. It is suggested that ordering of the polymer electrolyte accompanied by increased conduction properties is achieved by mutual coordination of local dipole moments of the polar CH 2 -CH 2 -O units during casting under a magnetic field

  16. 15-00544_SI.doc

    Indian Academy of Sciences (India)

    2] (2). S9. FT-IR spectrum of [C5H4N(BH3)-CH2NHP(BH3)Ph2] (1a). S10. FT-IR spectrum of [C5H4N(BH3)-CH2NHP(Se)Ph2] (2a). (Color code carbon is grey, hydrogen is white, phosphorous is orange, nitrogen is blue, oxygen is red, lithium is ...

  17. Sterics level the rates of proton transfer to [Ni(XPh){PhP(CH₂CH₂PPh₂)₂}]⁺ (X = O, S or Se). (United States)

    Alwaaly, Ahmed; Henderson, Richard A


    Rates of proton transfers between lutH(+) (lut = 2,6-dimethylpyridine) and [Ni(XPh)(PhP{CH2CH2PPh2}2)](+) (X = O, S or Se) are slow and show little variation (k(O) : k(S) : k(Se) = 1 : 12 : 9). This unusual behaviour is a consequence of sterics affecting the optimal interaction between the reactants prior to proton transfer.

  18. UV absorption spectra and kinetics for alkyl and alkyl peroxy radicals originating from di-tert-butyl ether

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.; Langer, S.


    Alkyl, (CH3)(3)COC(CH3)(2)CH2, and alkyl peroxy, (CH3)(3)COC(CH3)(2)CH2O2, radicals from di-tert-butyl ether (DTBE), have been studied in the gas phase at 296 K. A pulse radiolysis UV absorption technique was used to measure the spectra and kinetics. Absorption cross sections were quantified over...

  19. Synthesis and evaluation of alpha-(((2-haloethyl)amino)methyl)-2- nitro-1H-imidazole-1-ethanols as prodrugs of alpha-((1-aziridinyl)methyl)-2- nitro-1H-imidazole-1-ethanol (RSU-1069) and its analogues which are radiosensitizers and bioreductively activated cytotoxins

    Energy Technology Data Exchange (ETDEWEB)

    Jenkins, T.C.; Naylor, M.A.; O' Neill, P.; Threadgill, M.D.; Cole, S.; Stratford, I.J.; Adams, G.E.; Fielden, E.M.; Suto, M.J.; Stier, M.A. (Medical Research Council Radiobiology Unit, Didcot, Oxfordshire (England))


    alpha-((1-Aziridinyl)methyl)-2-nitro-1H-imidazole-1-ethanols, of general formula ImCH2CH(OH)CH2NCR1R2CR3R4, where Im = 2-nitroimidazole and R1, R2, R3, R4 = H, Me, are radiosensitizers and selective bioreductively activated cytotoxins toward hypoxic tumor cells in vitro and in vivo. Treatment of the aziridines with hydrogen halide in acetone or aqueous acetone gave the corresponding 2-haloethylamines of general formula ImCH2CH(OH)CH2(+)-NH2CR1R2CR3R4X X-, where R1, R2, R3, R4 = H, Me, and X = F, Cl, Br, I. These 2-haloethylamines were evaluated as prodrugs of the parent aziridines. The rates of ring closure in aqueous solution at pH approximately 6 were found to increase with increasing methyl substitution and to depend on the nature of the leaving group (I approximately Br greater than Cl much greater than F). A competing reaction of ImCH2CH(OH)CH2+NH2CH2CH2X X- (X = Cl, Br) with aqueous HCO3- ions gives 3-(2-hyroxy-3-(2-nitro-1H-imidazol-1-yl)propyl)-2-oxazolidinone. The activities of these prodrugs as radiosensitizers or as bioreductively activated cytotoxins were consistent with the proportion converted to the parent aziridine during the course of the experiment. alpha-(((2-Bromoethyl)amino)methyl)-2-nitro-1H-imidazole-1- ethanol (RB 6145, 10), the prodrug of alpha-((1-aziridinyl)methyl)-2-nitro-1H-imidazole-1-ethanol (RSU-1069, 3), is identified as the most useful compound in terms of biological activity and rate of ring closure under physiological conditions.

  20. Gold (III) pentafluorophenylarylazoimidazole: Synthesis and spectral ...

    Indian Academy of Sciences (India)

    AuIII(C6F5)3 (RaaiR')] [RaaiR' = -R-C6H4-N=N-C3H2-NN-1-R', (1-3), R = H (a), Me (b), Cl (c) and R' = Me (1), CH2CH3 (2), CH2Ph (3), tht is tetrahydrothiophen]. The nine new complexes are characterised by ES/MS as well as FAB, IR and ...

  1. Synthesis of Streptococcus pneumoniae type 3 neoglycoproteins varying in oligosaccharide chain length, loading and carrier protein

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Lefeber, D.J.; Kamerling, J.P.


    The preparation is described of a range of neoglycoproteins containing synthesised fragments of the capsular polysaccharide of Streptococcus pneumoniae type 3, that is beta-D-GlcpA-(1->4)-beta-D-Glcp-(1->O)-(CH2)3NH2 (1), beta-D-Glcp-(1->3)-beta-D-GlcpA-(1->4)-beta-D-Glcp-(1->O)-(CH2)3NH2 (2), and

  2. Activity, stability and kinetic parameters for α-chymotrypsin catalysed ...

    Indian Academy of Sciences (India)

    Three typical surfactants were selected based on their head group charges: a non-ionic surfactant Triton-X 100 and two zwitterionic sulphobetaine surfactants of the type CH2+1N+Me2 (CH2)3 SO 3 − (n = 10; SB3-10, n = 16; SB3-16). The kinetic parameters (such as cat and M) of the -CT at 27°C were determined ...

  3. Synthesis of ruthenium(II) complexes containing hydroxymethylphosphines and their catalytic activities for hydrogenation of supercritical carbon dioxide. (United States)

    Kayaki, Yoshihito; Shimokawatoko, Yoshiki; Ikariya, Takao


    Ligand substitution of RuCl2[P(C6H5)3]3 and Cp*RuCl(isoprene) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) complexes with hydroxymethylphosphines was investigated to develop new catalyst systems for CO2 hydrogenation. A reaction of P(C6H5)2CH2OH with RuCl2[P(C6H5)3]3 in CH2Cl2 gave Ru(H)Cl(CO)[P(C6H5)2CH2OH]3 (1), which was characterized by NMR spectroscopy and X-ray crystallographic analysis. An isotope labeling experiment using P(C6H5)213CH2OH indicated that the carbonyl moiety in complex 1 originated from formaldehyde formed by degradation of the hydroxymethylphosphine. Elimination of formaldehyde from PCy2CH2OH (Cy=cyclohexyl) was also promoted by treatment of RuCl2[P(C6H5)3]3 in ethanol to give RuCl2(PHCy2)4 under mild conditions. On the other hand, the substitution reaction using Cp*RuCl(isoprene) with the hydroxymethylphosphine ligands proceeded smoothly with formation of Cp*RuCl(L)2 [2a-2c; L=P(C6H5)2CH2OH, PCy(CH2OH)2, and P(CH2OH)3] in good yields. The isolable hydroxymethylphosphine complexes 1 and 2 efficiently catalyzed the hydrogenative amidation of supercritical carbon dioxide (scCO2) to N,N-dimethylformamide (DMF).

  4. SUPPLEMENTARY INFORMATION Bronsted acid functionalised ...

    Indian Academy of Sciences (India)


    In the above spectrum, the broad peak at 3307 cm-1 was due to stretching vibrations of. –CH2–OH group. The broadness of the peak could be due to hydrogen bonding of hydroxyl group with chloride in the zwitter ion. The –CH2 stretching vibrations were observed at 1473 cm-1. The –CH3 stretching vibrations were ...

  5. Extremely Low Noise Carbon Nanotubes for Peltier and Photo-Detector Device Applications (United States)


    negatively charged by adding mercaptoacetic acid (MAA). The silicon oxide substrate was decorated by octadecyltrichlorosilane (OTS) and converted to...Y. Jeong et al. Chirality-specific transport phenomena of isolated singlewalled carbon nanotube, Phys. Stat. Sol. B 244, 4204 (07). 2. Seung Yol...1hr, the precipitate was filtered and washed with methanol thrice. To prepare Me6TREN, (ClNH3CH2CH2)3NHCl, water, formic acid , and a formaldehyde

  6. Pentamethylcyclopentadienyl Zirconium and Hafnium Polyhydride Complexes : Synthesis, Structure, and Reactivity

    NARCIS (Netherlands)

    Visser, Cindy; Hende, Johannes R. van den; Meetsma, Auke; Hessen, Bart; Teuben, Jan H.


    The half-sandwich zirconium and hafnium N,N-dimethylaminopropyl complexes Cp*M[(CH2)3NMe2]Cl2 (Cp* = η5-C5Me5, M = Zr, 1; Hf, 2) and Cp*M[(CH2)3NMe2]2Cl (M = Zr, 3; Hf, 4) were synthesized by mono- or dialkylation of Cp*MCl3 with the corresponding alkyllithium and Grignard reagents. Hydrogenolysis

  7. AFOSR (Air Force Office of Scientific Research) Chemical & Atmospheric Sciences Program Review (27th). (United States)


    prepared for use as ligands in catalysis studies. Their cobalt complexes are active hydroformylation catalysts. c. M3SiCH2CHCH=CH2 was prepared and found...Park, PA 16802 SURFACE CHEMISTRY - CAPTAIN LEE E. MYERS A Mechanistic Study of Nitro - Jay B. Benziger methane Decomposition on Ni Department of diphthalocyanine complexes . Future directions for the program are difficult to predict. For the immediate future we plan to continue a

  8. Biphenolate Iron (II) Complexes with Intramolecularly Coordinating Nitrogen Lewis Bases

    NARCIS (Netherlands)

    Koten, G. van; Brandts, J.A.M.; Janssen, M.D.; Hogerheide, M.P.; Boersma, J.; Spek, A.L.


    The synthesis and characterisation of a novel Fe(II) bisphenolate complex [Fe(OC{6}H{4}CH{2}NMe{2}-2){2}]{2} (1) from [Na(OC{6}H{4}CH{2}NMe{2}-2)] and anhydrous FeCl{2} is reported. The solid state structure has been elucidated by single crystal X-ray analysis and shows a dimeric structure with two

  9. A proposal for positive cooperation in anion-cation binding in yttrium and lutetium complexes based on o-amino-substituted phenolate ligands. On the way to coordination polymers by self-assembly. Molecular structures of [ClLu(OAr)3Na] (X-ray) and [ClY(OAr')3Y(OAr')3Na] (X-ray and 89Y-NMR)

    NARCIS (Netherlands)

    Koten, G. van; Hogerheide, M.P.; Ringelberg, S.N.; Grove, D.M.; Jastrzebski, J.T.B.H.; Boersma, J.; Smeets, W.J.J.; Spek, A.L.


    Unique hetero(poly)metallic complexes [ClM(OAr)3Na] (M = Lu (3a), Y (3b)) and [ClY(OAr')3Y(OAr')3Na] (4) containing the bis (OAr = OC6H2(CH2NMe2)2-2,6-Me-4) and mono (OAr' = OC6H4(CH2NMe2)-2) o-amino-substituted phenolate ligands have been synthesized and characterized by NMR (1H, 13C, and 89Y) and

  10. Coordination Chemistry in Water of a Free and a Lipase-Embedded Cationic NCN-Pincer Platinum Center with Neutral and Ionic Triarylphosphines

    NARCIS (Netherlands)

    Wieczorek, B.; Snelders, D.J.M.; Dijkstra, H.P.; Versluis, C.; Lutz, M.; Spek, A.L.; Egmond, M.R.; Klein Gebbink, R.J.M.; van Koten, G.


    The coordination chemistry in aqueous media was studied for the platinum center of low-molecular-weight cationic NCN-pincer platinum complexes [RC6H2(CH2NMe2)2-3,5-Pt(H2O)-4]+ (R = −(CH2)3P(═O)(OEt)(OC6H4NO2-4) (1(OH2)), H (2(OH2))) as well as of the platinum center of the NCN-pincer platinum cation

  11. Optical Imaging of Mammaglobin Expression in Breast Cancer (United States)


    glutaconaldehyde dianilide monohydrochloride (2.84g, 9.97 mmol) and diisopropylethylamine ( DIEA , 2.60 g, 20.11 mmole) in DCM (20 mL). The resulting clear...O CH3 + X-N HOOC N COOH Reagents and Conditions: i. Ac2O/ DIEA /DCM/1h; ii.BrCH2CH2COOH/Dichlorobenzene/115 oC/16h; iii. CH3OH/reflux/16h. 1 2 3 4 i

  12. Uranium recovery process in phosphoric acid solutions

    International Nuclear Information System (INIS)

    Ginisty, Claude; Marteau, Michel; Mauborgne, Bernard.


    The description is given of a process for recovering uranium in a phosphoric acid solution by means of an organic solvent composed of a neutral phosphine oxide and an acid organophosphorated compound to the formulation R'R'' HPO 4 where R' and R'' which are identical or different, represent a linear or branched alkoxyalkyl radical comprising at least one -CH 2 -O-CH 2 - grouping or an aryloxyalkyl radical [fr

  13. Advanced Hybrid Materials for Aerospace Propulsion Applications (Briefing Charts) (United States)


    Ethylene glycol Dodecane Octane 5 mm Water Rapeseed oil Ethylene glycol Dodecane 5 mm Methanol ...Contact angles with water: DISTRIBUTION A. Approved for public release; distribution unlimited. 7 Methylene Iodide Octane Water Methanol ...unlimited. 8 Angew Chem 2008 Fluorinated POSS Synthesis Rf = -CH2CH2(CF2)nCF3 Si Si O O Si Si Si Si O O O O Si O Si O O O O O Rf Rf Rf Rf Rf Rf Rf Rf

  14. Methanofullerene-Based Palladium Bis(amino)aryl Complexes and Applications in Lewis Acid Catalysis

    NARCIS (Netherlands)

    Koten, G. van; Meijer, M.D.; Ronde, N.; Vogt, D.; Klink, G.P.M. van


    Synthetic routes have been developed for the attachment of palladium(II) bis(amino)aryl (NCN or C6H2{CH2NMe2}2-2,6)- complexes to C60. Using diazo and Bingel addition reactions, various methanofullerene NCN-SiMe3 compounds (C60-L-NCN-SiMe3, L = C(Me), C(CO2Et)CO2CH2, and C(Me)C6H4CC) have been

  15. Synthesis of N-Alkyl-2-thiomethyl Benzimidazoles: A Green Approach


    Rao, S. Srinivas; Reddy, Ch. Venkata Ramana; Dubey, P. K.


    A green approach for the synthesis of N-alkyl-2-thiomethyl benzimidazoles 2 (R=CH3, C2H5, CH2Ph) under different conditions has been developed from N-alkyl-2-chloromethyl benzimidazole (i.e., CH3, C2H5, CH2Ph) 1 by reaction with thiourea by physical grinding, or by using green solvents like ethanol and PEG-600, or by using microwave irradiation technique.

  16. Electronic nature of zwitterionic alkali metal methanides, silanides and germanides - a combined experimental and computational approach. (United States)

    Li, H; Aquino, A J A; Cordes, D B; Hase, W L; Krempner, C


    Zwitterionic group 14 complexes of the alkali metals of formula [C(SiMe 2 OCH 2 CH 2 OMe) 3 M], (M- 1 ), [Si(SiMe 2 OCH 2 CH 2 OMe) 3 M], (M- 2 ), [Ge(SiMe 2 OCH 2 CH 2 OMe) 3 M], (M- 3 ), where M = Li, Na or K, have been prepared, structurally characterized and their electronic nature was investigated by computational methods. Zwitterions M- 2 and M- 3 were synthesized via reactions of [Si(SiMe 2 OCH 2 CH 2 OMe) 4 ] ( 2 ) and [Ge(SiMe 2 OCH 2 CH 2 OMe) 4 ] ( 3 ) with MOBu t (M = Li, Na or K), resp., in almost quantitative yields, while M- 1 were prepared from deprotonation of [HC(SiMe 2 OCH 2 CH 2 OMe) 3 ] ( 1 ) with LiBu t , NaCH 2 Ph and KCH 2 Ph, resp. X-ray crystallographic studies and DFT calculations in the gas-phase, including calculations of the NPA charges confirm the zwitterionic nature of these compounds, with the alkali metal cations being rigidly locked and charge separated from the anion by the internal OCH 2 CH 2 OMe donor groups. Natural bond orbital (NBO) analysis and the second order perturbation theory analysis of the NBOs reveal significant hyperconjugative interactions in M- 1 -M- 3 , primarily between the lone pair and the antibonding Si-O orbitals, the extent of which decreases in the order M- 1 > M- 2 > M- 3 . The experimental basicities and the calculated gas-phase basicities of M- 1 -M- 3 reveal the zwitterionic alkali metal methanides M- 1 to be significantly stronger bases than the analogous silanides M- 2 and germanium M- 3 .

  17. Atmospheric lifetime of fluorotelomer alcohols

    DEFF Research Database (Denmark)

    Ellis, DA; Martin, JW; Mabury, SA


    Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with a series of fluorotelomer alcohols, F(CF2CF2)(n)-CH2CH2OH (n = 2, 3, 4), in 700 Torr of N-2 or air, diluent at 296 +/- 2K. The length of the F(CF2CF2)(n)- group had no discernible impact...

  18. Coordination studies of 1,2-bis(diphenylphosphinoethane with di-μ-hydroxo dinuclear complexes of tungsten(IV and molybdenum(IV

    Directory of Open Access Journals (Sweden)

    Minato Makoto


    Full Text Available The new trifluoroethoxo phosphine complexes [Cp2M(η1-dppe(CF3CH2O]+ and [Cp2(CF3CH2OM(μ-dppeMCp2(CF3CH2O]2+ (M = Mo or W, Cp = η-C5H5 and dppe = Ph2PCH2CH2PPh2 have been prepared by reaction of cationic di-μ-hydroxo dinuclear complex of molybdenocene or tungstenocene [Cp2M(μ-OH2MCp2]2+ with dppe. From the 1H and 31P NMR data, the configurations of the products could be assigned. Furtheremore, X-ray crystallography was used to definitively identify one of the product [Cp2(CF3CH2OMo(μ-dppeMoCp2(CF3CH2O]2+, which crystallizes in space group P21/c(#14 with a = 12.230(5 Å, b = 11.149(5 Å, c = 28.966(7 Å, β = 101.07(3°, V = 3876(2 Å3, and Z = 2. It was ascertained that the amount of dppe added to the reaction mixture could influence the product distribution. A mechanism involving initial replacement of the hydroxo ligand by the alkoxo group followed by nucleophilic attack of the phosphine is proposed on the basis of the reaction profile.

  19. Adsorption and reaction of propanal, 2-propenol and 1-propanol on Ni/Pt(111) bimetallic surfaces (United States)

    Murillo, Luis E.; Chen, Jingguang G.


    The hydrogenation of acrolein (CH 2dbnd CH sbnd CH dbnd O) can lead to the formation of three hydrogenation products, 2-propenol (CH 2dbnd CH sbnd CH 2sbnd OH), propanal (CH 3sbnd CH 2sbnd CH dbnd O), and 1-propanol (CH 3sbnd CH 2sbnd CH 2sbnd OH). In the current study the adsorption and reaction of these three molecules were investigated on Ni/Pt(111) surfaces to understand the different hydrogenation pathways of acrolein, using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). TPD experiments showed that 2-propenol underwent isomerization toward propanal on Pt(111) and the Pt sbnd Ni sbnd Pt(111) bimetallic surface, with a dominant decarbonylation pathway on the Pt(111) surface. A self-hydrogenation (disproportionation) pathway toward 1-propanol was observed on the Ni(111) film, however, the decarbonylation pathway was found to be the most dominant on this surface. Unlike 2-propenol, propanal did not undergo isomerization or self-hydrogenation pathways on any of the surfaces, with the dominant pathway being primarily the decarbonylation on Pt(111) and Ni(111). In contrast, 1-propanol underwent mainly molecular desorption from all three surfaces. These results provided additional understanding of previous studies of hydrogenation pathways of acrolein on the Ni/Pt(111) surfaces.

  20. Ru alkylidene compounds bearing tridentate, dianionic ligands: Lewis acid activation and olefin metathesis. (United States)

    McKinty, Adam M; Stephan, Douglas W


    The series of tridentate complexes of Ru-alkylidenes (L)Ru(CHPh)(SCH2CH2)2E (E = O, L = SIMes 1, PCy3 2, E = S, L = SIMes 3, PCy3 4; E = PPh 7, L = PCy3), (L)Ru(CHPh)(SC6H4)2S (L = SIMes 5, PCy3 6), (L)Ru(CHPh) (OCH2CH2)2O (L = SIMes 8, PCy3 9) were prepared and shown to react with one equivalent of BCl3 to give the complexes (L)Ru(CHPh)Cl[E(CH2CH2S)2BCl2] (E = O, L = SIMes 10, PCy3 11, E = S, L = SIMes 12a/b, PCy3 13, E = PPh, L = PCy3 16) and (L)Ru(CHPh)(SC6H4)2O (L = SIMes 14, PCy3 15). In the case of 1 and 2 reaction with two equivalents of BCl3 affording the corresponding cation via chloride abstraction. These cations coordinate MeCN to give the six coordinate Ru cation salts [(L)Ru(CHPh)- (NCMe)(O(CH2CH2S)2BCl2)][BCl4] L = SIMes 17, PCy3 18). The generated five coordinate cations derived from 2-9 via addition of two equivalents of BCl3 were evaluated in standard preliminary tests for olefin metathesis catalysis.

  1. Preparation Of 2-Aminoethylsulfonic Acid

    Directory of Open Access Journals (Sweden)



    Full Text Available Preparation process of 2-aminoethylsulfonic acid (taurine from ethanolamine, sulfuric acid and sodium sulfite has beenstudied. The process involves two steps of reactions, the first was esterification of ethanolamine (H2N-CH2-CH2-OHwith sulfuric acid to produce the intermediate product of 2-aminoethyl ester (H2N-CH2-CH2-OSO3H which then wasextended to the second step by sulfonation with sodium sulfite to produce 2-aminoethylsulfonic acid (H2N-CH2-CH2-SO3H. These two process conditions were observed by varying mole ratio of reactants, temperature and time period ofreactions. Taurine product was qualitatively analyzed using 1H-NMR and LC-MS. Physical-chemical analysis weredone by observing its melting point and determining its water, chloride and sulfate contents. Its melting point, watercontent, and sulfate content were 290oC, 0.303%, and 3 ppm, respectively, while its chloride content was undetected.After purification, the yield of process was 25.57%.

  2. Tunable N-substitution in zwitterionic benzoquinonemonoimine derivatives: metal coordination, tandemlike synthesis of zwitterionic metal complexes, and supramolecular structures. (United States)

    Yang, Qing-Zheng; Siri, Olivier; Braunstein, Pierre


    Full details on a very efficient transamination reaction for the synthesis of zwitterionic N,N-dialkyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium derivatives [C6H2(=NHR)2(=O)2] 5-16 are reported. The molecular structures of zwitterions 5 (R=CH3) in 5.H2O, 13 (R=CH2CH2OMe), 15 (R=CH2CH2NMe2), and of the parent, unsubstituted system [C6H2(=NH2)2(=O)2] 4 in 4.H2O have been established by single-crystal X-ray diffraction. This one-pot preparation can be carried out in water, MeOH, or EtOH and allows access to new zwitterions with N-substituents bearing functionalities such as -OMe (13), -OH (9-12), NR1R2 with R1 = or not equal R2 (14-16) or an alkene (8), leading to a rich coordination chemistry and allowing fine-tuning of the supramolecular arrangements in the solid state. As previously described for 15, which reacted with Zn(acac)2 to afford the octahedral Zn(II) complex [Zn[C6H2(NCH2CH2NMe2)O(O)(NHCH2CH2NMe2)]2] (20), ligands 13 and 16 with coordinating "arms" afforded with Zn(acac)2 the 2:1 adducts [Zn[C6H2(NCH2CH2X)O(=O)(NHCH2CH2NX)]2] 19 (X=OMe) and 21 (X=NHEt), with N2O4 and N4O2 donor sets around the octahedral Zn(II) center, respectively. Furthermore, zwitterions 15 and 16 reacted with ZnCl2 to give the stable, crystallographically characterized Zn(II) zwitterionic complexes [ZnCl2[C6H2(NCH2CH2NR1R2)O(=O)(NHCH2CH2NHR1R2)

  3. Post-transition state dynamics and product energy partitioning following thermal excitation of the F⋯HCH2CN transition state: Disagreement with experiment. (United States)

    Pratihar, Subha; Ma, Xinyou; Xie, Jing; Scott, Rebecca; Gao, Eric; Ruscic, Branko; Aquino, Adelia J A; Setser, Donald W; Hase, William L


    Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH 3 CN → HF + CH 2 CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. The experiments were performed at 300 K, and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F⋯HCH 2 CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH 2 CN and then trapping in the CH 2 CN⋯HF post-reaction potential energy well of ∼10 kcal/mol with respect to the HF + CH 2 CN products. In contrast to this IRC, five different trajectory types were observed: the majority proceeded by direct H-atom transfer and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH 2 CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. Simulations with an anharmonic zero-point energy constraint gave product distributions for relative translation, HF rotation, HF vibration, CH 2 CN rotation, and CH 2 CN vibration as 5%, 11%, 60%, 7%, and 16%, respectively. In contrast, the experimental energy partitioning percentages to HF rotation and vibration are 6% and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH 3 CN

  4. Unimolecular reactions of 1,1,1-trichloroethane, 1,1,1-trichloropropane, and 3,3,3-trifluoro-1,1,1-trichloropropane: determination of threshold energies by chemical activation. (United States)

    Turpin, Martha A; Smith, Kylie C; Heard, George L; Setser, D W; Holmes, Bert E


    The recombination of CCl3 radicals with CH3, CH3CH2, and CF3CH2 radicals was used to generate CH3CCl3, CH3CH2CCl3, and CF3CH2CCl3 molecules with approximately 87 kcal mol(-1) of vibrational energy in a bath gas at room temperature. The competition between collisional deactivation and unimolecular reaction by HCl elimination was used to obtain the experimental rate constants for each molecule. These experimental rate constants were matched to calculated statistical unimolecular rate constants to assign threshold energies to the three HCl elimination reactions. The models needed for the calculations of the rate constants were obtained from molecular structure calculations using density functional theory (DFT) with the hybrid density-functional MO6-2X recommended by Truhlar for transition states. The assigned threshold energies are 52 ± 2, 50 ± 2, and 52 ± 2 kcal mol(-1) for CH3CCl3, CH3CH2CCl3, and CF3CH2CCl3, respectively, and the CH3 and CF3 groups have only a minor effect on the threshold energies for HCl elimination. The DFT calculated threshold energies are in agreement with the experimentally assigned values. The addition of Cl atoms to the same carbon atom lowers the threshold energy for HCl elimination in the CH3CH2Cl, CH3CHCl2, and CH3CCl3 series. This trend, which is the opposite of that for CH3CH2F, CH3CHF2, and CH3CF3, is discussed in terms of transition-state structure and correlated with the relative stabilities of CH3CH2(+), CH3CHCl(+), and CH3CCl2(+) ions; the relative stabilities are based on the hydride affinities obtained from calculations. Comparison of the reactions of CH3CCl3 and CH2ClCHCl2 shows that the threshold energy is much higher for the isomer with chlorine atoms on both carbon atoms.

  5. Synthesis and insertion chemistry of mixed tether uranium metallocene complexes. (United States)

    Siladke, Nathan A; LeDuc, Jennifer; Ziller, Joseph W; Evans, William J


    The synthesis of mixed tethered alkyl uranium metallocenes has been investigated by examining the reactivity of the bis(tethered alkyl) metallocene [(η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)(2)U] (1) with substrates that react with only one of the U-C linkages. The effect of these mixed tether coordination environments on the reactivity of the remaining U-C bond has been studied by using CO insertion chemistry. One equivalent of azidoadamantane (AdN(3)) reacts with 1 to yield the mixed tethered alkyl triazenido complex [(η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)U(η(5)-C(5)Me(4)SiMe(2)-CH(2)NNN-Ad-κ(2)N(1,3))]. Similarly, a single equivalent of CS(2) reacts with 1 to form the mixed tethered alkyl dithiocarboxylate complex [(η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)U(η(5)-C(5)Me(4)SiMe(2)-CH(2)C(S)(2)-κ(2)S,S')], a reaction that constitutes the first example of CS(2) insertion into a U(4+)-C bond. Complex 1 reacts with one equivalent of pyridine N-oxide by C-H bond activation of the pyridine ring to form a mixed tethered alkyl cyclometalated pyridine N-oxide complex [(η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)(η(5)-C(5)Me(4)SiMe(3))U(C(6)H(4)NO-κ(2)C,O)]. The remaining (η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)(2-) ligand in each of these mixed tethered species show reactivity towards CO and tethered enolate ligands form by insertion. Subsequent rearrangement have been identified in [(η(5)-C(5)Me(4)SiMe(3))U(C(5)H(4)NO-κ(2)C,O)(η(5)-C(5)Me(4)SiMe(2)C(=CH(2))O-κO)] and [(η(5)-C(5)Me(4)SiMe(2)CH(2)NNN-Ad-κ(2)N(1,3))U(η(5)-C(5)Me(4)SiMe(2)C(=CH(2))O-κO)]. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Synthesis and insertion chemistry of mixed tether uranium metallocene complexes

    International Nuclear Information System (INIS)

    Siladke, Nathan A.; LeDuc, Jennifer; Ziller, Joseph W.; Evans, William J.


    The synthesis of mixed tethered alkyl uranium metallocenes has been investigated by examining the reactivity of the bis(tethered alkyl) metallocene [(η 5 -C 5 Me 4 SiMe 2 CH 2 -κC) 2 U] (1) with substrates that react with only one of the U-C linkages. The effect of these mixed tether coordination environments on the reactivity of the remaining U-C bond has been studied by using CO insertion chemistry. One equivalent of azidoadamantane (AdN 3 ) reacts with 1 to yield the mixed tethered alkyl triazenido complex [(η 5 -C 5 Me 4 SiMe 2 CH 2 -κC)U(η 5 -C 5 Me 4 SiMe 2 -CH 2 NNN-Ad-κ 2 N 1,3 )]. Similarly, a single equivalent of CS 2 reacts with 1 to form the mixed tethered alkyl dithiocarboxylate complex [(η 5 -C 5 Me 4 SiMe 2 CH 2 -κC)U(η 5 -C 5 Me 4 SiMe 2 - CH 2 C(S) 2 -κ 2 S,S ' )], a reaction that constitutes the first example of CS 2 insertion into a U 4+ -C bond. Complex 1 reacts with one equivalent of pyridine N-oxide by C-H bond activation of the pyridine ring to form a mixed tethered alkyl cyclometalated pyridine N-oxide complex [(η 5 -C 5 Me 4 SiMe 2 CH 2 -κC)(η 5 -C 5 Me 4 SiMe 3 )U(C 6 H 4 NO-κ 2 C,O)]. The remaining (η 5 -C 5 Me 4 SiMe 2 CH 2 -κC) 2- ligand in each of these mixed tethered species show reactivity towards CO and tethered enolate ligands form by insertion. Subsequent rearrangement have been identified in [(η 5 -C 5 Me 4 SiMe 3 )U(C 5 H 4 NO-κ 2 C,O)(η 5 -C 5 Me 4 SiMe 2 C(=CH 2 )O- κO)] and [(η 5 -C 5 Me 4 SiMe 2 CH 2 NNN-Ad-κ 2 N 1,3 )U(η 5 -C 5 Me 4 SiMe 2 C(=CH 2 )O-κO)]. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Host-guest complexation. 17. Design, syntheses, and complexation of macrocycles containing phosphoryl, pyridine oxide, and urea binding sites

    International Nuclear Information System (INIS)

    Kaplan, L.J.; Weisman, G.R.; Cram, D.J.


    Phosphoryl (P=O), urea (N 2 C=O), pyridine, and pyridine oxide (N → O) groups have been incorporated into the ring systems of macrocyclic polyethers. The association constants of the resulting eight new ligand systems toward Li + , Na + , K + , Rb + , Cs + , and NH 4 + picrates in CHCl 3 were surveyed, and the free energies of association were estimated. The P=O complexing sites were covalently bonded through two attached o-tolyl groups as in the unit RP(O)(C 6 H 4 CH 2 -o) 2 , in which different R groups were attached to phosphorus. The resulting unit, written as RPOD, was attached to two ether oxygens (0), which in turn were connected through CH 2 CH 2 or E units to form macrocycles. Ligand systems C 6 H 5 POD(OEOE) 2 O (9), C 6 H 5 POD(OEOEO) 2 E (10), o-HO 2 CC 6 H 4 POD(OEOE) 2 O (11), o-CH 3 O 2 CC 6 H 4 POD(OEOE) 2 O (12), CH 3 OPOD(OEOE) 2 O (13), and C 6 H 5 POD(OEO) 2 PODC 6 H 5 (14 and 15, the syn and anti isomers) were synthesized and examined. The urea complexing site was cyclic, CH 2 (CH 2 N) 2 C = O (abbreviated to UON), and was bonded through its two nitrogens to E units. The cycle prepared and examined was UON(EOEOE) 2 O (16). The pyridine and pyridine oxide complexing sites were bonded through CH 2 groups in their α,α' positions to comprise the units α-CH 2 (C 5 H 3 N)CH 2 -α and α-CH 2 (C 5 H 3 NO)CH 2 -α, respectively, the latter of which was abbreviated as POM. The new cycle prepared and examined was POM(OEOE) 2 O (18). The patterns of ΔG 0 values of complexation of these ligand systems were compared to those of 2,3-naphtho 18-crown-6 (19), 2,6-pyrido-18-crown-6 (20), and 1,3-benzo-18-crown-5 (21). The results suggest that those ligand systems whose organization of binding sites before and after complexation are the most similar show the highest structural recognition toward the anions

  8. Structural and Magnetic Diversity in Alkali-Metal Manganate Chemistry: Evaluating Donor and Alkali-Metal Effects in Co-complexation Processes. (United States)

    Uzelac, Marina; Borilovic, Ivana; Amores, Marco; Cadenbach, Thomas; Kennedy, Alan R; Aromí, Guillem; Hevia, Eva


    By exploring co-complexation reactions between the manganese alkyl Mn(CH2SiMe3)2 and the heavier alkali-metal alkyls M(CH2SiMe3) (M=Na, K) in a benzene/hexane solvent mixture and in some cases adding Lewis donors (bidentate TMEDA, 1,4-dioxane, and 1,4-diazabicyclo[2,2,2] octane (DABCO)) has produced a new family of alkali-metal tris(alkyl) manganates. The influences that the alkali metal and the donor solvent impose on the structures and magnetic properties of these ates have been assessed by a combination of X-ray, SQUID magnetization measurements, and EPR spectroscopy. These studies uncover a diverse structural chemistry ranging from discrete monomers [(TMEDA)2 MMn(CH2SiMe3)3] (M=Na, 3; M=K, 4) to dimers [{KMn(CH2SiMe3)3 ⋅C6 H6}2] (2) and [{NaMn(CH2SiMe3)3}2 (dioxane)7] (5); and to more complex supramolecular networks [{NaMn(CH2SiMe3)3}∞] (1) and [{Na2Mn2 (CH2SiMe3)6 (DABCO)2}∞] (7)). Interestingly, the identity of the alkali metal exerts a significant effect in the reactions of 1 and 2 with 1,4-dioxane, as 1 produces coordination adduct 5, while 2 forms heteroleptic [{(dioxane)6K2Mn2 (CH2SiMe3)4(O(CH2)2OCH=CH2)2}∞] (6) containing two alkoxide-vinyl anions resulting from α-metalation and ring opening of dioxane. Compounds 6 and 7, containing two spin carriers, exhibit antiferromagnetic coupling of their S=5/2 moments with varying intensity depending on the nature of the exchange pathways. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 31P nuclear magnetic resonance of phosphonic acid analogues of adenosine nucleotides as functions of pH and magnesium ion concentration

    International Nuclear Information System (INIS)

    Schliselfeld, L.H.; Burt, C.T.; Labotka, R.J.


    The 31 P NMR proton-decoupled spectra of α,β-methylene-ATP [Ap(CH 2 )pp], β,γ-methylene-ATP [App(CH 2 )p], and α,β-methylene-ADP [Ap(CH 2 )p] were measured as functions of pH and Mg 2+ concentration. Each ATP analogue yielded three resonances: two doublets and one doublet-of-a- doublet. Assignments of resonances were based upon spin-coupling multiplets, their coupling constant magnitudes (24-27 Hz for -P-O-P- and 4-10 Hz for -P-CH 2 -P-), and the magnitude of the chemical shift movement during proton titration or its direction of movement. All phosphonyl resonances are substantially downfield compared to phosphoryl resonances. The chemical shifts of terminal phosphonyl units moved upfield with increasing pH or rising Mg 2+ concentration. The chemical shifts of phosphonyl and phosphoryl anhydride plus ester units usually either moved downfield during proton titration and addition of Mg 2+ or remained constant. Accurate pK/sub a/' values were readily determined from chemical shift movements as a function of pH; 3.05 +/- 0.04 and 8.80 +/- 0.05 for App(CH 2 )p, 7.34 +/- 0.06 for Ap(CH 2 )pp, and 8.29 +/- 0.02 for AP(CH 2 )p. Addition of Mg 2+ or Tris produced an acidic shift of the alkaline pK/sub a/' values. Addition of Mg 2+ at pH 7.0 to the nucleotides caused large movements in the chemical shifts of their terminal two phosphorus atoms

  10. Comparisons of Box Model Calculations and Measurements of Formaldehyde from the 1997 North Atlantic Regional Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Frost, G. J.; Fried, Alan; Lee, Y.- N.; Wert, B.; Henry, B.; Drummond, J. R.; Evans, M. J.; Fehsenfeld, Fred C.; Goldan, P. D.; Holloway, J. S.; Hubler, Gerhard F.; Jakoubek, R.; Jobson, B Tom T.; Knapp, K.; Kuster, W. C.; Roberts, J.; Rudolph, Jochen; Ryerson, T. B.; Stohl, A.; Stroud, C.; Sueper, D. T.; Trainer, Michael; Williams, J.


    Formaldehyde (CH2O) measurements from two independent instruments are compared with photochemical box model calculations. The measurements were made on the National Oceanic and Atmospheric Administration P-3 aircraft as part of the 1997 North Atlantic Regional Experiment (NARE 97). The data set considered here consists of air masses sampled between 0 and 8 km over the North Atlantic Ocean which do not show recent influence from emissions or transport. These air masses therefore should be in photochemical steady state with respect to CH2O when constrained by the other P-3 measurements, and methane oxidation was expected to be the predominant source of CH2O in these air masses. For this data set both instruments measured identical CH2O concentrations to within 40 parts per trillion by volume (pptv) on average over the 0–800 pptv range, although differences larger than the combined 2s total uncertainty estimates were observed between the two instruments in 11% of the data. Both instruments produced higher CH2O concentrations than the model in more than 90% of this data set, with a median measured-modeled [CH2O] difference of 0.13 or 0.18 ppbv (depending on the instrument), or about a factor of 2. Such large differences cannot be accounted for by varying model input parameters within their respective uncertainty ranges. After examining the possible reasons for the model-measurement discrepancy, we conclude that there are probably one or more additional unknown sources of CH2O in the North Atlantic troposphere.

  11. Conformation and orientation effects in the x-ray photoelectron spectra of organic polymers

    International Nuclear Information System (INIS)

    Beamson, G.


    Conformation and orientation effects in the XPS spectra of organic polymers are small but can be observed with modem high performance equipment. This paper discusses some of the experimental factors that should be considered when attempting to detect such effects, and describes several recent studies which illustrate the subtle phenomena that can now be observed. Conformation effects, revealed by melting semicrystalline polymer samples in the analysis chamber of an XPS spectrometer, are reported for the valence band and C 1s spectra of nylon 12 and poly(ethylene adipate), and for the valence band spectrum of poly(ethylene succinate). For nylon 12 the changes in the C 2s region of the valence band spectrum are interpreted in terms of disordering of the planar zig-zag conformation of the (CH 2 ) 11 segments of the polymer chain. Pendant group surface orientation effects, detected by angle resolved XPS (with emission angles as low as 5 deg. relative to the sample surface), are reported for poly(2-chloroethyl methacrylate) (PCEMA), poly(lauryl methacrylate) (PLMA) and poly(2-hydroxyethyl methacrylate) (PHEMA). For PCEMA and PLMA the uppermost surfaces are enriched with -CH 2 CH 2 Cl and -(CH 2 ) 11 CH 3 pendant groups respectively, whereas for PHEMA the data suggest relatively few -CH 2 CH 2 OH pendant groups at the surface. The C 1s and Cl 2p spectra of PCEMA reveal surface core level binding energy shifts of - +0.2 eV, and the Cl L 23 M 23 M 23 spectrum a surface Auger kinetic energy shift of ∼ -0.6. The C 1s spectra of PLMA and PHEMA also reveal surface core level shifts and for PLMA this is interpreted in terms of a disordered and open arrangement of the -(CH 2 ) 11 CH 3 pendant groups at the polymer surface. (author)

  12. Formaldehyde Column Density Measurements as a Suitable Pathway to Estimate Near-Surface Ozone Tendencies from Space (United States)

    Schroeder, Jason R.; Crawford, James H.; Fried, Alan; Walega, James; Weinheimer, Andrew; Wisthaler, Armin; Mueller, Markus; Mikoviny, Tomas; Chen, Gao; Shook, Michael; hide


    In support of future satellite missions that aim to address the current shortcomings in measuring air quality from space, NASA's Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign was designed to enable exploration of relationships between column measurements of trace species relevant to air quality at high spatial and temporal resolution. In the DISCOVER-AQ data set, a modest correlation (r2 = 0.45) between ozone (O3) and formaldehyde (CH2O) column densities was observed. Further analysis revealed regional variability in the O3-CH2O relationship, with Maryland having a strong relationship when data were viewed temporally and Houston having a strong relationship when data were viewed spatially. These differences in regional behavior are attributed to differences in volatile organic compound (VOC) emissions. In Maryland, biogenic VOCs were responsible for approx.28% of CH2O formation within the boundary layer column, causing CH2O to, in general, increase monotonically throughout the day. In Houston, persistent anthropogenic emissions dominated the local hydrocarbon environment, and no discernable diurnal trend in CH2O was observed. Box model simulations suggested that ambient CH2O mixing ratios have a weak diurnal trend (+/-20% throughout the day) due to photochemical effects, and that larger diurnal trends are associated with changes in hydrocarbon precursors. Finally, mathematical relationships were developed from first principles and were able to replicate the different behaviors seen in Maryland and Houston. While studies would be necessary to validate these results and determine the regional applicability of the O3-CH2O relationship, the results presented here provide compelling insight into the ability of future satellite missions to aid in monitoring near-surface air quality.

  13. HPLC-UV, MALDI-TOF-MS and ESI-MS/MS analysis of the mechlorethamine DNA crosslink at a cytosine-cytosine mismatch pair.

    Directory of Open Access Journals (Sweden)

    Pornchai Rojsitthisak

    Full Text Available Mechlorethamine [ClCH(2CH(2N(CH(3CH(2CH(2Cl], a nitrogen mustard alkylating agent, has been proven to form a DNA interstrand crosslink at a cytosine-cytosine (C-C mismatch pair using gel electrophoresis. However, the atomic connectivity of this unusual crosslink is unknown.HPLC-UV, MALDI-TOF-MS, and ESI-MS/MS were used to determine the atomic connectivity of the DNA C-C crosslink formed by mechlorethamine, MALDI-TOF-MS of the HPLC-purified reaction product of mechlorethamine with the DNA duplex d[CTCACACCGTGGTTC]•d[GAACCACCGTGTGAG] (underlined bases are a C-C mismatch pair indicated formation of an interstrand crosslink at m/z 9222.088 [M-2H+Na](+. Following enzymatic digestion of the crosslinked duplex by snake venom phosphodiesterase and calf intestinal phosphatase, ESI-MS/MS indicated the presence of dC-mech-dC [mech = CH(2CH(2N(CH(3CH(2CH(2] at m/z 269.2 [M](2+ (expected m/z 269.6, exact mass 539.27 and its hydrolytic product dC-mech-OH at m/z 329.6 [M](+ (expected m/z 329.2. Fragmentation of dC-mech-dC gave product ions at m/z 294.3 and 236.9 [M](+, which are both due to loss of the 4-amino group of cytosine (as ammonia, in addition to dC and dC+HN(CH(3CH = CH(2, respectively. The presence of m/z 269.2 [M](2+ and loss of ammonia exclude crosslink formation at cytosine N(4 or O(2 and indicate crosslinking through cytosine N(3 with formation of two quaternary ammonium ions.Our results provide an important addition to the literature, as the first example of the use of HPLC and MS for analysis of a DNA adduct at the N(3 position of cytosine.

  14. Syntheses and structural characterizations of inorganic ansa-metallocene analogues: ansa-ferratricarbadecaboranes. (United States)

    Gleeson, Brendan; Carroll, Patrick J; Sneddon, Larry G


    New linked cyclopentadienyl-tricarbadecaboranyl and bis-tricarbadecaboranyl dianions have been used to form the first examples of ansa-metallatricarbadecaboranyl complexes. The hybrid cyclopentadienyl-tricarbadecaboranyl dianion, Li2(+)[6-C5H4-(CH2)2-nido-5,6,9-C3B7H9](2-) (1), was produced by an initial carbon-insertion reaction of a nitrile-substituted cyclopentadiene with the arachno-4,6-C2B7H12(-) anion, followed by deprotonation to the dianion with LiH. The linked-cage bis-tricarbadecaboranyl dianion, Li2(+)[6,6'-(CH2)2-nido-(5,6,9-C3B7H9)2](2-) (2), was produced by a similar carbon-insertion route involving the reaction of two equivalents of arachno-4,6-C2B7H12(-) with succinonitrile. The reaction of 1 with an equivalent of FeCl2 produced the hybrid complex, ansa-(2-(CH2)2)-(1-η(5)-C5H4-closo-1,2,3,4-C3B7H9)Fe (3), with a crystallographic determination confirming the formation of a sandwich structure where the ring and cage are linked by the ansa -CH2CH2- group with attachment to the cage at the C2 carbon. The reaction of 2 with FeCl2 produced three isomeric ansa-(CH2)2-ferrabistricarbadecaboranyl sandwich complexes, ansa-(CH2)2-(closo-C3B7H9)2Fe (4, 5 and 6). Crystallographic determinations showed that in 4, the two tricarbadecaboranyl ligands are linked by the ansa-CH2CH2- group at the C2 and C2' cage carbons, whereas in 5 and 6 they are linked at their C2 and C4' carbons, with the structures of 5 and 6 differing in the relative positions of the C4' carbons in the two cages of each complex. The structural determinations also showed that, depending upon the linking position of the ansa-tether, constraints in cage-orientation, such as observed in 4, produce unfavorable intercage steric interactions. However, the cage fragments in these complexes can readily undergo a cage-carbon migration that moves one -carbon and its tether linkage to the more favorable 4-position. This isomerization reduces the cage steric interactions and produces configurations, such as

  15. Combining vibrational biomolecular spectroscopy with chemometric techniques for the study of response and sensitivity of molecular structures/functional groups mainly related to lipid biopolymer to various processing applications. (United States)

    Yu, Gloria Qingyu; Yu, Peiqiang


    The objectives of this project were to (1) combine vibrational spectroscopy with chemometric multivariate techniques to determine the effect of processing applications on molecular structural changes of lipid biopolymer that mainly related to functional groups in green- and yellow-type Crop Development Centre (CDC) pea varieties [CDC strike (green-type) vs. CDC meadow (yellow-type)] that occurred during various processing applications; (2) relatively quantify the effect of processing applications on the antisymmetric CH3 ("CH3as") and CH2 ("CH2as") (ca. 2960 and 2923 cm(-1), respectively), symmetric CH3 ("CH3s") and CH2 ("CH2s") (ca. 2873 and 2954 cm(-1), respectively) functional groups and carbonyl C=O ester (ca. 1745 cm(-1)) spectral intensities as well as their ratios of antisymmetric CH3 to antisymmetric CH2 (ratio of CH3as to CH2as), ratios of symmetric CH3 to symmetric CH2 (ratio of CH3s to CH2s), and ratios of carbonyl C=O ester peak area to total CH peak area (ratio of C=O ester to CH); and (3) illustrate non-invasive techniques to detect the sensitivity of individual molecular functional group to the various processing applications in the recently developed different types of pea varieties. The hypothesis of this research was that processing applications modified the molecular structure profiles in the processed products as opposed to original unprocessed pea seeds. The results showed that the different processing methods had different impacts on lipid molecular functional groups. Different lipid functional groups had different sensitivity to various heat processing applications. These changes were detected by advanced molecular spectroscopy with chemometric techniques which may be highly related to lipid utilization and availability. The multivariate molecular spectral analyses, cluster analysis, and principal component analysis of original spectra (without spectral parameterization) are unable to fully distinguish the structural differences in the

  16. The magnetic resonance spectroscopy analysis for fatty acid of cooking oil

    International Nuclear Information System (INIS)

    Yu, Seung Man


    The aim of this study was to evaluate possibility for chemical changes analysis of the Soybean and Olive oil using a medical magnetic resonance imaging/spectrometer. The two edible oils including soybean and olive oil were selected for manufacturing the phantom series. For the acquisition of data without any physical environment change, 5 ml was transferred to a sealed plastic vial. All MRI and 1H-MRS experiments were performed on a 3.0 Tesla MRI scanner using a 32-channel brain array coil. The total lipid ((-CH2-)n/noise), total saturated fatty acid, total unsaturated fatty acid, total unsaturated bond, and poly unsaturated bond were quantified by separating each peak area of -CH 3 , (-CH 2 -)n, -CH 2 -C=C-CH 2 -, =C-CH 2 -C=, and -CH=CH-byCH 3 by MRS analysis. Soybean oil had the highest concentration of methyl protons and methane protons, expressed as 0.9 and 5.3 ppm compared to olive oil. However, its methylene protons at 1.3 ppm were the lowest. Olive oil had the highest amount of methylene protons and allylic protons and the lowest amount of methyl protons. Through the magnetic resonance spectroscopic analysis it was to analyze the chemical characteristics of Olive oil and soybean oil. And it was confirmed that it is possible to proceed to an extended study using magnetic resonance spectroscopy

  17. Ionic liquid electrolytes based on multi-methoxyethyl substituted ammoniums and perfluorinated sulfonimides: Preparation, characterization, and properties

    International Nuclear Information System (INIS)

    Han Hongbo; Liu Kai; Feng Shaowei; Zhou Sisi; Feng Wenfang; Nie Jin; Li Hong; Huang Xuejie; Matsumoto, Hajime; Armand, Michel; Zhou Zhibin


    Graphical abstract: New functionalized ionic liquids based on multi-methoxyethyl substituted quaternary ammonium cations and perfluorinated sulfonimide anions are introduced. -- Abstract: New functionalized ionic liquids (ILs), comprised of multi-methoxyethyl substituted quaternary ammonium cations (i.e. [N(CH 2 CH 2 OCH 3 ) 4-n (R) n ] + ; n = 1, R = CH 3 OCH 2 CH 2 ; n = 1, R = CH 3 , CH 2 CH 3 ; n = 2, R = CH 3 CH 2 ), and two representative perfluorinated sulfonimide anions (i.e. bis(fluorosulfonyl)imide (FSI - ) and bis(trifluoromethanesulfonyl)imide (TFSI - )), were prepared. Their fundamental properties, including phase transition, thermal stability, viscosity, density, specific conductivity and electrochemical window, were extensively characterized. These multi-ether functionalized ionic liquids exhibit good capability of dissolving lithium salts. Their binary electrolytes containing high concentration of the corresponding lithium salt ([Li + ] >1.6 mol kg -1 ) show Li + ion transference number (t Li + ) as high as 0.6-0.7. Their electrochemical stability allows Li deposition/stripping realized at room temperature. The desired properties of these multi-ether functionalized ionic liquids make them potential electrolytes for Li (or Li-ion) batteries.

  18. Study of RF-excited Diethylene Glycol Dimethyl Ether Plasmas by Mass Spectrometry

    International Nuclear Information System (INIS)

    Algatti, M A; Mota, R P; Júnior, P W P Moreira; Honda, R Y; Kayama, M E; Kostov, K G


    This paper deals with the study of the fragmentation process of diethylene glycol dimethyl ether (CH 3 O(CH 2 CH 2 O) 2 CH 3 ) (diglyme here in) molecule in low pressure RF excited plasma discharges. The study was carried out using mass spectrometry. The results showed that for a fixed pressure, the increase of the RF power coupled to the plasma chamber from 1 to 35 W produced a plasma environment much more reactive which increases the population of the ionized species like CH 2 + (15 amu), C 2 H 4 + (28 amu), CH 3 O + (31 amu), C 2 H 4 O + (44 amu), CH 3 OCH 2 CH 2 + (59 amu) and CH 3 OCH 2 CH 2 O + (75 amu). This fact may be attributed to the increase of the electronic temperature that makes predominant the occurrence of inelastic processes that promotes molecular fragmentation. For a fixed value of RF power the increase of pressure from 50 mTorr to 100 mTorr produces the decreasing of the above mentioned chemical species due the lower electronic mean free path. These results suggest that if one wants to keep the monomer's functionality within the plasma deposited films resulting from such kind of discharges one must operate in low power conditions.

  19. 4-Alkynylphenylsilatranes: Insecticidal activity, mammalian toxicity, and mode of action

    International Nuclear Information System (INIS)

    Horsham, M.A.; Palmer, C.J.; Cole, L.M.; Casida, J.E.


    4-Ethynyl- and 4-(prop-1-ynyl)phenylsilatranes [N(CH 2 CH 2 O) 3 SiR, R = C 6 H 4 -4-C triple-bond CH or C 6 H 4 -4-C triple-bond CCH 3 ] are highly toxic to houseflies (pretreated with piperonyl butoxide) and milkweed bugs (topical LD 50 s 3-14 μg/g) and to mice (intraperitoneal LD 50 s 0.4-0.9 mg/kg), and they are moderately potent inhibitors of the [ 35 S]-tert-butylbicyclophosphorothionate or TBPS binding site (GABA-gated chloride channel) of mouse brain membranes. Scatchard analysis indicates noncompetitive interaction of 4-ethynylphenylsilatrane with the TBPS binding site. Phenylsilatrane analogues with 4-substituents of H, CH 3 , Cl, Br, and C triple-bond CSi(CH 3 ) 3 are highly toxic to mice but have little or no activity in the insect and receptor assays. Radioligand binding studies with [4- 3 H]phenylsilatrane failed to reveal a specific binding site in mouse brain. Silatranes with R = H, CH 3 , CH 2 Cl, CH double-bond CH 2 , OCH 2 CH 3 , and C 6 H 4 -4-CH 2 CH 3 are of little or no activity in the insect and mouse toxicity and TBPS binding site assays as are the trithia and monocyclic analogues of phenylsilatrane. 4-Alkynylphenylsilatranes are new probes to examine the GABA receptor-ionophore complex of insects and mammals

  20. Insertion, reduction, and carbon-carbon coupling induced by monomeric aluminum hydride compounds bearing substituted pyrrolyl ligands. (United States)

    Lin, Che-Yu; Tsai, Chia-Fu; Chen, Hsing-Jen; Hung, Chen-Hsiung; Yu, Ru-Ching; Kuo, Pei-Cheng; Lee, Hon Man; Huang, Jui-Hsien


    A monomeric aluminum hydride complex bearing substituted pyrrolyl ligands, AlH[C(4)H(3)N(CH(2)NMe(2))-2](2) (1), was synthesized and structurally characterized. To further confirm the presence of Al--H bonds, the compound AlD[C(4)H(3)N(CH(2)NMe(2))-2](2) ([D]1) was synthesized by reacting LiAlD(4) with [C(4)H(4)N(CH(2)NMe(2))-2]. Compound 1 and [D]1 react with phenyl isothiocyanate yielding Al[C(4)H(3)N(CH(2)NMe(2))-2](2)[eta(3)-SCHNPh] (2) and Al[C(4)H(3)N(CH(2)NMe(2))-2](2)[eta(3)-SCDNPh] ([D]2) by insertion. The reactions of 1 with 9-fluorenone and benzophenone generated the unusual aluminum alkoxide complexes 3 and 4, respectively, through intramolecular proton abstraction and C-C coupling. A mechanistic study shows that 9-fluorenone coordinates to [D]1 and releases one equivalent of HD followed by C-C coupling and hydride transfer to yield the final product. Reduction of benzil with 1 affords aluminum enediolate complex 5 in moderate yield. Mechanistic studies also showed that the benzil was inserted into the aluminum hydride bond of [D]1 through hydroalumination followed by proton transfer to generate the final product [D]5. All new complexes have been characterized by (1)H and (13)C NMR spectroscopy and X-ray crystallography.

  1. Syntheses, characterization and antifungal activity of heteroleptic nickel(II) complexes with N-alkylsulfonyldithiocarbimates and phosphines (United States)

    Vidigal, Antonio E. C.; Rubinger, Mayura M. M.; Oliveira, Marcelo R. L.; Guilardi, Silvana; Souza, Rafael A. C.; Ellena, Javier; Zambolim, Laércio


    Four nickel(II) complexes of general formula [Ni(RSO2Ndbnd CS2) (PPh3)2] where R = CH3 (2a), CH3CH2 (2b), CH3(CH2)3 (2c) and CH3(CH2)7 (2d) and PPh3 = triphenylphosphine; and two nickel(II) complexes of general formula [Ni(RSO2Ndbnd CS2)dppe] where R = CH3(CH2)3 (3c) and CH3(CH2)7 (3d) and dppe = 1,2-bis(diphenylphosphine)ethane) were prepared. These new complexes were obtained by the reaction of nickel(II) chloride hexahydrate with potassium N-alkylsulfonyldithiocarbimates and the appropriate phosphine using ethanol/water as solvent. The IR, UV-Vis and 1H, 13C and 31P NMR spectra, elemental analysis of Ni and the HR-ESI-MS were consistent with the formation of square planar nickel(II) complexes with mixed ligands. The structures of the compounds 2b and 2c were determined by single crystal X-ray diffraction. The compounds are isostructural and crystallize in the space group P 1 bar of the triclinic system. The activities of the complexes were investigated in vitro against Botrytis cinerea, Colletotrichum acutatum and Alternaria solani, fungi species that affect various commercially important plants. All the complexes were active.

  2. Radiation-induced transformations of isolated CH3CN molecules in noble gas matrices (United States)

    Kameneva, Svetlana V.; Volosatova, Anastasia D.; Feldman, Vladimir I.


    The transformations of isolated CH3CN molecules in various solid noble-gas matrices (Ne, Ar, Kr, and Xe) under the action of X-ray irradiation at 5 K were investigated by FTIR spectroscopy. The main products are CH3NC, CH2CNH and CH2NCH molecular isomers as well as CH2CN and CH2NC radicals. The matrix has a strong effect on the distribution of reaction channels. In particular, the highest relative yield of keteneimine (CH2CNH) was found in Ne matrix, whereas the formation of CH3NC predominates in xenon. It was explained by differences in the matrix ionization energy (IE) resulting in different distributions of hot ionic reactions. The reactions of neutral excited states are mainly involved in Xe matrix with low IE, while the isomerization of the primary acetonitrile positive ions may be quite effective in Ne and Ar. Annealing of the irradiated samples results in mobilization of trapped hydrogen atoms followed by their reactions with radicals to yield parent molecule and its isomers. The scheme of the radiation-induced processes and its implications for the acetonitrile chemistry in cosmic ices are discussed.

  3. Using microkinetic analysis to search for novel anhydrous formaldehyde production catalysts (United States)

    Li, Han-Jung; Lausche, Adam C.; Peterson, Andrew A.; Hansen, Heine A.; Studt, Felix; Bligaard, Thomas


    Direct dehydrogenation of methanol to produce anhydrous formaldehyde is investigated using periodic density functional theory (DFT) and combining the microkinetic model to estimate rates and selectivities on stepped (211) surfaces under a desired reaction condition. Binding energies of reaction intermediates and transition state energies for each elementary reaction can be accurately scaled with CHO and OH binding energies as the only descriptors. Based on these two descriptors, a steady-state microkinetic model is constructed with a piecewise adsorbate-adsorbate interaction model that explicitly includes the effects of adsorbate coverage on the rates and selectivities as well as the volcano plots are obtained. Our results show that most of the stepped (211) pure-metallic surfaces such as Au, Pt, Pd, Rh, Ru, Ni, Fe, and Co are located in a region of low activity and selectivity toward CH2O production due to higher rate for CH2O dehydrogenation than CH2O desorption. The selectivities toward CH2O production on Zn, Cu, and Ag surfaces are located on the boundary between the high and low selectivity regions. To find suitable catalysts for anhydrous CH2O production, a large number of A3B-type transition metal alloys are screened based on their predicted rates and selectivities, as well as their estimated stabilities and prices. We finally propose several promising candidates for the dehydrogenation of CH3OH.

  4. Theoretical Study of Ethylene Oligomerization by an Organometallic Nickel Catalyst. (United States)

    Fan, L.; Krzywicki, A.; Somogyvari, A.; Ziegler, T.


    The mechanism for ethylene oligomerization by (acac)NiH has been studied using density functional theory (DFT). The transition states for chain propagation and chain termination were optimized and the related reaction barriers calculated. Several possible mechanisms were considered for the chain termination step. Chain termination by beta-hydrogen elimination was found to be energetically unfavorable, and is not likely to be important. Instead, beta-hydrogen transfer to the incoming ethylene unit seems to be operative. The most favorable beta-hydrogen transfer pathway has two transition states. The first leads from a weak pi-complex between an incoming ethylene unit and (acac)NiCH(2)CH(2)R to an intermediate in which the two olefins C(2)H(4) and H(2)CCHR both are strongly pi-complexed to the nickel hydride (acac)NiH. The second barrier takes the intermediate to another weak pi-complex between (acac)NiCH(2)CH(3) and H(2)C=CHR from which the oligomer H(2)C=CHR can be released and the catalyst (acac)NiCH(2)CH(3) regenerated. Due to the mechanism of chain termination, the actual catalyst is proposed to be (acac)NiCH(2)CH(3) whereas (acac)NiH serves as a precursor or precatalyst.

  5. Detergent for radioactive decontamination and laundry waste treatment

    International Nuclear Information System (INIS)

    Takeuchi, Takashi; Tsuji, Takao; Iwafuji, Yosaburo; Hamada, Shoichi.


    Object: To provide a detergent for radioactive decontamination which can enrich a laundry waste to a high concentration without producing foaming carry-over. Structure: In order to treat a laundry waste by a detergent containing, as essential constituents, a nonion surface active agent 0.2 - 3 wt% represented by HO (CH 2 CH 2 O)sub(l) (CH 2 CH 3 CHO)sub(m) (CH 2 CH 2 O)sub(n)H (where m = 15 - 35, l + n = 0.2m - 1.4m), tripolypotassium metal salt 40 - 90 wt%, alkali silicate metal salt 0.2 - 2 wt%, and 2-mercaptobenzothiazole or alkali metal salt 0.01 - 1 wt%, a heat-resisting foam inhibitor such as polypropylene glycol, polyoxypropylenealkyl ether or the like is added to the waste which is heated and concentrated to reduce capacity. This treatment enables the waste to be reduced to 1/300 to 1/400. (Kamimura, M.)

  6. Reaction of N(2D) atoms with bromomethyl radicals: A theoretical study

    International Nuclear Information System (INIS)

    Cimas, A.; Rayon, V.M.; Barrientos, C.; Aschi, M.; Sordo, J.A.; Largo, A.


    The singlet potential energy surface for the N( 2 D) + CH 2 Br reaction has been studied employing both MP2 and DFT(B3LYP) methods. The energies of the involved species have been refined using the G2, CBS and CCSD(T) methods, respectively. The reaction proceeds through the formation of an initial intermediate which does not involve any activation barrier. Based on the singlet PES, the most exothermic products result from elimination of either HBr or H 2 , instead of elimination of either Br or H. The preferred channel is predicted to be HCN + HBr. The analysis of the possible spin crossing between the triplet and singlet [CH 2 NBr] potential surfaces suggests that the N( 4 S) + CH 2 Br reaction should take place with no change in the spin angular momentum

  7. Intracavity absorption spectroscopy of formaldehyde from 6230 to 6420 cm-1 (United States)

    Fjodorow, Peter; Hellmig, Ortwin; Baev, Valery M.; Levinsky, Howard B.; Mokhov, Anatoli V.


    We apply intracavity absorption spectroscopy for measurements of the absorption spectrum of formaldehyde, CH2O, from 6230 to 6420 cm-1, of which only a small fraction (6351-6362 cm-1) has been recorded elsewhere. The measurements are performed in the cavity of a broadband Er3+-doped fiber laser, with a sensitivity corresponding to the effective absorption path length of 45 m and a spectral resolution of 0.1 cm-1. The noise-equivalent detection limit of CH2O achieved with the strongest absorption line at 6252.64 cm-1 is estimated to be 5 ppm. High tolerance to broadband losses and the accessible time resolution of 50 µs make it possible to apply this detection system for time-resolved monitoring of CH2O together with other molecules in harsh combustion environments, e.g., in combustion engines.

  8. Assessment and Selection of Materials for Melbourne City Council House 2

    Directory of Open Access Journals (Sweden)

    Dominique Hes


    Full Text Available This paper highlights the role of material selection in the development and contribution toward environmental excellence in the building project Council House 2 (CH2. The paper focuses on the assessment of material and the strategies used by the design team in CH2to ensure the best environmental result. The paper then goes on to explore in a case study the application of these strategies in the selection and specification of concrete on CH2. The purpose of the paper is to explore the difficulties and rewards of careful research of manufacturers' claims and the relative benefits of different materials. The paper concludes that the process of material selection adopted on this project has increased the education of architects and manufacturers alike as well as being environmentally beneficial.

  9. UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Sehested, J.


    Alkyl and alkyl peroxy radicals from 1-butyl alcohol (TBA), HOC (CH3)2CH2. and HOC(CH3)2CH2O2. have been studied in the ps phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR......) and k(HOC(CH3)2CH2O2. + NO2) were determined to be (4.9 +/- 0.9) X 10(-12) and (6.7 +/- 0.9) x 10(-12) cm3 molecule-1 s-1, respectively. In the FTIR experiments products were studied using chlorine-initiated oxidation in TBA/N2/Cl2 and TBA/N2/O2/Cl2 mixtures....

  10. 1.2.2.Synthesis, crystal structure and in vitro anti-tumor activity of dibutyltin complex of 2,4-dichloro-5-fluorobenzoic acid

    Directory of Open Access Journals (Sweden)

    Ming Li, Liqin Wang, Zhenlei Zhang, Yue Xin, Laijin Tian*


    Full Text Available The dibutyltin complex of 2,4-dichloro-5- fluorobenzoic acid, [(2,4-Cl2 -5-FC6 H2 C(OOSnBu2 2 O]2 (Bu = CH2 CH2 CH2 CH3 (1 , has been synthesized and characterized by elemental analysis, FT-IR, 119 Sn NMR spectroscopy, and Xray single crystal diffraction. Compound 1 is a centrosymmetric dimmer with two distinct types of carboxylate moieties and tin atoms with distorted trigonal bipyramidal geometries. The in vitro  anti-tumor activity of 1 against two human tumor cell lines was found to be higher than that for cis-platin [cis diaminedichloroplatinum( II] used clinically. Supporting information : FT-IR, 119 Sn NMR, X-Ray, Proliferation inhibitory rate, Cif file.

  11. Piperazines as nootropic agents: New derivatives of the potent cognition-enhancer DM235 carrying hydrophilic substituents. (United States)

    Martino, Maria Vittoria; Guandalini, Luca; Di Cesare Mannelli, Lorenzo; Menicatti, Marta; Bartolucci, Gianluca; Dei, Silvia; Manetti, Dina; Teodori, Elisabetta; Ghelardini, Carla; Romanelli, Maria Novella


    The piperazine ring of the potent nootropic drug DM235 has been decorated with H-bond donor and acceptor groups (CH 2 OH, CH 2 OMe, CH 2 OCOMe, COOEt); the aim was to insert new functional groups, suitable for further chemical manipulation. The influence of these modifications on nootropic activity was assessed by means of the mouse passive avoidance test; some of the newly synthesized molecules (alcohol 7b, acetate 8b and ester 10d) showed interesting in vivo potency. This makes it possible to use these functional groups for adding other residues, in order to increase molecular diversity, or for anchoring a biotin group, to obtain compounds useful to capture the biological target. Moreover, the new compounds will improve our knowledge of structure activity relationships of this family of drugs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Synthesis, crystal structure, DNA binding and molecular docking studies of zinc(II) carboxylates (United States)

    Muhammad, Niaz; Ikram, Muhammad; Wadood, Abdul; Rehman, Sadia; Shujah, Shaukat; Erum; Ghufran, Mehreen; Rahim, Shahnaz; Shah, Muzamil; Schulzke, Carola


    New zinc(II) carboxylate complexes [Zn(3-F-C6H4CH2COO)2]n (1), [Zn3(3-F-C6H4CH2COO)6(Phen)2] (2) and [Zn3(3-F-C6H4CH2COO)6(bipy)2] (3) were synthesized and characterized by atomic absorption, single crystal structural analysis and IR studies. Complex 1 crystallizes as a coordination polymer constituting a web of μ - η1,η1 carboxylate bridged tetrahedral zinc centers. Complexes 2 and 3 comprise trinuclear zinc centers with two terminal fivefold coordinated slightly distorted square-pyramidal and central sixfold coordinated octahedral zinc centers. The complexes were also assessed for their DNA binding ability by UV/- Vis spectroscopy and their behavior rationalized theoretically by molecular docking studies. A DNA binding study has shown groove binding interactions with the complexes.

  13. Mechanistic studies on the phosphoramidite coupling reaction in oligonucleotide synthesis. I. Evidence for nudeophilic catalysis by tetrazole and rate variations with the phosphorus substituents

    DEFF Research Database (Denmark)

    Dahl, Bjarne H.; Nielsen, John; Dahl, Otto


    Tetrazole catalyzed reactions of a series of phosphoramidites, 5′ -O- DMTdT-3′-O-P(OR 1)NRNR22 (1a-h), with 3′ O-SiBu tPh 2-6-N-benzoyl-dA (2a) in acetonitrite solution have been studied. It is found that the coupling rate depends very much on whether tetrazole is added before or after 2a......, and that dialkylammonium tetrazolide salts are inhibitors. These and other facts are evidence that the reactions are subjected to nucleophilic catalysis by tetrazole, in addition to acid catalysis. The rate variations with phosphorus substituents of 1a-h are NEt 2 > NRr12 > N(CH 2CH 2)O > NMePh, and OMe > OCH 2CH 2CN...

  14. Thermo-acoustical molecular interaction study in binary mixtures of glycerol and ethylene glycol (United States)

    Kaur, Kirandeep; Juglan, K. C.; Kumar, Harsh


    Ultrasonic velocity, density and viscosity are measured over the entire composition range for binary liquid mixtures of glycerol (CH2OH-CHOH-CH2OH) and ethylene glycol (HOCH2CH2OH) at different temperatures and constant frequency of 2MHz using ultrasonic interferometer, specific gravity bottle and viscometer respectively. Measured experimental values are used to obtained various acoustical parameters such as adiabatic compressibility, acoustic impedance, intermolecular free length, relaxation time, ultrasonic attenuation, effective molar weight, free volume, available volume, molar volume, Wada's constant, Rao's constant, Vander Waal's constant, internal pressure, Gibb's free energy and enthalpy. The variation in acoustical parameters are interpreted in terms of molecular interactions between the components of molecules of binary liquid mixtures.

  15. Synthesis, characterization, and antifungal activity of novel (Z)-N-(2-cyano-3-phenylprop-2-en-1-yl)-alkyl/aryl-sulfonamides derived from a Morita-Baylis-Hillman adduct (United States)

    Tavares, Eder C.; Rubinger, Mayura M. M.; Zacchi, Carlos H. C.; Silva, Simone A.; Oliveira, Marcelo R. L.; Guilardi, Silvana; Alcântara, Antônio F. de C.; Piló-Veloso, Dorila; Zambolim, Laércio


    A series of allyl sulfonamides prepared from the reaction of the Morita-Baylis-Hillman adduct 2-[hydroxy(phenyl)methyl]acrylonitrile with primary sulfonamides (RSO2NH2), where R = C6H5 (1), 4-Fsbnd C6H4 (2), 4-Clsbnd C6H4 (3), 4-Brsbnd C6H4 (4), 4-NO2sbnd C6H4 (5), CH3 (6), CH3CH2 (7), CH3(CH2)3 (8), and CH3(CH2)7 (9), were characterized by IR, 1H and 13C NMR spectroscopies, mass spectrometry and elemental analyses. BLYP/6-31G* calculations suggested stereoselective reactions, resulting in the exclusive formation of the thermodynamically more stable Z-products. The Z-configuration of the products was confirmed by NOE difference spectroscopy and single crystal X-ray diffraction measurements. The allyl sulfonamides were active against Colletotrichum gloeosporioides, an important agent of anthracnose in plants.

  16. N,N′-Bis(4-chlorophenylsulfonylsuberamide

    Directory of Open Access Journals (Sweden)

    Vinola Z. Rodrigues


    Full Text Available The asymmetric unit of the title compound, C20H22Cl2N2O6S2, contains one half-molecule with a center of symmetry at the mid-point of the central C—C bond. The conformations of all the N—H, C=O and C—H bonds in the central amide and aliphatic segments are anti to their adjacent bonds. The molecule is bent at the S atom with a C—SO2—NH—C(O torsion angle of −80.6 (4°. The dihedral angle between the benzene ring and the SO2—NH—C(O—CH2CH2CH2 segment is 79.5 (2°. In the crystal, intermolecular N—H...O(C and N—H...O(S hydrogen bonds link the molecules into chains along the b axis.

  17. Dynamics of Low-Energy Electron Induced Reactions in Condensed (United States)

    Boyer, Michael; Soe, Chanmyaemyae; Chamberlain, Kristal; Shyur, Yomay; Arumainayagam, Christopher


    We present insights into the dynamics of low-energy electron-induced reactions in thin films of methanol (CH3 OH). Low-energy electrons in matter can initiate chemical reactions though electron impact ionization of a molecule, electron impact excitation of a molecule, or through dissociation of a transient negative ion formed by electron attachment to a molecule. Our studies focus on the dynamics by which low-energy electron interaction with condensed methanol initiates chemical reactions which lead to the formation of methoxymethanol (CH3 O CH2 OH) and ethylene glycol (HO CH2 CH2 OH). The results of our post-irradiation temperature programmed desorption experiments indicate that both products can form from irradiating methanol with electrons at subionization energies. In addition, we find evidence that dissociative electron attachment plays a role in the formation of methoxymethanol but not in ethylene glycol.

  18. Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic Hydroaminoalkylation Reactions

    KAUST Repository

    Hamzaoui, Bilel


    Intermolecular catalytic hydroaminoalkylation of unactivated alkene occurs with silica-supported azazirconacyclopropane [[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)(η2-NMeCH2)(NMe2)]. Mechanistic studies were conducted using surface organometallic chemistry (SOMC) concepts to identify the key surface intermediates. The azametallacyclopentene intermediate {[TRIPLE BOND]Si[BOND]O[BOND]Zr(HNMe2)[η2-NMeCH2CH(Me)CH2](NMe2)} was isolated after treating with 1-propylene and characterized by FT-IR spectroscopy, elemental analysis, 1H 13C HETCOR, DARR SS-NMR and DQ TQ SS-NMR. The regeneration of the catalyst was conducted by dimethylamine protonolysis to yield the pure amine.

  19. Hydroquinone–pyrrole dyads with varied linkers

    Directory of Open Access Journals (Sweden)

    Hao Huang


    Full Text Available A series of pyrroles functionalized in the 3-position with p-dimethoxybenzene via various linkers (CH2, CH2CH2, CH=CH, C≡C has been synthesized. Their electronic properties have been deduced from 1H NMR, 13C NMR, and UV–vis spectra to detect possible interactions between the two aromatic subunits. The extent of conjugation between the subunits is largely controlled by the nature of the linker, with the largest conjugation found with the trans-ethene linker and the weakest with the aliphatic linkers. DFT calculations revealed substantial changes in the HOMO–LUMO gap that correlated with the extent of conjugation found experimentally. The results of this work are expected to open up for use of the investigated compounds as components of redox-active materials in sustainable, organic electrical energy storage devices.

  20. Rotational spectroscopic studies of C-H · · · F interactions in the vinyl fluoride · · · difluoromethane complex. (United States)

    Christenholz, Cori L; Obenchain, Daniel A; Peebles, Rebecca A; Peebles, Sean A


    Rotational spectra of the normal isotopic species and three (13)C isotopologues of the 1:1 complex between vinyl fluoride (CH2 ═ CHF) and difluoromethane (CH2F2) have been measured using 480 MHz bandwidth chirped-pulse Fourier-transform microwave spectroscopy in the 6.5-20 GHz region. A structure for this dimer has been determined by fitting the moments of inertia of all isotopologues and confirmed by calculation of Kraitchman single isotopic substitution coordinates. The structure is consistent with that determined by ab initio geometry optimization at the MP2/6-311++G(2d,2p) level and has the difluoromethane subunit located on the CHF side of the vinyl fluoride subunit with three C-H · · · F contacts and with the hydrogen atoms of the CH2F2 straddling the vinyl fluoride symmetry plane.

  1. [A comparative study on the resolution of second derivative and Fourier self-deconvolution]. (United States)

    Wang, Dong-mei; Wang, Hai-shui; Zeng, Guang-fu; Xi, Shi-quan


    Infrared spectra of 2-alkyl-7,7,8,8-tetracyanoquinodimethane (C12H25 TCNQ, C15H31 TCNQ, C18H37 TCNQ) were measured with the resolution of 1 and 4 cm(-1). In order to identify the peak number correctly in the CH2 stretching region, second derivative and Fourier self-deconvolution were applied to the infrared spectra, respectively. The overlapping bands in the CH2 stretching region could be identified when the infrared spectra, which were measured with the resolution of 4 cm(-1), were dealt with by Fourier self-deconvolution. However, the bands overlapped in the CH2 symmetric stretching region could not be observed when these infrared spectra were dealt with by second derivative. The above results reveal that Fourier self-deconvolution method is more powerful than second derivative in identifying bands that are involved in an overlapping band feature.

  2. Nitrogen Containing Organosilicon Bonded an Al2O3-Cellulose Acetate Hybrid Material: Preparation, Characterization and Use for Adsorption of Fe(III, Cu(II and Zn(II from Ethanol Solutions

    Directory of Open Access Journals (Sweden)

    Lazarin Angélica M.


    Full Text Available This work describes the preparation and characterization of a cellulose acetate fiber coated with Al2O3, resulting in the organic-inorganic hybrid Cella/Al2O3. Furthermore, it was modified by attaching organofunctional groups, by reaction with the precursor reagents (RO3Si(CH23L (L = -NH2, NH(CH22NH2, NH(CH22NH(CH2 2NH2 and NC3H3N, resulting in Cella/Al2O3/Si(CH2 3NH2 (1, Cella/Al2O3/Si(CH2 3NH(CH22NH2 (2, Cella/Al2O3/Si(CH 23NH(CH22 NH(CH22NH2 (3 and Cella/Al2O3/Si(CH2 3NC3H3N (imidazole (4. The amount of attached organofunctional groups were (in mmol per gram of the material: 1 = 1.90, 2 = 1.89, 3 = 1.66 and 4 = 1.35. The adsorption isotherms from ethanol solutions of FeCl3, CuCl2 and ZnCl2 by Cella/Al2O3/Si(CH2 3L were obtained at 298 K. The results obtained in flow experiments showed a retention and recovery of ca. 100% of the metal ions by Cella/Al2O3/Si(CH2 3L packed in a column, for a solution containing either one or mixture of the ions.

  3. Gene Transfection in High Serum Levels: Case Studies with New Cholesterol Based Cationic Gemini Lipids (United States)

    Misra, Santosh K.; Biswas, Joydeep; Kondaiah, Paturu; Bhattacharya, Santanu


    Background Six new cationic gemini lipids based on cholesterol possessing different positional combinations of hydroxyethyl (-CH2CH2OH) and oligo-oxyethylene -(CH2CH2O)n- moieties were synthesized. For comparison the corresponding monomeric lipid was also prepared. Each new cationic lipid was found to form stable, clear suspensions in aqueous media. Methodology/Principal Findings To understand the nature of the individual lipid aggregates, we have studied the aggregation properties using transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential measurements and X-ray diffraction (XRD). We studied the lipid/DNA complex (lipoplex) formation and the release of the DNA from such lipoplexes using ethidium bromide. These gemini lipids in presence of a helper lipid, 1, 2-dioleoyl phophatidyl ethanol amine (DOPE) showed significant enhancements in the gene transfection compared to several commercially available transfection agents. Cholesterol based gemini having -CH2-CH2-OH groups at the head and one oxyethylene spacer was found to be the most effective lipid, which showed transfection activity even in presence of high serum levels (50%) greater than Effectene, one of the potent commercially available transfecting agents. Most of these geminis protected plasmid DNA remarkably against DNase I in serum, although the degree of stability was found to vary with their structural features. Conclusions/Significance -OH groups present on the cationic headgroups in combination with oxyethylene linkers on cholesterol based geminis, gave an optimized combination of new genera of gemini lipids possessing high transfection efficiency even in presence of very high percentage of serum. This property makes them preferential transfection reagents for possible in vivo studies. PMID:23861884

  4. Reaction rates of Criegee intermediates with water vapor and hydrogen sulfide (United States)

    Smith, M. C.; Boering, K. A.


    Criegee intermediates are byproducts of the reaction of alkenes with ozone. Bimolecular reactions of Criegee intermediates can lead to the production of low-volatility organic compounds and acids in the atmosphere, which in turn play a role in determining the concentration, size, and optical properties of aerosols. Recently, a novel method for producing measurable quantities of stabilized Criegee intermediates in the laboratory paved the way for the development of new experimental techniques to study their chemical properties and predict their importance in the atmosphere. Our lab uses transient UV absorption spectroscopy to measure the formation and decay of Criegee intermediates in a flow cell, using 8-pass absorption of a bright plasma light source combined with sensitive balanced photodiode detection. Here we measured the transient absorption of CH2OO and obtained rate coefficients for its reaction with water dimer from 283 to 324 K. The fast reaction of CH2OO with water dimer is thought to dominate CH2OO removal in the atmosphere, but reaction rates can vary considerably under different conditions of temperature, humidity, and pressure. The rate of the reaction of CH2OO with water dimer was found to exhibit a strong negative temperature dependence. Due to the strong temperature dependence, and shifting competition between water dimer and water monomer (which has a positive temperature dependence), the effective loss rate of CH2OO by reaction with water vapor is highly sensitive to atmospheric conditions. We also present the first measurements of the reaction rate between CH2OO and hydrogen sulfide, which is analogous to the water molecule and may have significance in areas with volcanic activity.

  5. C(sp₃)-H bond activation with triel metals: indium and gallium zwitterions through internal hydride abstraction in rigid salan ligands. (United States)

    Maudoux, Nicolas; Fang, Jian; Roisnel, Thierry; Dorcet, Vincent; Maron, Laurent; Carpentier, Jean-François; Sarazin, Yann


    The hydropyrimidine salan (salan=N,N'-dimethyl-N,N'-bis[(2-hydroxyphenyl)methylene]-1,2-diaminoethane) proteo-ligands with a rigid backbone {ON^(CH2)^NO}H2 react with M(CH2SiMe3)3 (M=Ga, In) to yield the zwitterions {ON^(CH(+))^NO}M(-)(CH2SiMe3)2 (M=Ga, 2; In, 3) by abstraction of a hydride from the ligand backbone followed by elimination of dihydrogen. By contrast, with Al2Me6, the neutral-at-metal bimetallic complex [{ON^(CH2)^NO}AlMe]2 ([1]2) is obtained quantitatively. The formation of indium zwitterions is also observed with sterically more encumbered ligands containing o-Me substituents on the phenolic rings, or an N (CHPh) N moiety in the heterocyclic core. Overall, the ease of C(sp3)-H bond activation follows the order Al≪Gahydride species. DFT calculations indicate that the systems {ON^(CH2)^NO}H2+M(CH2SiMe3)3 (M=Al, Ga, In) all initially lead to the formation of the neutral monophenolate dihydrocarbyl species through a single protonolysis. From here, the thermodynamic product, the model neutral-at-metal complex 1, is formed in the case of aluminum after a second protonolysis. On the other hand, lower activation energy pathways lead to the generation of zwitterionic complexes 2 and 3 in the cases of gallium and indium, and the formation of these zwitterions obeys a strict kinetic control; the computations suggest that, as inferred from the experimental data, the reaction proceeds through an instable metal-hydride species, which could not be isolated synthetically. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Brominated methanes as photoresponsive molecular storage of elemental Br2. (United States)

    Kawakami, Kazumitsu; Tsuda, Akihiko


    The photochemical generation of elemental Br(2) from brominated methanes is reported. Br(2) was generated by the vaporization of carbon oxides and HBr through oxidative photodecomposition of brominated methanes under a 20 W low-pressure mercury lamp, wherein the amount and situations of Br(2) generation were photochemically controllable. Liquid CH(2)Br(2) can be used not only as an organic solvent but also for the photoresponsive molecular storage of Br(2), which is of great technical benefit in a variety of organic syntheses and in materials science. By taking advantage of the in situ generation of Br(2) from the organic solvent itself, many organobromine compounds were synthesized in high practical yields with or without the addition of a catalyst. Herein, Br(2) that was generated by the photodecomposition of CH(2)Br(2) retained its reactivity in solution to undergo essentially the same reactions as those that were carried out with solutions of Br(2) dissolved in CH(2)Br(2) that were prepared without photoirradiation. Furthermore, HBr, which was generated during the course of the photodecomposition of CH(2)Br(2), was also available for the substitution of the OH group for the Br group and for the preparation of the HBr salts of amines. Furthermore, the photochemical generation of Br(2) from CH(2)Br(2) was available for the area-selective photochemical bleaching of natural colored plants, such as red rose petals, wherein Br(2) that was generated photochemically from CH(2)Br(2) was painted onto the petal to cause radical oxidations of the chromophoric anthocyanin molecules. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Effect of Fc-Glycan Structure on the Conformational Stability of IgG Revealed by Hydrogen/Deuterium Exchange and Limited Proteolysis. (United States)

    Fang, Jing; Richardson, Jason; Du, Zhimei; Zhang, Zhongqi


    Human therapeutic immunoglobulin gamma (IgG) molecules contain an N-glycan on each of their Fc CH2 domains. These glycans include high-mannose, hybrid, and complex types. Recombinant IgG molecules containing high-mannose glycans have been shown to clear faster in human blood, and exhibit decreased thermal stability. The molecular mechanism behind these observations, however, is not well understood. In this work, we used hydrogen/deuterium exchange combined with mass spectrometry (HDX MS), as well as proteolytic degradation under a native-like condition, to assess the impact of different glycoforms on the molecular structure and stability of recombinant IgG1 and IgG2 molecules expressed from Chinese hamster ovary cells. Our HDX MS data indicate that the conformation of these IgG molecules was indeed influenced by the glycan structure. IgG molecules containing high-mannose and hybrid glycans showed more conformational flexibility in the CH2 domain. This conclusion was further supported by the analysis of glycopeptides released from these molecules by trypsin digestion under a native-like condition. The higher CH2 conformational flexibility of IgG molecules with high-mannose and hybrid glycans contributes to their decreased thermal stability. IgG molecules containing sialylated glycans in the CH2 domain exhibited similar enzymatic degradation behavior as high-mannose glycans, suggesting decreased CH2-domain stability compared to shorter complex glycans, likely resulting from steric effect that decreased the glycan-CH2 domain interaction.

  8. Signatures of a quantum diffusion limited hydrogen atom tunneling reaction. (United States)

    Balabanoff, Morgan E; Ruzi, Mahmut; Anderson, David T


    We are studying the details of hydrogen atom (H atom) quantum diffusion in highly enriched parahydrogen (pH 2 ) quantum solids doped with chemical species in an effort to better understand H atom transport and reactivity under these conditions. In this work we present kinetic studies of the 193 nm photo-induced chemistry of methanol (CH 3 OH) isolated in solid pH 2 . Short-term irradiation of CH 3 OH at 1.8 K readily produces CH 2 O and CO which we detect using FTIR spectroscopy. The in situ photochemistry also produces CH 3 O and H atoms which we can infer from the post-photolysis reaction kinetics that display significant CH 2 OH growth. The CH 2 OH growth kinetics indicate at least three separate tunneling reactions contribute; (i) reactions of photoproduced CH 3 O with the pH 2 host, (ii) H atom reactions with the CH 2 O photofragment, and (iii) long-range migration of H atoms and reaction with CH 3 OH. We assign the rapid CH 2 OH growth to the following CH 3 O + H 2 → CH 3 OH + H → CH 2 OH + H 2 two-step sequential tunneling mechanism by conducting analogous kinetic measurements using deuterated methanol (CD 3 OD). By performing photolysis experiments at 1.8 and 4.3 K, we show the post-photolysis reaction kinetics change qualitatively over this small temperature range. We use this qualitative change in the reaction kinetics with temperature to identify reactions that are quantum diffusion limited. While these results are specific to the conditions that exist in pH 2 quantum solids, they have direct implications on the analogous low temperature H atom tunneling reactions that occur on metal surfaces and on interstellar grains.

  9. Precursors to New Molecular Tube Ligands. 1. Double-Capped Trinuclear Cobalt Complexes of Aminoethanethiol. (United States)

    Arnold, Alan P.; Bhula, Rajumati; Chen, Xiangna; Geue, Rodney J.; Jackson, W. Gregory


    Co(SCH(2)CH(2)NH(2))(3) has been capped on the facial amines through protection of the thiolates by coordination of two such complexes to a central Co(III) ion. The trinuclear species forming the framework is the complex ion [Co{Co(SCH(2)CH(2)NH(2))(3)}(2)](3+), 1, in meso and rac forms which have been chromatographically separated and identified. Hexaimine derivatives of 1, [Co{Co(SCH(2)CH(2)N=CH(2))(3)}(2)](3+), 2, have been synthesized in good yield by reaction with excess paraformaldehyde and base in CH(3)CN. The hexaimines have been reacted with NH(3) to yield dicapped aza species [Co{Co(SCH(2)CH(2)NHCH(2))(3)N}(2)](3+), 3, or reacted with nitromethane to yield the nitro-capped ions [Co{Co(SCH(2)CH(2)NHCH(2)C)(3)CNO(2)}(2)](3+), 4. The reactions are retentive; i.e., meso reactant yields meso product. All of the products have been characterized by (1)H NMR, (13)C NMR, and UV-vis spectroscopy. Electrochemical measurements (CV and dc coulometry) in CH(3)CN indicate that the central Co(III) ion in all of the species is reduced first, followed by the two terminal Co(III) centers. The formal potentials show that the Co(III) oxidation state is stabilized by the six thiolate bridging ligands in comparison to six thioether donor atoms, whereas capping has a destabilizing effect.

  10. Presolvated Electron Reactions with Methyl Acetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-Atom Abstraction

    Directory of Open Access Journals (Sweden)

    Alex Petrovici


    Full Text Available Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3 at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-COOCH3 in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•OH-CH2-COOCH3. The ESR spectrum of CH3-C(•OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K, CH3-C(•OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT support the radical assignments.

  11. Presolvated Electron Reaction with Methylacetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-atom Abstraction (United States)

    Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D.


    Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methylacetoacetate (MAA, CH3-CO-CH2-CO-OCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-CO-OCH3) in the temperature range (77 to ca. 170 K) have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-CO-OCH3. The ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylen protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-CO-OCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-CO-OCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments. PMID:25255751

  12. Presolvated electron reactions with methyl acetoacetate: electron localization, proton-deuteron exchange, and H-atom abstraction. (United States)

    Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D


    Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•--CH2-COOCH3) in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-COOCH3. The ESR spectrum of CH3-C(•)OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments.

  13. Fast magnetization tunneling in tetranickel(II) single-molecule magnets. (United States)

    Yang, En-Che; Wernsdorfer, Wolfgang; Zakharov, Lev N; Karaki, Yoshitomo; Yamaguchi, Akira; Isidro, Rose M; Lu, Guo-Di; Wilson, Samuel A; Rheingold, Arnold L; Ishimoto, Hidehiko; Hendrickson, David N


    A series of Ni(4) cubane complexes with the composition [Ni(hmp)(ROH)Cl](4) complexes 1-4 where R= -CH(3) (complex 1), -CH(2)CH(3) (complex 2), -CH(2)CH(2)(C(4)H(9)) (complex 3), -CH(2)CH(2)CH(2)(C(6)H(11)) (complex 4), hmp(-) is the anion of 2-hydroxymethylpyridine, t-Buhmp(-) is the anion of 4-tert-butyl-2-hydroxymethylpyridine, and dmb is 3,3-dimethyl-1-butanol] and [Ni(hmp)(dmb)Br](4) (complex 5) and [Ni(t-Buhmp)(dmb)Cl](4) (complex 6) were prepared. All six complexes were characterized by dc magnetic susceptibility data to be ferromagnetically coupled to give an S = 4 ground state with significant magnetoanisotropy (D approximately equal to -0.6 cm(-1)). Magnetization hysteresis measurements carried out on single crystals of complexes 1-6 establish the single-molecule magnet (SMM) behavior of these complexes. The exchange bias observed in the magnetization hysteresis loops of complexes 1 and 2 is dramatically decreased to zero in complex 3, where the bulky dmb ligand is employed. Fast tunneling of magnetization is observed for the high-symmetry (S(4) site symmetry) Ni(4) complexes in the crystal of complex 3, and the tunneling rate can even be enhanced by destroying the S(4) site symmetry, as is the case for complex 4, where there are two crystallographically different Ni(4) molecules, one with C(2) and the other with C(1) site symmetry. Magnetic ordering temperatures due to intermolecular dipolar and magnetic exchange interactions were determined by means of very low-temperature ac susceptibility measurements; complex 1 orders at 1100 mK, complex 3 at 290 mK, complex 4 at approximately 80 mK, and complex 6 at lower temperatures for those complexes with the bulkiest ligands.

  14. Computational study of the double C-Cl bond activation of dichloromethane and phosphine alkylation at [CoCl(PR3)3]. (United States)

    Algarra, Andrés G; Braunstein, Pierre; Macgregor, Stuart A


    Density functional theory calculations have been employed to model the double C-Cl bond activation of CH(2)Cl(2) at [CoCl(PR(3))(3)] to give [CoCl(3)(CH(2)PR(3))(PR(3))(2)]. Calculations incorporating dichloromethane solution (PCM approach) on a [CoCl(PMe(3))(3)] model system showed the two C-Cl cleavage steps to involve different mechanisms. The first C-Cl cleavage step occurs on the triplet surface and proceeds via Cl abstraction with a barrier of 19.1 kcal mol(-1). Radical recombination would then give singlet mer,trans-[CoCl(2)(CH(2)Cl)(PMe(3))(3)] with an overall free energy change of +1.8 kcal mol(-1). Alternative C-Cl activation processes based on nucleophilic attack by the Co centre at dichloromethane with loss of Cl(-) have significantly higher barriers. The second C-Cl cleavage occurs via nucleophilic attack of PMe(3) at the CH(2)Cl ligand with formation of a new P-C bond and displacement of Cl(-). This may either occur in an intermolecular fashion (after prior PMe(3) dissociation) or intramolecularly. Both processes have similar barriers of ca. 12 kcal mol(-1). The comproportionation of [CoCl(3)(CH(2)PMe(3))(PMe(3))(2)] with [CoCl(PMe(3))(3)] to give [CoCl(2)(CH(2)PMe(3))(PMe(3))], [CoCl(2)(PMe(3))(2)] and 2 PMe(3) is computed to be strongly exergonic, consistent with the observation of this process in analogous experimental systems.

  15. The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes (United States)

    Phanopoulos, Andreas; Long, Nicholas; Miller, Philip


    Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the hydroxylmethylene phosphine precursor with ammonia in methanol under a nitrogen atmosphere. The N-triphosPh ligand precipitates from the solution after approximately 1 hr of reflux and can be isolated analytically pure via simple cannula filtration procedure under nitrogen. Reaction of the N-triphosPh ligand with [Ru3(CO)12] under reflux affords a deep red solution that show evolution of CO gas on ligand complexation. Orange crystals of the complex [Ru(CO)2{N(CH2PPh2)3}-κ3P] (2) were isolated on cooling to RT. The 31P{1H} NMR spectrum showed a characteristic single peak at lower frequency compared to the free ligand. Reaction of a toluene solution of complex 2 with oxygen resulted in the instantaneous precipitation of the carbonate complex [Ru(CO3)(CO){N(CH2PPh2)3}-κ3P] (3) as an air stable orange solid. Subsequent hydrogenation of 3 under 15 bar of hydrogen in a high-pressure reactor gave the dihydride complex [RuH2(CO){N(CH2PPh2)3}-κ3P] (4), which was fully characterized by X-ray crystallography and NMR spectroscopy. Complexes 3 and 4 are potentially useful catalyst precursors for a range of hydrogenation reactions, including biomass-derived products such as levulinic acid (LA). Complex 4 was found to cleanly react with LA in the presence of the proton source additive NH4PF6 to give [Ru(CO){N(CH2PPh2)3}-κ3P{CH3CO(CH2)2CO2H}-κ2O](PF6) (6). PMID:25938678

  16. 3.0-3.7μm infrared sensor system for cell analysis (United States)

    van den Driesche, Sander; Witarski, Wojciech; Vellekoop, Michael J.


    In this contribution we present a novel LED-photodiode based infrared absorbance sensor in the wavelength range of 3.0 - 3.7 μm for cell analysis. Instead of using time consuming and expensive labelling and staining techniques to distinguish healthy from malignant cell types, this IR sensor system can perform faster, cheaper and without the need of additional chemicals. Depending on the used narrow bandpass filters, absorbance due to specific molecular vibration can be measured, such as the functional absorbance peaks at 3.38 μm (CH3-antisymmetric stretch), 3.42 μm (CH2- antisymmetric stretch), 3.48 μm (CH3-symmetric stretch) and 3.51 μm (CH2-symmetric stretch). For normalization and baseline correction the absorbance at wavelengths 3.33 and 3.57 μm are used. By recording the IR absorbance spectra of healthy and malignant epithelial kidney cell lines with an IR spectroscope, we found significant differences in the absorbance ratio 3.51 μm / 3.42 μm (CH2-symmetric/antisymmetric stretch). This result has led us to a sensor concept where only four wavelengths are being measured. In the 3.0 - 3.7 μm wavelength region a low cost LED-photodiode system can be used instead of a spectroscope. Yeast cells, which also contain the CH2 symmetric and antisymmetric stretch bands, are used to validate this sensor system and to make a first comparison of the system to spectroscopic recordings. Sensor experiments on dried spots of baker's yeast on calcium-fluoride slides yielded a comparable CH2 stretch ratio with the IR spectroscope measurement. This confirms the usability of the sensor to measure the CH2 stretch ratio and its potential for fast, label-free and low cost screening of cell samples.

  17. Interactions of Hg(ii) with oligonucleotides having thymine-thymine mispairs. Optimization of an impedimetric Hg(ii) sensor. (United States)

    Kamal, Ajar; She, Zhe; Sharma, Renu; Kraatz, Heinz-Bernhard


    The present work describes the effect of the number of thymine-thymine mispairs in single strand DNA probes on Hg(ii) interactions and further to develop a highly sensitive DNA based impedimetric sensor for Hg(ii) detection. To achieve this goal, the influence of the number of T-T mispairs on the signal response prompted by DNA-Hg(ii) binding interactions was examined on three designed DNA probes: 5'-OH-(CH 2 ) 6 -S-S-(CH 2 ) 6 -AGTCCACACGTTCCTTACGC-3', 5'-OH-(CH 2 ) 6 -S-S-(CH 2 ) 6 -AGTCCACATTTTCCTTTTGC-3', 5'-OH-(CH 2 ) 6 -S-S-(CH 2 ) 6 -AGTCCATTTTTTCCTTTTTT-3' having 2T-T, 4T-T and 6T-T mispairs with identical length, respectively. This study revealed that the number of T-T mispairs plays a critical role in maximizing the signal intensity of DNA-Hg(ii) binding interactions. Based on these results, DNA comprising maximum number of T-T mispairs was further utilized for construction of the Hg(ii) sensor, which exhibited a linear correlation between the change in charge transfer resistance (ΔR CT ) and the concentration of Hg(ii) over the range of 1.0 × 10 -5 M to 1.0 × 10 -10 M with a lower detection limit of 3.2 × 10 -11 M. The selectivity was tested against 12 different metal ions including Hg(ii). The ΔR CT response from Hg(ii) is 3 times higher than the nearest competitor Pb(ii) and approximately 10 times than other ions. The potential application of such a robust and label-free DNA sensor was demonstrated by analyzing environmental samples collected from Lake Ontario.

  18. The N- and C-Terminal Domains Differentially Contribute to the Structure and Function of Dystrophin and Utrophin Tandem Calponin-Homology Domains. (United States)

    Singh, Surinder M; Bandi, Swati; Mallela, Krishna M G


    Dystrophin and utrophin are two muscle proteins involved in Duchenne/Becker muscular dystrophy. Both proteins use tandem calponin-homology (CH) domains to bind to F-actin. We probed the role of N-terminal CH1 and C-terminal CH2 domains in the structure and function of dystrophin tandem CH domain and compared with our earlier results on utrophin to understand the unifying principles of how tandem CH domains work. Actin cosedimentation assays indicate that the isolated CH2 domain of dystrophin weakly binds to F-actin compared to the full-length tandem CH domain. In contrast, the isolated CH1 domain binds to F-actin with an affinity similar to that of the full-length tandem CH domain. Thus, the obvious question is why the dystrophin tandem CH domain requires CH2, when its actin binding is determined primarily by CH1. To answer, we probed the structural stabilities of CH domains. The isolated CH1 domain is very unstable and is prone to serious aggregation. The isolated CH2 domain is very stable, similar to the full-length tandem CH domain. These results indicate that the main role of CH2 is to stabilize the tandem CH domain structure. These conclusions from dystrophin agree with our earlier results on utrophin, indicating that this phenomenon of differential contribution of CH domains to the structure and function of tandem CH domains may be quite general. The N-terminal CH1 domains primarily determine the actin binding function whereas the C-terminal CH2 domains primarily determine the structural stability of tandem CH domains, and the extent of stabilization depends on the strength of inter-CH domain interactions.

  19. The cysteine radical cation: structures and fragmentation pathways. (United States)

    Zhao, Junfang; Siu, K W Michael; Hopkinson, Alan C


    A theoretical study on the structures, relative energies, isomerization reactions and fragmentation pathways of the cysteine radical cation, [NH(2)CH(CH(2)SH)COOH].+, is reported. Hybrid density functional theory (B3LYP) has been used in conjunction with the 6-311++G(d,p) basis set. The isomer at the global minimum, Captodative-1, has the structure NH(2)C.(CH(2)SH)C(OH)(2)+; the stability of this ion is attributed to the captodative effect in which the NH(2) functions as a powerful pi-electron donor and C(OH)(2)+ as a powerful pi-electron acceptor. Ion Distonic-S-1, H(3)N(+)CH(CH(2)S.)COOH, in which the radical is formally situated on the S atom, is higher in enthalpy (DeltaH degrees (0)) than Captodative-1 by 6.1 kcal mol(-1), but is lower in enthalpy than another isomer Distonic-C-1, H(3)N(+)C.(CH(2)SH)COOH, by 8.2 kcal mol(-1). Isomerization of the canonical radical cation of cysteine, [H(2)NCH(CH(2)SH)COOH].+, (Canonical-1), to Captodative-1 has an enthalpy of activation of 25.8 kcal mol(-1), while the barrier against isomerization of Canonical-1 to Distonic-S-1 is only 9.6 kcal mol(-1). Two additional transient tautomers, one with the radical located at C(alpha) and the charge on SH(2), and the other a carboxy radical with the charge on NH(3), are reported. Plausible fragmentation pathways (losses of small molecules, CO(2), CH(2)S, H(2)S and NH(3), and neutral radicals COOH. , HSCH(2). and NH(2).) from Canonical-1 are examined.

  20. The Synthesis, Characterization and Dehydrogenation of Sigma‐Complexes of BN‐Cyclohexanes (United States)

    Kumar, Amit; Ishibashi, Jacob S. A.; Hooper, Thomas N.; Mikulas, Tanya C.; Dixon, David A.


    Abstract The coordination chemistry of the 1,2‐BN‐cyclohexanes 2,2‐R2‐1,2‐B,N‐C4H10 (R2=HH, MeH, Me2) with Ir and Rh metal fragments has been studied. This led to the solution (NMR spectroscopy) and solid‐state (X‐ray diffraction) characterization of [Ir(PCy3)2(H)2(η2η2‐H2BNR2C4H8)][BArF 4] (NR2=NH2, NMeH) and [Rh(iPr2PCH2CH2CH2PiPr2)(η2η2‐H2BNR2C4H8)][BArF 4] (NR2=NH2, NMeH, NMe2). For NR2=NH2 subsequent metal‐promoted, dehydrocoupling shows the eventual formation of the cyclic tricyclic borazine [BNC4H8]3, via amino‐borane and, tentatively characterized using DFT/GIAO chemical shift calculations, cycloborazane intermediates. For NR2=NMeH the final product is the cyclic amino‐borane HBNMeC4H8. The mechanism of dehydrogenation of 2,2‐H,Me‐1,2‐B,N‐C4H10 using the {Rh(iPr2PCH2CH2CH2PiPr2)}+ catalyst has been probed. Catalytic experiments indicate the rapid formation of a dimeric species, [Rh2(iPr2PCH2CH2CH2PiPr2)2H5][BArF 4]. Using the initial rate method starting from this dimer, a first‐order relationship to [amine‐borane], but half‐order to [Rh] is established, which is suggested to be due to a rapid dimer–monomer equilibrium operating. PMID:26602704

  1. Synthesis and Characterization of Bis-benzyl and Bis-allyl Complexes of Titanium(III) and Vanadium(III); Catalytic Isomerization of Alkenes with CpV(η3-C3H5)2

    NARCIS (Netherlands)

    Nieman, J.; Pattiasina, J.W.; Teuben, J.H.


    Reactions of CpTiCl2 (Cp = η5-C5H5) with RMgX (X = Cl, Br) yield the complexes CpTiR2 (R = CH2Ph, η3-C3H5). The complex Cp*Ti(η3-C3H5)2 (Cp* = η5-C5Me5) was prepared analogously from Cp*TiCl2(THF). CpVCl2(PEt3)2 and Cp´VCl2(PEt3)2 (Cp´ = η5-C5H4Me) were used for the preparation of CpV(CH2Ph)2,

  2. compounds with N=N, C≡C or conjugated double-bonded systems

    Indian Academy of Sciences (India)

    thiocyanate CH2(6-t-Bu-4-Me-C6H2O)2P-NCS (12) also gives a similar heterocycle along with an un- usual tri-phosphorus compound.12. We have recorded variable time 31P NMR spectra for 24b. After 15 min of the addition of DIAD to a solution of CH2(6-t-Bu-4-Me-C6H2O)2P-NCO (9) in. C6D6, we observed a peak at ...

  3. Reação de bis-inserção de 1,2-difenilacetileno na ligação Pd-C de ciclometalados Bis insertion reaction of 1,2-diphenylacetilene into Pd-C bond of cyclometallated species

    Directory of Open Access Journals (Sweden)

    Sandra Regina Ananias


    Full Text Available The present paper deals with the bis-insertion reactions of 1,2-diphenylacetylene into Pd-C bond of the cyclopalladated complexes [Pd(dmba(µ-NCO]2 (1 and [Pd(dmba(MeCN2](NO3 (2 (dmba = N,N-dimethylbenzylamine, MeCN = acetonitrile. Two new complexes [Pd{PhC=CPh-CPh=CPhC6H4CH2N(CH 32}(NCO] (3 and [Pd{PhC=CPh-CPh=CPhC6H4CH2N(CH 32}(NO3 ] (4 were obtained and characterized by IR and NMR spectroscopy and elemental analysis.

  4. Production of radiation crosslinked polymeric compositions using diacetylenes

    International Nuclear Information System (INIS)

    Patel, G.N.


    Crosslinked polymeric compositions, useful as electrical insulators, heat shrinkable packaging, and lightweight foam plastics, are described. The crosslinked polymeric compositions are produced by admixing a diacetylene monomer, oligomer, polymer or mixture thereof, wherein the monomer has the formula, RNHCO-O-CH 2 -C==C-C==C-CH- 2 -O-OCNHR' in which R and R' are the same or different and are alkyl containing 1 to 20 carbon atoms, with a thermoplastic crosslinkable polymer and then subjecting the resulting mixture to actinic radiation

  5. High-pressure viscosity behavior of x 1,1,1,2-tetrafluoroethane (HFC-134a)+(1-x) triethylene glycol dimethylether (TriEGDME) mixtures: Measurements and modeling

    DEFF Research Database (Denmark)

    Monsalvo, Matias Alfonso; Baylaucq, A.; Cisneros, Sergio


    In this work new dynamic viscosity measurements for binary mixtures containing a refrigerant (HFC-134a, CF3CH2F) and a lubricant (TriEGDME, CH3O(CH2OCH2)(3)CH3) are reported. The measurements were carried out at temperatures between 293.15 and 373.15 K and pressures from 10 to 100 MPa, for two mole...... with a physical and theoretical background, such as the hard-sphere scheme, the free-volume model, and the friction theory....

  6. Development of Army High-Energy Fuel for Diesel/Turbine Powered Surface Equipment (United States)


    titanium, yttrtum, zirconium , cerium, and tungsten have all been investigated. The upper limit for liquid hydrocarbon fiels is about 170,000 Btu/gal...Poly(methyl vinyl ether/maleic anhydride) S A 42. Free acid of complex organic phosphate ester L A ൳. Heterocyclic tertiary amine S C 44...pharmaceuticals, cosmetics, paint, ink, rubber , and plastics.( 2 3 ) CH20COC17H35 CHOCOC 17H33 00 CH2-0-P/ 0 OCH 2CH2N(CH3 V 3𔃽! FIGURE 12. TYPICAL STRUCTURE

  7. Isolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O-O bond

    KAUST Repository

    Hayashi, Yukiko


    The reaction of RhCl3·H2O with tBu2P(CH2)5PtBu 2 afforded several complexes including [RhIII(H)Cl{ tBu2- P(CH2)2CH(CH2) 2PtBu2}] (1), [RhIIIHCl 2{tBu2P(CH2)5P tBu2}]2 (2), [RhICl{ tBu2P(CH2)2CH=CHCH2P tBu2}] (3) and [RhICl{tBu 2PCH2C(O)CH=CHCH2PtBu2}] (4). X-ray crystal structures of 3 and 4 showed that the C=C bond on the C 5 unit of tBu2P(CH2) 5PtBu2 is bound to Rh(I) in a η2 configuration. In 4, the Rh atom has a trigonal pyramidal coordination geometry. The X-ray crystal structure of 2 consists of two rhodium( III) centers bridged by two tBu2P(CH2)5P tBu2 ligands with two phosphorus atoms, one from each ligand, trans to one another. The crystal structure of the rhodium oxygen adduct with 1,3-bis(di-t-butylphosphinomethyl) benzene [RhO2{ tBu2PCH2(C6H3)CH 2PtBu2}] (5) was also investigated. In this species the O2 is η2 coordinated to the Rh(I) center with asymmetric Rh-O bond lengths (2.087(7) and 1.998(8) Å). The O-O bond distance is short (1.337(11) Å) with νO-O of 990.5 cm -1. DFT calculations on complex 5 yielded two η2- O2 structures that differed in energy by only 0.76 kcal/mol. The lower energy one (5a) had near C2 symmetry, and had nearly equal Rh-O bond lengths, while the higher energy structure (5b) had near Cs symmetry and generally good agreement with the experimental structure. The calculated UV-Vis and IR spectra of complex 5 are in excellent agreement with experiment. © 2012 Elsevier Ltd. All rights reserved.


    African Journals Online (AJOL)

    7.47-7.60 (m, 3H), 7.85-7.90 (m, 3H), 8.31 (d, J = 8.4 Hz, 1H), 13C NMR (125 MHz, CDCl3), δ: -0.054, 63.4, 92.5, 104.9, 124.1, 124.9, 125.3, 125.9, 126.5, 128.8, 129.5, 130.8, 134.1, 135.5. IR (CH2Cl2), νmax: 1503, 1695, 2163, 2296, 2894, 2959, 3041 cm-1; UV/Vis (CH2Cl2), λmax (ε) = 233 (11100), 273 (9330), 282 (7750) ...

  9. Reaction Mechanisms of Energetic Materials in the Condensed Phase: Long-term Aging, Munition Safety and Condensed-Phase Processes in Propellants and Explosives (United States)


    decomposition is the elimination of N2 and NO2. This would leave behind several different types of biradicals as follows: N N N NO NO2O2N N N N N...NO2O2N OH N N CH2 NO2 OH N N CH2 O2N OH N N O2N NO2 OH MRXPolyI-1 MRXPolyI-2 MRXPolyI-3 ONDNTA The biradical could possibly reform a ring structure

  10. Infrared intensity of 1-monolaurin-water systems in the gel phase (United States)

    Kanesaka, Isao; Ishizaka, Makiko; Shimizu, Kunihiko


    The infrared spectra of 1-monolaurin-water systems, where KSCN is added as the intensity standard, were observed and the infrared intensity of the bands due to acyl groups measured relatively to that of the CN stretching. The infrared intensities of the bands parallel and perpendicular to the paraffin chains decrease and increase, respectively, on going from the crystalline β phase to the gel phase, confirming that these intensity changes result from the long-range interaction among oscillating dipoles. The infrared spectra with no CH 2 rocking and the splitting of the CH 2 rocking are also discussed with the same interaction model.

  11. Investigação do mecanismo de catálise ROMP do norborneno utilizando métodos de funcional de densidade Investigation of the ROMP catalysis mechanism of norbornene using methods of density functional

    Directory of Open Access Journals (Sweden)

    Carlos Pereira da Silva


    Full Text Available This work presents a density functional theory study of the norbornene ROMP metathesis reactions. The energies have been calculated in a Grubbs catalyst model Cl2(PH32Ru=CH2. The geometries and energy profile are similar to the Grubbs metilydene (Cl2(PCy32Ru=CH2 real model. It was found that the metathesis reaction proceeds via associative mechanism (catalyst-norbonene followed by dissociative substitution of a phosphine ligand with norbonene, giving a monophosphine complex. The results are in reasonable agreement with the available experimental data. The dissociation energy of the phosphines is predicted to be 23.2 kcal mol-1.

  12. Synthesis of oligogalacturonates conjugated to BSA

    DEFF Research Database (Denmark)

    Clausen, Mads Hartvig; Madsen, Robert


    The synthesis of three oligogalacturonates with an aldehyde spacer attached at the reducing end is described. Trigalacturonates a-D-GalpA-(1-4)-a-D-GalpA-(1-4)-a-D-GalpA-(1-O(CH2)7CHO and a-D-GalpA(Me)-(1-4)-a-D-GalpA(Me)-(1-4)-a-D-GalpA(Me)-(1-O(CH2)7CHO as well as hexagalacturonate a-D-GalpA-(1...

  13. Long-term halocarbon observations from a coastal and an inland site in Sabah, Malaysian Borneo (United States)

    Robinson, A. D.; Harris, N. R. P.; Ashfold, M. J.; Gostlow, B.; Warwick, N. J.; O'Brien, L. M.; Beardmore, E. J.; Nadzir, M. S. M.; Phang, S. M.; Samah, A. A.; Ong, S.; Ung, H. E.; Peng, L. K.; Yong, S. E.; Mohamad, M.; Pyle, J. A.


    Short-lived halocarbons are believed to have important sources in the tropics, where rapid vertical transport could provide a significant source to the stratosphere. In this study, quasi-continuous measurements of short-lived halocarbons are reported for two tropical sites in Sabah (Malaysian Borneo), one coastal and one inland (rainforest). We present the observations for C2Cl4, CHBr3, CH2Br2* (actually ~80% CH2Br2 and ~20% CHBrCl2) and CH3I from November 2008 to January 2010 made using our μDirac gas chromatographs with electron capture detection (GC-ECD). We focus on the first 15 months of observations, showing over one annual cycle for each compound and therefore adding significantly to the few limited-duration observational studies that have been conducted thus far in southeast Asia. The main feature in the C2Cl4 behaviour at both sites is its annual cycle, with the winter months being influenced by northerly flow with higher concentrations, typical of the Northern Hemisphere, and with the summer months influenced by southerly flow and lower concentrations representative of the Southern Hemisphere. No such clear annual cycle is seen for CHBr3, CH2Br2* or CH3I. The baseline values for CHBr3 and CH2Br2* are similar at the coastal (overall median: CHBr3 1.7 ppt, CH2Br2* 1.4 ppt) and inland sites (CHBr3 1.6 ppt, CH2Br2* 1.1 ppt), but periods with elevated values are seen at the coast (overall 95th percentile: CHBr3 4.4 ppt, CH2Br2ast 1.9 ppt), presumably resulting from the stronger influence of coastal emissions. Overall median bromine values from [CHBr3 × 3] + [CH2Br2* × 2] are 8.0 ppt at the coast and 6.8 ppt inland. The median values reported here are largely consistent with other limited tropical data and imply that southeast Asia generally is not, as has been suggested, a hot spot for emissions of these compounds. These baseline values are consistent with the most recent emissions found for southeast Asia using the p-TOMCAT (Toulouse Off-line Model of

  14. A genetic approach to improvements of Candida tropicalis as a biocatalyst


    Perry, Patricia Mair


    It is well documented in the literature that, in addition to carbon sources such as glucose, Candida species are able to utilise a wide variety of n-alkanes which are degraded via beta-oxidation. Prior to beta-oxidation a primary oxidation system acts on the end terminal methyl groups to generate carboxyl groups. The main industrial aim of the work was to optimise the bioconversion of pelargonate [CH3(CH2)7COOH] to azeleate [HOOC(CH2)7COOH], i.e. the primary oxidation steps, by blocking the b...

  15. Observational studies of X-ray binary systems

    International Nuclear Information System (INIS)

    Klis, M. van der.


    The subject of Chapter 1 is theoretical. The other chapters, Ch. 2 to 6, contain original observational data and efforts towards their interpretation. Of these, Ch. 3, 4 and 5 deal with massive X-ray binaries, Ch. 6 with low-mass systems and Ch. 2 with Cygnus X-3, which we have not yet been able to assign to any of these two classes. The X-ray observations described were made with the COS-B satellite. Work based on UV and optical observations is described in Ch. 5. The UV observations were made with the IUE satellite, the optical observations at several ground-based observatories. (Auth.)

  16. Regio- and stereoselective hydrosilylation of immobilized terminal alkynes

    DEFF Research Database (Denmark)

    Pedersen, Palle Jacob; Henriksen, Jonas; Gotfredsen, Charlotte Held


    Regio- and stereoselective hydrosilylation of terminal alkynes on solid support using diisopropyl hydrosilanes yielding b-(E)-vinyl silanes with excellent selectivity is reported. The hydrosilylation is catalyzed by Pt(DVDS)/P(iBuNCH2CH2)3N (DVDS = 1,3-divinyl-1,1,3,3-tetramethyl-disiloxane), in ......Regio- and stereoselective hydrosilylation of terminal alkynes on solid support using diisopropyl hydrosilanes yielding b-(E)-vinyl silanes with excellent selectivity is reported. The hydrosilylation is catalyzed by Pt(DVDS)/P(iBuNCH2CH2)3N (DVDS = 1,3-divinyl-1,1,3,3-tetramethyl...

  17. Low pressure gas detectors for molecular-ion break up studies

    International Nuclear Information System (INIS)

    Breskin, A.; Chechik, R.; Zwang, N.


    Two detector systems for Molecular ions like OH + and CH 2 + and like H 2 + and H 3 + were developed and are described. The first detector is installed in a magnetic spectrometer. Both systems are made of various types of gas detectors operating at low pressures. In the study of the Coulomb explosion of molecular ions like OH + , CH 2 + or H 3 + these detectors provide the position and time coordinates of all the fragments of the molecular ion, in coincidence, in order to determine their energy and angular distribution. In the case of molecules containing atoms other than hydrogen, information on the electronic charge state is obtained. (H.K.)

  18. Metal, bond energy, and ancillary ligand effects on actinide-carbon σ-bond hydrogenolysis. A kinetic and mechanistic study

    International Nuclear Information System (INIS)

    Lin, Z.; Marks, T.J.


    A kineticmechanistic study of actinide hydrocarbyl ligand hydrogenolysis (An-R + H 2 → An-H + RH) is reported. For the complex Cp' 2 TH(CH 2 -t-Bu)(O-t-Bu)(Cp' = eta 5 -Me 5 C 5 ), the rate law is first-order in organoactinide and first-order in H 2 , with k/sub H2/k/sub D2/ = 2.5 (4) and k/sub THF/k/sub toluene/ = 2.9 (4). For a series of complexes, hydrogenolysis rates span a range of ca. 10 5 with Cp' 2 ThCH 2 C(CH 3 ) 2 CH 2 ≅ Cp' 2 U(CH 2 -t-Bu) (too rapid to measure accurately) > Cp' 2 Th(CH 2 -t-Bu)[OCH(t-Bu) 2 ] = Cp' 2 Th(CH 2 -t-Bu)(O-t-Bu) > Cp' 2 Th(CH 2 -t-Bu)(Cl) > Me 2 Si(Me 4 C 5 ) 2 Th(n-Bu) 2 > Cp' 2 Th(n-Bu) 2 ≅ Cp' 2 ThMe 2 > Cp' 2 Th(Me)(O 3 SCF 3 ) > Cp' 2 Th(n-Bu)[OCG(t-Bu) 2 ] ≅ Cp' 2 Th(Me)[OSiMe 2 (t-Bu)] > Cp' 2 ZrMe 2 = Cp' 2 Th(rho-C 6 H 4 NMe 2 )(O-tu-Bu) > Cp' 2 Th(Ph)(O-t-Bu) > Cp' 2 U(Me)[OCH(t-Bu) 2 ] > Cp' 2 Th(Me)[OCH(t-Bu) 2 ]. In the majority of cases, the rate law is cleanly first-order in organoactinide over 3 or more half-lives. However, for Cp' 2 ThMe 2 → (Cp' 2 ThH 2 ) 2 , an intermediate is observe by NMR that is probably [Cp' 2 Th(Me)(μ-H)] 2 . For Cp' 2 Th(Me)(O 3 SCF 3 ), a follow-up reaction, which consumes Cp' 2 TH(H)(O 3 SCF 3 ) is detected. Variable-temperature kinetic studies yield ΔH** = 3.7 (2) kcalmol and ΔS double dagger = -50.8 (7) eu for Cp' 2 Th(CH 2 -t-Bu)(O-t-Bu) and ΔH double dagger = 9 (2) kcalmol and ΔS double dagger = -45 (5) eu for Cp' 2 U(Me)[OCH(O-t-Bu) 2

  19. An IR investigation of solid amorphous ethanol - Spectra, properties, and phase changes (United States)

    Hudson, Reggie L.


    Mid- and far-infrared spectra of condensed ethanol (CH3CH2OH) at 10-160 K are presented, with a special focus on amorphous ethanol, the form of greatest astrochemical interest, and with special attention given to changes at 155-160 K. Infrared spectra of amorphous and crystalline forms are shown. The refractive index at 670 nm of amorphous ethanol at 16 K is reported, along with three IR band strengths and a density. A comparison is made to recent work on the isoelectronic compound ethanethiol (CH3CH2SH), and several astrochemical applications are suggested for future study.

  20. Indium(III)-catalyzed synthesis of N-substituted pyrroles under solvent-free conditions


    Chen, Jiu-Xi; Liu, Miao-Chang; Yang, Xiao-Liang; Ding, Jin-Chang; Wu, Hua-Yue


    A variety of N-substituted pyrroles have been synthesized by reacting γ-diketones (R¹C(O)CH2CH2C(O)R²: R¹, R² = Me, Ph) with amines (RNH2: R=Alkyl, Aryl, TsNH) or diamines (1,6-diaminohexane and 1,2-diaminoethane) in the presence of indium tribromide, indium trichloride or indium trifluoromethanesulfonate at room temperature under solvent-free conditions. The experiment protocol features simple operations, and the products are isolated in high to excellent yields (81-98%). Vários pirróis N...

  1. Supplementary Information Table: S1 Calculated vibrational wave ...

    Indian Academy of Sciences (India)


    3 C-H i.p bend. 1235. 1245 w. C7-H14 i.p bend +CH2 twisting. 1201. 1207 s. 1207 vvw. C7-H14 i.p bend + CH2 twisting. 1180. 1189 m. 1184 s. 9a C-H i.p bend. 1176. 1173 sh. 1165 m. 15 C-H i.p bend. 1078. 1071 w. 1078 vw. 18b C-H i.p bend. 1024. 1029 w. 1030 m. 1 ring breath. 1008. 1005 m. 1012 vs. 12 ring i.p bend.

  2. Cross-linked polybenzimidazole membranes for high temperature proton exchange membrane fuel cells with dichloromethyl phosphinic acid as a cross-linker

    DEFF Research Database (Denmark)

    Noye, Pernille; Li, Qingfeng; Pan, Chao


    Phosphoric acid doped polybenzimidazole (PBI) membranes have been covalently cross-linked with dichloromethyl phosphinic acid (DCMP). FT-IR measurements showed new bands originating from bonds between the hydrogen bearing nitrogen in the imidazole group of PBI and the CH2 group in DCMP. The produ......Phosphoric acid doped polybenzimidazole (PBI) membranes have been covalently cross-linked with dichloromethyl phosphinic acid (DCMP). FT-IR measurements showed new bands originating from bonds between the hydrogen bearing nitrogen in the imidazole group of PBI and the CH2 group in DCMP.......e. within the temperature range of operation of PBI-based fuel cells....

  3. Molecular determinants for drug-receptor interactions. Part 2. An ab initio molecular orbital and dipole moment study of the novel nootropic agent piracetam (2-oxopyrrolidin-1-ylacetamide) (United States)

    Lumbroso, H.; Liégeois, C.; Pappalardo, G. C.; Grassi, A.

    From the ab initio molecular energies of the possible conformers and from a classical dipole moment analysis of 2-oxopyrrolidin-l-ylacetamide (μ = 4.02 D in dioxan at 30.0°C), the preferred conformation in solution of this novel nootropic agent has been determined. The exocyclic N-CH 2 bond is rotated in one sense by 90° and the exocyclic CH 2-C bond rotated in the same sense by 120° from the "planar" ( OO)- cis conformation. The structures of the two enantiomers in solution differ from that of the crystalline molecule.

  4. Supersaturated Self-Assembled Charge-Selective Interfacial Layers for Organic Solar Cells (United States)


    layers (IFLs) on the tin-doped indium oxide (ITO) anodes of organic photovoltaic (OPV) cells , a series of Ar2N-(CH2)n-SiCl3 precursors with Ar = 3,4...applications such as organic photovoltaics ,1−6 thin-film transistors ,7−9 and organic/ polymer light-emitting diodes.10−13 Using SAM surface mod- ification...oxide (ITO) anodes of organic photovoltaic (OPV) cells , a series of Ar2N-(CH2)n-SiCl3 precursors with Ar = 3,4-difluorophenyl, n = 3, 6, 10, and 18, was

  5. Organic Derivatives of Layered Group (4) Phosphates (United States)


    by a Mannich type reaction the phosphonate was of the type H2 O3 P-CH2 (NHCH 2 CH2 ),-NH2 . A small sampling of the compounds prepared (in all 38... reactions are important as potential water splitting techniques, the work has been suspended pending our obtaining additional funding. E. Polyether and...yield a totally new structure as shown in Fig. 17 in which all the sodium was sequestered from solution. If this reaction is reversible, we will have

  6. trans-(2-Benzoylpyridine-κ2N,Odichlorido[2-(2-pyridylcarbonylphenyl-κ2C1,N]iridium(III dichloromethane solvate

    Directory of Open Access Journals (Sweden)


    Full Text Available The title compound, [Ir(C12H8NOCl2(C12H9NO]·CH2Cl2, which was obtained from the reaction of iridium(III chloride trihydrate and 2-benzoylpyridine, contains an IrIII atom coordinated by two N, one O, one C and two Cl atoms in trans positions, forming a distorted octahedral environment. The solvent molecule CH2Cl2 is disordered over two positions with an occupancy of 0.8:0.2.

  7. Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates. (United States)

    Chadwick, F Mark; McKay, Alasdair I; Martinez-Martinez, Antonio J; Rees, Nicholas H; Krämer, Tobias; Macgregor, Stuart A; Weller, Andrew S


    Single-crystal to single-crystal solid/gas reactivity and catalysis starting from the precursor sigma-alkane complex [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(η 2 η 2 -NBA)][BAr F 4 ] (NBA = norbornane; Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) is reported. By adding ethene, propene and 1-butene to this precursor in solid/gas reactions the resulting alkene complexes [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(alkene) x ][BAr F 4 ] are formed. The ethene ( x = 2) complex, [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(ethene) 2 ][BAr F 4 ]-Oct , has been characterized in the solid-state (single-crystal X-ray diffraction) and by solution and solid-state NMR spectroscopy. Rapid, low temperature recrystallization using solution methods results in a different crystalline modification, [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(ethene) 2 ][BAr F 4 ]-Hex , that has a hexagonal microporous structure ( P 6 3 22). The propene complex ( x = 1) [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(propene)][BAr F 4 ] is characterized as having a π-bound alkene with a supporting γ-agostic Rh···H 3 C interaction at low temperature by single-crystal X-ray diffraction, variable temperature solution and solid-state NMR spectroscopy, as well as periodic density functional theory (DFT) calculations. A fluxional process occurs in both the solid-state and solution that is proposed to proceed via a tautomeric allyl-hydride. Gas/solid catalytic isomerization of d 3 -propene, H 2 C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111

  8. A crystallographic and spectroscopic study on the reactions of WCl6 with carbonyl compounds. (United States)

    Dolci, Sara; Marchetti, Fabio; Pampaloni, Guido; Zacchini, Stefano


    WCl6, 1, reacted with two equivalents of HC(O)NR2 (R = Me, Et) in CH2Cl2 to afford the W(VI) oxo-derivatives WOCl4(OCHNR2) (R = Me, 2a; R = Et, 2b) as main products. The hexachlorotungstate(V) salts [{O=C–N(Me)CH2CH2CH2}2(μ-H)][WCl6], 3, and [PhNHC(Me)N(Ph)C(O)Me][WCl6], 4, were isolated in moderate yields from the 1:2 molar reactions of 1 with N-methyl-2-pyrrolidone (in CH2Cl2) and acetanilide (in CDCl3), respectively. The additions of two equivalents of ketones/aldehydes to 1/CH2Cl2 yielded the complexes WOCl4[OC(R)(R′)] (R = Me, R′ = Ph, 5a; R = R′ = Ph, 5b; R = R′ = Me, 5c; R = R′ = Et, 5d; R = H, R′ = 2-Me-C6H4, 5e) and equimolar amounts of C(R)(R′)Cl2. Analogously, WOCl3[κ(2)-{1,2-C6H4(O)(CHO)}], 5f, and 1,2-C6H4(OH)(CHCl2) were obtained from 1 and salicylaldehyde. The 1:1 reaction of 1 with acetone in CH2Cl2 resulted in the clean formation of WOCl4 and 2,2-dichloropropane. Compounds 5a,b,f were isolated as crystalline solids, whereas 5c,d,e could be detected by solution NMR only. The interaction of 1/CH2Cl2 with isatin, in a 1:1 molar ratio, revealed to be a new, convenient route for the synthesis of 3,3-dichloro-2,3-dihydro-1H-indol-2-one, 6. The 1:1 reactions of 1 with R′OCH(R)CO2Me (R = H, R′ = Me; R = Me, R′ = H) in a chlorinated solvent afforded the tungsten(V) adducts WCl4[κ(2)-OCH(R)CO2Me] (R = H, 7a; R = Me, 7b). 1/CH2Cl2 reacted sluggishly with equimolar quantities of trans-(CO2Et)CH=CH(CO2Et) and CH2(CO2Me)2 to give, respectively, the W(IV) derivatives WCl4[κ(2)-CH2(CO2Me)2], 8a, and [WCl4-κ(2)-{trans-(CO2Et)CH=CH (CO2Et)}]n, 8b, in about 70% yields. The molecular structures of 2a, 3, 4, 5a, 5f, 7a and 7b were ascertained by X-ray diffraction studies.

  9. Surfactant selection principle for reducing critical micelle concentration in mixtures of oppositely charged gemini surfactants. (United States)

    Liu, Zhang; Fan, Yaxun; Tian, Maozhang; Wang, Ruijuan; Han, Yuchun; Wang, Yilin


    Cationic quaternary ammonium gemini surfactants C(n)H(2n+1)(CH3)2N(+)CH2CHCHCH2(CH3)2N(+)C(n)H(2n+1)2Br(-) (C(n)C4C(n), n = 12, 8, 6) with alkyl spacers, C(n)H(2n+1)(CH3)2N(+)CH2CHOHCHOHCH2(CH3)2N(+)C(n)H(2n+1)2Br(-) (C(n)C4(OH)2C(n), n = 12, 8, 6, 4) with two hydroxyl groups in alkyl spacers, and cationic ammonium single-chain surfactants C(n)H(2n+1)(CH3)2N(+)Br(-) (C(n)TAB, n = 12, 8, 6) have been chosen to fabricate oppositely charged surfactant mixtures with anionic sulfonate gemini surfactant C12H25N(CH2CH2CH2SO3(-))CH2CH2CH2(CH3)2N(CH2CH2CH2SO3(-))C12H252Na (C12C3C12(SO3)2). Surface tension, electrical conductivity, and isothermal titration microcalorimetry (ITC) were used to study their surface properties, aggregation behaviors, and intermolecular interactions. The mixtures of C12C3C12(SO3)2/C(n)C4(OH)2C(n) (n = 12, 8) and C12C3C12(SO3)2/C12C4C12 show anomalous larger critical micelle concentration (CMC) than C12C3C12(SO3)2, while the mixtures of C12C3C12(SO3)2/C(n)C4(OH)2C(n) (n = 6, 4), C12C3C12(SO3)2/C(n)C4(OH)2C(n) (n = 6, 4), and C12C3C12(SO3)2/C(n)TAB (n = 12, 8, 6) exhibit much lower CMC than C12C3C12(SO3)2. The results indicate that strong hydrophobic interactions between the alkyl chains assisted by strong electrostatic attractions between the headgroups and hydrogen bonds between the spacers lead to the formation of less surface active premicellar aggregates in bulk solution, resulting in the increase of CMC. If these interactions are weakened or inhibited, less surface active premicellar aggregates are no longer formed in the mixtures, and thus the CMC values are reduced. The work reveals that the combination of two surfactants with great self-assembling ability separately may have strong intermolecular binding interactions; however, their mixtures do not always generate superior synergism properties. Only moderate intermolecular interaction can generate the strongest synergism in CMC reduction.

  10. Mechanistic features of isomerizing alkoxycarbonylation of methyl oleate

    KAUST Repository

    Roesle, Philipp


    The weakly coordinated triflate complex [(P̂P)Pd(OTf)] +(OTf)- (1) (P̂P = 1,3-bis(di-tert- butylphosphino)propane) is a suitable reactive precursor for mechanistic studies of the isomerizing alkoxcarbonylation of methyl oleate. Addition of CH 3OH or CD3OD to 1 forms the hydride species [(P ̂P)PdH(CH3OH)]+(OTf)- (2-CH3OH) or the deuteride [(P̂P)PdD(CD 3OD)]+(OTf)- (2D-CD3OD), respectively. Further reaction with pyridine cleanly affords the stable and isolable hydride [(P̂P)PdH(pyridine)]+(OTf) - (2-pyr). This complex yields the hydride fragment free of methanol by abstraction of pyridine with BF3OEt2, and thus provides an entry to mechanistic observations including intermediates reactive toward methanol. Exposure of methyl oleate (100 equiv) to 2D-CD 3OD resulted in rapid isomerization to the thermodynamic isomer distribution, 94.3% of internal olefins, 5.5% of α,β-unsaturated ester and <0.2% of terminal olefin. Reaction of 2-pyr/BF3OEt 2 with a stoichiometric amount of 1-13C-labeled 1-octene at -80 °C yields a 50:50 mixture of the linear alkyls [(P ̂P)Pd13CH2(CH2) 6CH3]+ and [(P̂P)PdCH 2(CH2)6 13CH3] + (4a and 4b). Further reaction with 13CO yields the linear acyls [(P̂P)Pd13C(=O)12/13CH 2(CH2)6 12/13CH3(L)] + (5-L; L = solvent or 13CO). Reaction of 2-pyr/BF 3·OEt2 with a stoichiometric amount of methyl oleate at -80 °C also resulted in fast isomerization to form a linear alkyl species [(P̂P)PdCH2(CH2) 16C(=O)OCH3]+ (6) and a branched alkyl stabilized by coordination of the ester carbonyl group as a four membered chelate [(P̂P)PdCH{(CH2)15CH 3}C(=O)OCH3]+ (7). Addition of carbon monoxide (2.5 equiv) at -80 °C resulted in insertion to form the linear acyl carbonyl [(P̂P)PdC(=O)(CH2)17C(=O)OCH 3(CO)]+ (8-CO) and the five-membered chelate [(P ̂P)PdC(=O)CH{(CH2)15CH3}C(=O) OCH3]+ (9). Exposure of 8-CO and 9 to 13CO at -50 °C results in gradual incorporation of the 13C label. Reversibility of 7 + CO ⇄ 9 is also evidenced by ΔG = -2.9 kcal mol-1 and

  11. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    type of interaction between C-H groups of adamantane and cloud of benzene is found as the important attraction for complex formation. The study also reveals that the methylene (-CH2) and methine (-CH) groups of adamantane interact with benzene resulting in different geometrical structures. And it is found that the ...

  12. Poly(ethylene glycol or Poly(ethylene oxide?: Magnitude of end-group Contribution to the Partitioning of Ethylene Oxide Oligomers and Polymers between Water and Organic Phases

    Directory of Open Access Journals (Sweden)

    Spitzer Marcos


    Full Text Available PEO partitioning from water to CH2Cl2 and CHCl3 increases with its molar mass, leveling off at ca. 3 000 g mol-1. Such a behaviour is related to PEO end-group contributions, suggesting a polyglycol to polyether transition at ca. 3 000 g mol-1.

  13. The Total Synthesis of Chlorophyll

    Indian Academy of Sciences (India)

    IAS Admin

    led to the porphyrin14, which when held at 110oC in AcOH afforded the purpurine 15. This is the first example of porphyrin → purpurin change. Indeed Woodward anticipated this because such a change not only makes 7 and 8 tetrahedral, but also relieves the strain around the lower bridge! As the next step, the CH. 2. CH.

  14. Highly efficient solvent-free synthesis of pyranopyrazoles by a ...

    Indian Academy of Sciences (India)

    ... of dihydropyrano[2,3-c]pyrazole derivatives is developed by a four component reaction of various benzaldehydes, ethyl acetoacetate, hydrazine hydrate and malononitrile in the presence of 3-methyl-1-(4-sulphonic acid)butylimidazolium hydrogen sulphate [(CH2)4SO3HMIM][HSO4], an acidic ionic liquid and as a catalyst, ...

  15. Theoretical study of the structural stability for fcc-CHx phases using density functional theory

    Directory of Open Access Journals (Sweden)

    M Dadsetani


    Full Text Available  Recently, a new carbon modification, namly n-diamond, have been reported, whose structure is still a matter of debate. It is important to note that the synthesis of n-diamond was carried out in the presence of hydrogen or methan. In this work we evaluate the structural stability of five fcc-CHx phases by means of first-principle calculation. The total energy is obtained as a function of the isotropic, tetragonal and rhombohedral deformations for the bulk structures. First, we analyze the C2H (cuprite, CH (zincblende, CH (rocksalt and CH2 (fluorite structures.It is found that the four systems show a minimum in the total energy for the isotropic and rhombohedral deformations, but are unstable against tetragonal deformation. In the second part, we explore the structural stability of CH2 in the pyrite structure. We find that CH2 (pyrite with the hydrogen atoms defined by the internal parameter u=0.35 and a lattice parameter of 3.766 Å is elastically stable, providing a possible explanation for the experimental observation of fcc-carbon in materials prepared in the presence of hydrogen or methan. In final, we calculate density of states, band structure and EELS spectrum of CH2 (pyrite and compare them with n-diamond.

  16. A V1-vascular vasopressin antagonist suitable for radioiodination and photoaffinity labeling

    International Nuclear Information System (INIS)

    Thibonnier, M.; Chehade, N.; Hinko, A.


    We have previously characterized the V1-vascular arginine vasopressin (AVP) receptors of human platelets. We now report on a radiomonoiodinated and photoreactive V1-vascular AVP antagonist (V1-ag) to be used for the purification of human V1-vascular AVP receptors. The V1-ag, d(CH2)5Tyr(Me)Tyr(NH2)AVP was modified by radiomonoiodination of d(CH2)5-Tyr(Me)Tyr(NH2)AVP with the Iodogen technique, and derivatization of d(CH2)5Tyr(Me)Tyr[125I](NH2)-AVP with the photoreactive crosslinker, N-hydroxysuccinimidyl-4-azidobenzoate (HSAB) (each step included HPLC purification). In competition experiments, the affinity of these V1-ag for the human platelet AVP receptors remained excellent. Irreversible photoaffinity labeling of the platelet V1-vascular AVP receptor was successfully achieved by UV lamp exposure (365 nm, 20 min). Thus, AzBz-d(CH2)5Tyr(Me)Tyr[125I](NH2)AVP is a promising tool to use for the purification of human V1-vascular AVP receptors

  17. Synthesis of isobutenyl-telechelic polyisobutylene by functionalization with isobutenyl trimethylsilane

    DEFF Research Database (Denmark)

    Nielsen, Lars Valentin; Nielsen, Rasmus R.; Gao, Bo


    Isobutenyl-telechelic polyisobutylenes (PIBs) were synthesized by reacting telt-chlorine-telechelic and living PIBs with isobutenyltrimethylsilane (IBTMS) in the presence of TiCl4 in CH2Cl2/hexane (40/60 v/v) solvent mixtures at -78 degrees C. In order to obtain PIE oligomers, living polymerization......, chain coupling between the living PIE chains and isobutenyl-ended polymers also occurred. This side reaction was avoided by isobutenylation of tert-chlorine-telechelic PIE with IBTMS in the presence of TiCl4. The resulting isobutenyltelechelic PIE contains exclusively exo-CH2-C(CH3)=CH2 endgroups...... of isobutylene was induced by the di-(2-hydroxy-2-propyl)-5-tert-butylbenzene (tBuDiCumOH)/BCl3 combination in CH2Cl2 followed by addition of required amounts of hexane and TiCl4 to avoid polymer precipitation and permanent termination. Although quantitative end-quenching of living PIE was achieved with IBTMS...

  18. Stimulus Responsive Poly(ferrocenylsilanes): Redox Chemistry of Iron in the Main Chain

    NARCIS (Netherlands)

    Giannotti, M.I.; Lv, H.; Ma, Y.; Steenvoorden, M.P.; Overweg, A.R.; Roerdink, M.; Hempenius, Mark A.; Vancso, Gyula J.


    Redox chemistry of organometallic poly(ferrocenylsilane) polymers (soluble in organic or aqueous environment) is discussed. Poly(ferrocenyldimethylsilane) (PFDMS) was oxidized in CH2Cl2 solution with different oxidants. Oxidation was accomplished with stepwise increasing amounts of ferric chloride

  19. Iodine-catalyzed addition of 2-mercaptoethanol to chalcone derivatives: Synthesis of the novel β-mercapto carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Gürkan Yerli


    Full Text Available In this study, a series of novel β-mercapto carbonyl derivatives (3-(2-hydroxyethylthio-1,3-diarylpropan-1-one (5a-i were prepared by addition of 2-mercaptoethanol (4 to chalcones (3a-i in the presence of catalytic amount of iodine (10 mol % in CH 2Cl 2.

  20. Carbon Dioxide Capture from Air Using Amine-Grafted Porous Polymer Networks

    NARCIS (Netherlands)

    Lu, W.; Sculley, J.P.; Yuan, D.; Krishna, R.; Zhou, H.C.


    Amine-grafted porous polymer networks were investigated for CO2 capture directly from air (400 ppm CO2, 78.96% N-2, and 21% O-2). Under these ultradilute conditions, PPN-6-CH(2)DETA has an extraordinarily high CO2 selectivity (3.6 x 10(10)) and loading capacity (1.04 mol/kg) as calculated using

  1. Experiments with a double solenoid system: Measurements of the 6He + p Resonant Scattering

    Directory of Open Access Journals (Sweden)

    Pampa Condori R.


    Full Text Available A recent experiment has been performed in the double solenoid system Radioactive Ion Beams in Brasil (RIBRAS by impinging a pure 6He secondary beam on a thick CH2 target to measure the 6He + p excitation function. Results of this experiment will be presented.

  2. Ring opening of monocyclic dimethyl cyclopropene via metathesis ...

    Indian Academy of Sciences (India)

    Metathesis reaction of 3,3-disubstituted cyclopropene mediated by the model catalyst tungsten alkylidene W(NH)(CH2)(OCH3)2 has been studied at the B3LYP/LANL2DZ level of theory. The stationary points on the potential energy surface for ring opening metathesis were calculated considering all stereochemically distinct ...

  3. Nigerian Food Journal - Vol 33, No 2 (2015)

    African Journals Online (AJOL)

    In-vivo Effect of Oral Administration of Bifidobacterium adolescentis CH2 of Avian Origin on Male Albino Rats · EMAIL FULL TEXT EMAIL FULL TEXT DOWNLOAD FULL TEXT DOWNLOAD FULL TEXT. J.E. Onyibe, O.B. Oluwole, G.N. Elemo, A.I. Sanni, 46–60 ...

  4. Utilization of softwood kraft lignin as adhsive for the manufacture of reconstituted wood (United States)

    Lin-Wu Zhao; Bruce F. Griggs; Chen-Loung Chen; Josef S. Gratzl; Chung-Yun Hse


    Reaction conditions for hydroxymethylation of pine kraft lignin (KL) were optimized by kinetic studies of the reaction. Characterization of the resulting hydroxymethylated kraft lignin (HMKL) indicated that about 0.36 mole of the -CH2OH/C9 unit was introduced into the ognin under the optimal reaction conditions, of which...

  5. Molecular mechanisms of apoptosis and cell selectivity of zinc dithiocarbamates functionalized with hydroxyethyl substituents. (United States)

    Tan, Yee Seng; Ooi, Kah Kooi; Ang, Kok Pian; Akim, Abdah Md; Cheah, Yoke-Kqueen; Halim, Siti Nadiah Abdul; Seng, Hoi-Ling; Tiekink, Edward R T


    In the solid state each of three binuclear zinc dithiocarbamates bearing hydroxyethyl groups, {Zn[S2CN(R)CH2CH2OH]2}2 for R = iPr (1), CH2CH2OH (2), and Me (3), and an all alkyl species, [Zn(S2CNEt2)2]2 (4), features a centrosymmetric {ZnSCS}2 core with a step topology; both 1 and 3 were isolated as monohydrates. All compounds were broadly cytotoxic, specifically against human cancer cell lines compared with normal cells, with greater potency than cisplatin. Notably, some selectivity were indicated with 2 being the most potent against human ovarian carcinoma cells (cisA2780), and 4 being more cytotoxic toward multidrug resistant human breast carcinoma cells (MCF-7R), human colon adenocarcinoma cells (HT-29), and human lung adenocarcinoma epithelial cells (A549). Based on human apoptosis PCR-array analysis, caspase activities, DNA fragmentation, cell apoptotic assays, intracellular reactive oxygen species (ROS) measurements and human topoisomerase I inhibition, induction of apoptosis in HT-29 cells is demonstrated via both extrinsic and intrinsic pathways. Compounds 2-4 activate the p53 gene while 1 activates both p53 and p73. Cell cycle arrest at the S and G2/M phases correlates with inhibition of HT-29 cell growth. Cell invasion is also inhibited by 1-4 which is correlated with down-regulation of NF-κB. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. Intracavity absorption spectroscopy of formaldehyde from 6230 to 6420 cm(-1)

    NARCIS (Netherlands)

    Fjodorow, Peter; Hellmig, Ortwin; Baev, Valery M.; Levinsky, Howard B.; Mokhov, Anatoli V.

    We apply intracavity absorption spectroscopy for measurements of the absorption spectrum of formaldehyde, CH2O, from 6230 to 6420 cm(-1), of which only a small fraction (6351-6362 cm(-1)) has been recorded elsewhere. The measurements are performed in the cavity of a broadband Er3+-doped fiber laser,

  7. Ultrasonic Examination of Double-Shell Tank 241-AP-106. Examination Completed November 2004

    Energy Technology Data Exchange (ETDEWEB)

    Pardini, Allan F.; Posakony, Gerald J.


    COGEMA Engineering Corporation (COGEMA), under a contract from CH2M Hill Hanford Group (CH2M Hill), has performed an ultrasonic nondestructive examination of selected portions of Double-Shell Tank 241-AP-106. The purpose of this examination was to provide information that could be used to evaluate the integrity of the wall of the primary tank. The requirements for the ultrasonic examination of Tank 241-AP-106 were to detect, characterize (identify, size, and locate), and record measurements made of any wall thinning, pitting, or cracks that might be present in the wall of the primary tank. Any measurements that exceed the requirements set forth in the Engineering Task Plan (ETP), RPP-22571 (Jensen 2004) and summarized on page 1 of this document, are reported to CH2M Hill and the Pacific Northwest National Laboratory (PNNL) for further evaluation. Under the contract with CH2M Hill, all data is to be recorded on disk and paper copies of all measurements are provided to PNNL for third-party evaluation. PNNL is responsible for preparing a report that describes the results of the COGEMA ultrasonic examinations.

  8. Reactivity studies of pincer bis-protic N-heterocyclic carbene complexes of platinum and palladium under basic conditions

    Directory of Open Access Journals (Sweden)

    David C. Marelius


    Full Text Available Bis-protic N-heterocyclic carbene complexes of platinum and palladium (4 yield dimeric structures 6 when treated with sodium tert-butoxide in CH2Cl2. The use of a more polar solvent (THF and a strong base (LiN(iPr2 gave the lithium chloride adducts monobasic complex 7 or analogous dibasic complex 8.

  9. Identification and Development of Biological Markers of Human Exposure to the Insecticide Permethrin (United States)


    packed into aluminum sample holders, and carbon isotope ratios were measured on the spectrometer. Typical AMS measurement times were 3 min/sample...chloride (5 mL) was added to an ice-cooled suspension of powdered alumi- num trichloride (2.66 g, 20 mmol) in dry CH2Cl2 (15 mL), in which bromine (3.4 g

  10. Optimization of biodiesel production from rice bran oil via ...

    African Journals Online (AJOL)

    ... 9,12-octadecadienoic and 9-octadecadienoic acid. The fourier transform infrared spectrum of biodiesel also showed the characteristic bands of C=O, O-C-O, C=C and –(CH2)n-. Key words: Rice bran oil, biodiesel, response surface methodology, gas chromatography mass spectrometry, fourier transform infrared spectrum ...

  11. Photodissociation of gaseous CH3COSH at 248 nm by time-resolved Fourier-transform infrared emission spectroscopy: Observation of three dissociation channels

    International Nuclear Information System (INIS)

    Hu, En-Lan; Tsai, Po-Yu; Fan, He; Lin, King-Chuen


    Upon one-photon excitation at 248 nm, gaseous CH 3 C(O)SH is dissociated following three pathways with the products of (1) OCS + CH 4 , (2) CH 3 SH + CO, and (3) CH 2 CO + H 2 S that are detected using time-resolved Fourier-transform infrared emission spectroscopy. The excited state 1 (n O , π * CO ) has a radiative lifetime of 249 ± 11 ns long enough to allow for Ar collisions that induce internal conversion and enhance the fragment yields. The rate constant of collision-induced internal conversion is estimated to be 1.1 × 10 −10 cm 3 molecule −1 s −1 . Among the primary dissociation products, a fraction of the CH 2 CO moiety may undergo further decomposition to CH 2 + CO, of which CH 2 is confirmed by reaction with O 2 producing CO 2 , CO, OH, and H 2 CO. Such a secondary decomposition was not observed previously in the Ar matrix-isolated experiments. The high-resolution spectra of CO are analyzed to determine the ro-vibrational energy deposition of 8.7 ± 0.7 kcal/mol, while the remaining primary products with smaller rotational constants are recognized but cannot be spectrally resolved. The CO fragment detected is mainly ascribed to the primary production. A prior distribution method is applied to predict the vibrational distribution of CO that is consistent with the experimental findings.

  12. Alkaloids from a panamanian poison frog, Dendrobates speciosus: identification of pumiliotoxin-A and allopumiliotoxin class alkaloids, 3,5-disubstituted indolizidines, 5-substituted 8-methylindolizidines, and a 2-methyl-6-nonyl-4-hydroxypiperidine. (United States)

    Edwards, M W; Daly, J W; Myers, C W


    Dendrobates speciosus is a small red or orange frog that occupies a small geographic range in the highlands of western Panama, where it occurs abundantly in some cloud forest habitats. Gc-ms analysis indicated the presence of at least 30 alkaloids in MeOH skin extracts from population samples at the extreme eastern end of the known geographic range. Eleven alkaloids were isolated by cc in quantities sufficient for 2D-nmr spectral analysis, which in some cases confirmed their identity with alkaloids known from other species and in other cases led to assignment of structures. Pumiliotoxin 251D, pumiliotoxin A [307A], pumiliotoxin B [323A], and allopumiliotoxin 267A were identified as major constituents. N-Oxides of 323A and 267A were also isolated. Indolizidines 195B and 223AB with 3-butyl-5-methyl and 3-butyl-5-propyl substituents, respectively, were identified. The 5-substituents of the 8-methyl-indolizidines 207A and 235B' were assigned as -(CH2)3CH = CH2 and -(CH2)5CH = CH2, respectively; indolizidine 235B' from D. speciosus is, thus, a positional double-bond isomer of indolizidine 235B previously isolated from a closely related poison frog, Dendrobates pumilio. A piperidine 241D was isolated and assigned the structure cis-cis-2-methyl-6-nonyl-4-hydroxypiperidine.

  13. 76 FR 23333 - Notice of Proposed Withdrawal Extension and Opportunity for Public Meeting; Wyoming (United States)


    ... location and entry under the United States mining laws to protect unique topographic characteristics and... action and announces the date, time, and location of a public meeting. DATES: Comments must be received... Caribou Counties, Wyoming, from location and entry under the United States mining laws (30 U.S.C. ch. 2...

  14. 75 FR 63856 - Public Land Order No. 7753; Extension of Public Land Order No. 7464; Montana (United States)


    ...-Landusky mining area which would otherwise expire on October 4, 2010. DATES: Effective Date: October 5... protection of the Zortman-Landusky mining area until reclamation is completed. The withdrawal has been... mining laws (30 U.S.C. ch. 2), to protect the Zortman-Landusky Mining Area, is hereby further extended...

  15. 76 FR 45848 - Notice of Application for Withdrawal and Public Meeting; Oregon (United States)


    ... temporarily segregates the lands for up to 2 years from location and entry under the United States mining laws... date, time, and location of a public meeting. DATES: Comments must be received by October 31, 2011... States mining laws (30 U.S.C. ch. 2), and operation of the mineral and geothermal leasing laws, subject...

  16. A Novel Potentiometric Sensor for Determination of Neurotoxin β-N-Oxalyl-L-α, β-Diaminopropionic Acid

    Directory of Open Access Journals (Sweden)

    Omer Isildak


    Full Text Available A novel potentiometric sensor based on ionophore (Cd(NH2CH2CH2OCH2CH2OCH2CH2NH2Ag3(CN5 for the determination of β-N-oxalyl-l-α, β-diaminopropionic acid (ODAP is developed. The ODAP-selective membrane sensor demonstrates high sensitivity and short response time. The detection limit of the ODAP-selective membrane sensor is about 2×10-6 mol L-1 and the response time is shorter than 6 s. The linear dynamic range of the ODAP-selective membrane sensor is between ODAP concentrations of 1.0×10-2 and 1×10-6 mol L-1. The ODAP-selective membrane sensor exhibits good operational stability for at least one week in dry conditions at 4–6°C. It has a reproducible and stable response during continuous work for at least 10 h with a relative standard deviation of 0.28% (n = 18.

  17. [Time-resolved FTIR emission studies of laser photofragmentation and radical reactions

    International Nuclear Information System (INIS)


    Fourier transform infrared emission experiments were used to study photofragmentation processes, single collision reactions, energy transfer events, and laser-initiated radical-radical reactions: CH 3 + O, Cl + C 2 H 5 , CF 3 CH 2 + D, H + H 2 O, H + HF, and H + NH 2

  18. An efficient one-pot procedure for asymmetric bifunctionalization of 5,15-disubstituted porphyrins: a simple preparation of meso acyl-, alkoxycarbonyl-, and carbamoyl-substituted meso-formylporphyrins. (United States)

    Takanami, Toshikatsu; Wakita, Atsushi; Matsumoto, Jun; Sekine, Sadashige; Suda, Kohji


    An efficient one-pot procedure which converts 5,15-disubstituted porphyrins into their corresponding meso acyl-, alkoxycarbonyl-, and carbamoyl-substituted meso-formylporphyrins has been developed, where the procedure involves a sequential S(N)Ar reaction of porphyrins with PyMe(2)SiCH(2)Li, followed by acylation or related reactions and oxidation.

  19. Effects of Polyethylene Glycol on the Mechanical Properties of ...

    African Journals Online (AJOL)

    The effect of polyethylene glycol [H(OCH2CH2)nOH] as quenchant was studied with a view to investigate the mechanical properties and microstructural evaluation of steel. The test samples were subjected to a conventional heat treatment process followed by quenching using prepared polymer solution with a definite ...

  20. Thallium trinitrate mediated ring contraction of cis-2-decalones

    Directory of Open Access Journals (Sweden)

    Ferraz Helena M. C.


    Full Text Available The reaction of some cis-2-decalones with TTN in CH2Cl2 at room temperature was investigated. The ring contraction reactions occurred in good yields, however the regio- and diastereoselectivity were low. The effect of the alkyl groups in the regiochemistry of the reaction depends on their position at the decalone ring system.