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31.
Obenchain DA Bills BJ Christenholz CL Elmuti LF Peebles RA Peebles SA Neill JL Steber AL 《The journal of physical chemistry. A》2011,115(44):12228-12234
The microwave spectra of four isotopologues of the CHBrF(2)···HCCH weakly bound dimer have been measured in the 6-18 GHz region using chirped-pulse and Balle-Flygare Fourier-transform microwave spectroscopy. Spectra of (13)CH(79)BrF(2) and (13)CH(81)BrF(2) monomers have also been measured, and spectroscopic constants are reported. Measurement of spectra for the (79)Br and (81)Br isotopologues of CHBrF(2) complexed with both (12)C(2)H(2) and (13)C(2)H(2) have allowed the determination of a structure with C(s) symmetry for this complex. CHBrF(2) interacts with the triple bond of acetylene via a C-H···π contact (R(H···π) = 2.670(8) ?) with the Br atom lying in the ab plane, located 3.293(40) ? from a hydrogen atom of the HCCH molecule. The structure of CHBrF(2)···HCCH has been compared with recently studied related acetylene complexes, including a comparison with (and further structural analysis of) the CHClF(2)···HCCH complex. 相似文献
32.
Systematic investigation of asymmetric trimethylsilylcyanation of heterocyclic azomethines has been realized. The addition of trimethylsilyl cyanide to optically active furan, thiophene and pyridine aldimines, derived from (R)‐ and (S)‐1‐phenylethylamine, was studied in the presence of Lewis acids, and a series of the corresponding α‐amino nitriles was obtained in fair to good yields (up to 91%). Unsaturated nitriles were also formed from pyridine imines. The sense of asymmetric induction and the degree of diastereoselectivity in the synthesis of α‐amino nitriles were determined by means of 1H NMR. The stereochemical outcome is a result of the same sense of asymmetric induction: Re face attack to the (S)‐imines and Si face addition to the (R)‐imines took place. The (R,R)‐ (up to 81%) or (S,S)‐ (up to 87%) α‐amino nitriles predominated in the products obtained from the all furan, thiophene and pyridine (R)‐ or (S)‐imines respectively. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
33.
Kenneth S. Pitzer 《Journal of solution chemistry》1975,4(3):249-265
The contribution of higher-order electrostatic terms (beyond the Debye-Hückel approximation) to the thermodynamic properties of mixed and pure electrolytes is investigated. It is found that these effects are important for cases of unsymmetrical mixing, especially when one ion has a charge of three units or more. The appropriate correction can be made by a purely electrostatic function since the mutual repulsion of ions of the same sign keeps them far enough apart that short-range forces have little effect. This function is evaluated, and several convenient approximations are also given. Application is made to systems mixing ions of the type 1–2 and 1–3. Higher-order limiting laws exist for symmetrical mixtures and for pure, unsymmetrical solutes, but these effects were not found to be significant in relationship to existing activity or osmotic-coefficient data. 相似文献
34.
The activity coefficient of saturated aqueous Na2SO4 is calculated from the properties of the solid and the infinitely dilute solution as well as the solubility. These values are compared with those given by the equation of Rogers and Pitzer which is based on the measured dependence of heat capacity upon molality together with other solution properties at low temperature. Excellent agreement is found from 30 to 280°C. Consequently the equation of Rogers and Pitzer is given an extended range of validity to saturated molality and to 280°C. The trend of solubility with temperature is discussed in relation to the Cp of solution. 相似文献
35.
Thermodynamics of electrolytes. X. Enthalpy and the effect of temperature on the activity coefficients 总被引:2,自引:0,他引:2
Heat of dilution and of solution data are fitted to the form of equation corresponding to that used successfully for activity and osmotic coefficients over a wide range of concentrations. The resulting parameters give the change with temperature of the activity and osmotic coefficients. Results are reported for 84 electrolytes of 1-1, 2-1, 3-1, and 2-2 valence types. 相似文献
36.
Kenneth S. Pitzer John R. Peterson Leonard F. Silvester 《Journal of solution chemistry》1978,7(1):45-56
The extensive data for the osmotic coefficients, heats of dilution, and densities of aqueous solutions of rare earth chlorides, nitrates, and perchlorates are fitted to a single type of equation found satisfactory for many other solutes Good agreement is obtained. The various parameters do not show simple trends with cation radius. While there are some plausible explanations of these complexities, the total picture is far from clear. 相似文献
37.
William P. White Russell M. Pitzer C. Weldon Mathews Thom H. Dunning 《Journal of Molecular Spectroscopy》1979,75(2):318-326
Hartree-Fock and multiconfiguration Hartree-Fock calculations are reported on some low-lying Rydberg states of CF and the ground state of CF+. For the CF+ ground state, 1Σ+, the calculations give a bond length of 1.55 Å, a fundamental frequency of 1821 cm?1, and a dissociation energy of 6.9 eV. Many interactions between the valence and Rydberg state manifolds are revealed. Also a strong mixing of the 3dσ and 4sσ components due to an accidental degeneracy is described. 相似文献
38.
Background
Granulocyte colony stimulating factor (G-CSF) is a growth factor essential for generation of neutrophilic granulocytes. Apart from this hematopoietic function, we have recently uncovered potent neuroprotective and regenerative properties of G-CSF in the central nervous system (CNS). The G-CSF receptor and G-CSF itself are expressed in α motoneurons, G-CSF protects motoneurons, and improves outcome in the SOD1(G93A) transgenic mouse model for amyotrophic lateral sclerosis (ALS). In vitro, G-CSF acts anti-apoptotically on motoneuronal cells. Due to the pleiotrophic effects of G-CSF and the complexity of the SOD1 transgenic ALS models it was however not possible to clearly distinguish between directly mediated anti-apoptotic and indirectly protective effects on motoneurons. Here we studied whether G-CSF is able to protect motoneurons from purely apoptotic cell death induced by a monocausal paradigm, neonatal sciatic nerve axotomy. 相似文献39.
Schaffner AP Lena G Roussel S Wawrezinieck A Aubry A Briand JP Didierjean C Guichard G 《Chemical communications (Cambridge, England)》2006,(39):4069-4071
Enantiopure dipeptide-derived 1,3,5-triazepan-2,6-diones and form H-bonded 3(1) helical molecular tapes with P chirality in the solid state; in the case of , these columnar tapes self-assemble through aromatic-aromatic interactions to give hollow tubular structures. 相似文献
40.
Lena Scherthan Sebastian F. M. Schmidt Hendrik Auerbach Tim Hochdrffer Juliusz A. Wolny Wenli Bi Jiyong Zhao Michael Y. Hu Tom Toellner E. Ercan Alp Dennis E. Brown Christopher E. Anson Annie K. Powell Volker Schünemann 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(11):3482-3487
Time‐domain synchrotron Mössbauer spectroscopy (SMS) based on the Mössbauer effect of 161Dy has been used to investigate the magnetic properties of a DyIII‐based single‐molecule magnet (SMM). The magnetic hyperfine field of [Dy(Cy3PO)2(H2O)5]Br3?2 (Cy3PO)?2 H2O?2 EtOH is with B0=582.3(5) T significantly larger than that of the free‐ion DyIII with a 6H15/2 ground state. This difference is attributed to the influence of the coordinating ligands on the Fermi contact interaction between the s and 4f electrons of the DyIII ion. This study demonstrates that 161Dy SMS is an effective local probe of the influence of the coordinating ligands on the magnetic structure of Dy‐containing compounds. 相似文献