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41.
Application of linear free energy relationships (correlation between kinetics and thermodynamics) to catalytic hydrogenation
of aromatic compounds in the liquidphase over supported metal catalysts is discussed. 相似文献
42.
Reversible storage of molecular hydrogen by sorption into multilayered TiO2 nanotubes 总被引:4,自引:0,他引:4
Bavykin DV Lapkin AA Plucinski PK Friedrich JM Walsh FC 《The journal of physical chemistry. B》2005,109(41):19422-19427
The sorption of hydrogen between the layers of the multilayered wall of nanotubular TiO2 was studied in the temperature range of -195 to 200 degrees C and at pressures of 0 to 6 bar. Hydrogen can intercalate between layers in the walls of TiO2 nanotubes forming host-guest compounds TiO2 x xH2, where x < or = 1.5 and decreases at higher temperatures. The rate of hydrogen incorporation increases with temperature and the characteristic time for hydrogen sorption in TiO2 nanotubes is several hours at 100 degrees C. The rate of intercalate formation is limited by the diffusion of molecular hydrogen inside the multilayered walls of the TiO2 nanotube. 1H NMR-MAS and XRD data confirm the incorporation of hydrogen between the layers in the walls of TiO2 nanotubes. The nature and possible applications of the observed intercalates are considered. 相似文献
43.
An (15)N NMR R(1rho) relaxation experiment is presented for the measurement of millisecond time scale exchange processes in proteins. On- and off-resonance R(1rho) relaxation profiles are recorded one residue at a time using a series of one-dimensional experiments in concert with selective Hartmann-Hahn polarization transfers. The experiment can be performed using low spin-lock field strengths (values as low as 25 Hz have been tested), with excellent alignment of magnetization along the effective field achieved. Additionally, suppression of the effects of cross-correlated relaxation between dipolar and chemical shift anisotropy interactions and (1)H-(15)N scalar coupled evolution is straightforward to implement, independent of the strength of the (15)N spin-locking field. The methodology is applied to study the folding of a G48M mutant of the Fyn SH3 domain that has been characterized previously by CPMG dispersion experiments. It is demonstrated through experiment that off-resonance R(1rho) data measured at a single magnetic field and one or more spin-lock field strengths, with amplitudes on the order of the rate of exchange, allow a complete characterization of a two-site exchange process. This is possible even in the case of slow exchange on the NMR time scale, where complementary approaches involving CPMG-based experiments fail. Advantages of this methodology in relation to other approaches are described. 相似文献
44.
45.
Sergey?P.?BabailovEmail author Dmitry?A.?Mainichev Lubov?D.?Nikulina Svetlana?S.?Petrova 《Journal of inclusion phenomena and macrocyclic chemistry》2005,51(1-2):73-78
Earlier the intramolecular inversion of the 18-crown-6 molecules was found in the complex ion pairs [Ln(ptfa)2 (18-crown-6)]+ [Ln(ptfa)4]− (H2O)4 where Ln = La(1), Ce (2), Pr (3), Nd (4), and ptfa is 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione. In this work the peculiarities of the molecular structure and dynamics were studied for [Eu(ptfa)2 (18-crown-6)]+ [Eu(ptfa)4]− (H2O)4 (5) by NMR spectroscopy techniques. Through VT-NMR spectra analysis the temperature dependence was obtained for the rate constant. The free energy ΔG‡(320) of 18-crown-6 ring inversion activation was found to be 65 ± 5 kJ mol−1 for 5 in CDCl3. This result is comparable with the earlier data [S.P. Babailov and D.A. Mainichev: J. Inclusion Phenom. Macrocyclic Chem. 43, 187–193 (2002)] for complexes 2, 3, 4 in deuterated toluene (ΔG‡(320)=65 ± 9, 64 ± 9, 64 ± 9 kJ mol−1 respectively). It was found by relaxation NMR spectroscopy that the effective distance between Ln and protons of the crown molecule is 4.5 ± 0.2 Å. The analysis of structural parameters testifies that the crown ether and chelated anions are in the first coordination sphere of a Ln cation. Obtained geometrical parameters show that the complex cations of Eu, Ce and Pr have similar spatial structures.This revised version was published online in July 2005 with a corrected issue number. 相似文献
46.
We have conducted a high-level quantum chemistry study of the interactions of 1,2-dimethoxyethane (DME) with water for complexes representing both hydrophilic and hydrophobic hydration. It was found that our previous quantum chemistry-based force field for poly(ethylene oxide) (PEO) and its oligomers in aqueous solution did a poor job in describing the hydrophobic binding of water to the ether, consistent with our recent calculations of the excess free energy and entropy of hydration of DME. Our original force field was revised to more accurately reproduce the interaction of water with the carboneous portions of DME. Molecular dynamics simulations of aqueous DME solutions using the revised quantum chemistry-based potential yielded good agreement with experiment for excess free energy, enthalpy, and volume as well as excess solution viscosity and the self-diffusion of water. Comparison with our original potential revealed that the relatively hydrophobic ether-water interactions in the new potential strongly reduced the favorable excess free energy and enthalpy but have relatively little influence on the excess entropy for dilute DME solutions. Other properties of DME and PEO solutions including conformational populations and dynamics, solution viscosity, hydrogen bonding, water translational and rotational diffusion and neutron structure factor as a function of solution composition were found to be largely unchanged from those obtained using the original potential. 相似文献
47.
Simplified method for the Re-Os dating of molybdenite using acid digestion and isotope dilution ICP-MS 总被引:1,自引:0,他引:1
An analytical method was developed for Os-Re dating of molybdenite. The method is based on determination of Os and Re concentrations in molybdenite by isotope dilution inductively-coupled plasma mass spectrometry (ID-ICP-MS). Sample digestion and sample/spike equilibration were achieved by a two-stage autoclave-based procedure using a mixture of nitric and sulphuric acids. Os was separated from the sample digest by modified single-stage distillation of osmium tetraoxide (OsO4) using elevated temperature and on-line addition of hydrogen peroxide. OsO4(g) was trapped in a mixture of 0.05% thiourea in 0.05 M sodium hydroxide. An anion-exchange column was used to separate Re from excess Mo in the solution remaining after distillation. Os and Re isotope ratio measurements were performed by single-collector, double focusing inductively-coupled plasma mass spectrometry (ICP-MS) with on-line mass-bias correction. Typical instrumental precision was in the range 0.02-0.2% relative standard deviation (R.S.D.) depending on the analyte concentrations. Notorious Os memory effects in the ICP-MS introduction system were eliminated using 5% ammonia solution, both as matrix for final dilution of the trap mixture as well as for washing between the samples. The reproducibility of the entire analytical procedure was accessed by replicate dating of two molybdenite standards and three molybdenite separates, and was found to be in the range 0.87-1.52% R.S.D. Though accuracy of the method is limited by difficulties in evaluating exact concentration of Os in spike solution, ages obtained in the course of these work agrees well with previously published data. 相似文献
48.
Removal from air and decomposition of dimethyl methylphosphonate (DMMP) over high surface area anatase TiO(2) at ambient temperature have been quantitatively studied by employing Fourier transform infrared (FTIR) technique under static conditions. In the first scenario of air purification, DMMP underwent reactive adsorption that upon completion was followed by photocatalytic oxidation. DMMP was captured over the TiO(2) surface at the speed of external diffusion. Hydrolysis of adsorbed DMMP led to methanol and methyl methylphosphonate (MMP). At low DMMP coverage quantity, it hydrolyzed completely with the formation of completely surface-bound methanol at 1% relative humidity (RH) and mostly gaseous methanol at 50% RH. Photocatalytic oxidation generated CO(2) as the only carbonaceous gaseous product and bidentate formates as the intermediate surface product. At high DMMP coverage quantity, it was captured incompletely and hydrolyzed partially with CH(3)OH in the gas phase only, 50% RH enhancing both processes. Photocatalytic oxidation generated gaseous HCOOH, CO, and CO(2) and was incomplete due to catalyst deactivation by nonvolatile products. In the second scenario of air purification, DMMP underwent adsorption, hydrolysis, and photooxidation at the same time. It resulted in the quickest removal of DMMP from the gas phase and completion of oxidation in 30 min, suggesting this process for practical air decontamination. At least 0.8 nm(2) of TiO(2) surface per each DMMP molecule should be available for complete purification of air. 相似文献
49.
The temperature dependence of the rate of electron transfer is analyzed in the framework of a molecular theory presented recently, characterized by decoupling the total solvent reorganization energy into two contributions featuring reorganizations of permanent dipoles as well as solvent density. The inclusion of the temperature dependence of liquid density reorganization can give rise to a maximum in the Arrhenius coordinates for electron transfer in the inverted region and for exothermic reactions with small activation barriers as well. 相似文献
50.
Dmitry S. Perekalin Pavel V. Petrovskii Bohumil Štíbr Alexander R. Kudinov 《Journal of organometallic chemistry》2005,690(11):2775-2779
The reaction of the tricarbollide salt Tl[7-tBuNH-7,8,9-C3B8H10] (Tl1) with [(cod)Rh(THF)x]+ gives the rhodium complex [1-(cod)-12-tBuNH-1,2,4,12-RhC3B8H10] in almost quantitative yield. Analogous reactions of Tl1 with [(ring)M(THF)x]2+ ((ring)M = Cp*Rh and (1,3,5-C6H3Me3)Ru) afford the corresponding metallatricarbollides [1-(ring)-12-tBuNH-1,2,4,12-MC3B8H10] in ca. 50% yield. Refluxing Tl1 with [Mn(CO)3(MeCN)3]+ in THF give the tricarbollide analogue of cymantrene, [1,1,1-(CO)3-12-tBuNH-1,2,4,12-MnC3B8H10], the structure of which was determined by single-crystal X-ray diffraction analysis. In all cases, the formation of the metallatricarbollide complexes is accompanied by polyhedral rearrangement leading to the maximum separation of the cage carbon atoms. 相似文献