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1.
The reaction of KCN with Al(CH3)3 to form K[Al(CH3)3CN] is greatly facilitated by the presence of an aromatic solvent: for p-xylene a solid complex, K[Al(CH3)3CN]·C6H4(CH3)2, has been isolated. The crystal structure of potassium cyanotrimethylaluminate has been determined from three-dimensional X-ray data measured by counter methods. K[Al(CH3)3CN] crystallizes in the monoclinic space group C2/c with cell dimensions a = 19.902(7), b = 9.211(4), c = 9.615(4) Å, β = 107.74(5)°, and pcalcd. = 1.09 g cm?1 for Z = 8. Least squares refinement gave a conventional weighted R factor of 4.9% for 807 independent reflections. The monomeric [Al(CH3)3CN]? units possess no crystallographic symmetry, and the packing in the unit cell is such that the nitrogen atoms on three such units approach the potassium atom to within 3.11 Å. The average aluminum-methyl carbon bond distance is 1.971 (7) Å, while the aluminum-cyano carbon distance is 2.047 (7) Å. This significant lengthening is attributed to partial electron deficiency in the aluminum-cyano carbon bond. 相似文献
2.
Cardenas RL Cheng KH Verhey LJ Xia P Davis L Cannon B 《Magnetic resonance imaging》2002,20(9):667-679
In a clinical setting, mixed and inconsistent results have been reported using Magnetic Resonance Relaxation imaging of irradiated aqueous polymeric gels as a three-dimensional dosimeter, for dose verification of conformal radiation therapy. The problems are attributed to the difficulty of identifying an accurate dose calibration protocol for each delivered gel at the radiation site in a clinical setting. While careful calibration is done at the gel manufacturing site in a controlled laboratory setting, there is no guarantee that the dose sensitivity of the gels remains invariant upon delivery, irradiation, magnetic resonance imaging and storage at the clinical site. In this study, we have compared three different dose calibration protocols on aqueous polymeric gels for a variety of irradiation scenarios done in a clinical setting. After acquiring the three-dimensional proton relaxation maps of the irradiated gels, the dose distributions were generated using the off-site manufacturer provided calibration curve (Cal-1), the on-site external tube gel calibration (Cal-2) and the new on-site internal normalized gel calibration (Cal-3) protocols. These experimental dose distributions were compared with the theoretical dose distributions generated by treatment-planning systems. We observed that the experimental dose distributions generated from the Cal-1 and Cal-2 protocols were off by 10% to 40% and up to 200% above the predicted maximum dose, respectively. On the other hand, the experimental dose distributions generated from the Cal-3 protocol matched reasonably well with the theoretical dose distributions to within 10% difference. Our result suggests that an independent on-site normalized internal calibration must be performed for each batch of gel dosimeters at the time of MR relaxation imaging in order to account for the variations in dose sensitivity caused by various uncontrollable conditions in a clinical setting such as oxygen contamination, temperature changes and shelf life of the delivered gel between manufacturing and MR acquisitions. 相似文献
3.
4.
Summary When two immiscible fluids in a porous medium are in contact with one another, an interface is formed and the movement of
the fluids results in a free boundary problem for determining the location of the interface along with the pressure distribution
throughout the medium. The pressure satisfies a nonlinear parabolic partial differential equation on each side of the interface
while the pressure and the volumetric velocity are continuous across the interface. The movement of the interface is related
to the pressure through Darcy’s law. Two kinds of boundary conditions are considered. In Part I the pressure is prescribed
on the known boundary. A weak formulation of the classical problem is obtained and the existence of a weak solution is demonstrated
as a limit of a sequence of classical solutions to certain parabolic boundary value problems. In Part II the same analysis
is carried out when the flux is specified on the known boundary, employing special techniques to obtain the uniform parabolicity
of the sequence of approximating problems.
Entrata in Redazione il 29 novembre 1975.
This research was supported in part by the National Science Foundation, the Senior Fellowship Program of the North Atlantic
Treaty Organization, the Italian Consiglio Nazionale delle Ricerche, and the Texas Tech. University. 相似文献
5.
Jiang H Li Y Pelzer M Cannon MJ Randlett C Junga H Jiang X Ji QC 《Journal of chromatography. A》2008,1192(2):230-238
A sensitive and selective bioanalytical assay was developed and validated for the determination of enantiomeric molindone in human plasma using high-performance liquid chromatography-tandem mass spectrometry along with supported liquid extraction procedures. The chiral separation was evaluated and optimized on macrocyclic antibiotic type chiral stationary phases (CSPs) based on teicoplanin aglycone (Chirobiotic TAG) in polar organic, polar ionic, and reversed-phase mode chromatography, respectively. Complete baseline separation was achieved on a Chirobiotic TAG column under isocratic condition in reversed-phase chromatography. The method validation was conducted using a Chirobiotic TAG column (100 mm x 2.1 mm) over the curve range 0.100-100 ng/ml for each molindone enantiomer using 0.0500 ml of plasma sample. The flow rate was 0.8 ml/min and the total run time was 9 min. Supported liquid extraction in a 96-well plate format was used for sample preparation. Parameters including recovery, matrix effect, linearity, sensitivity, specificity, carryover, precision, accuracy, dilution integrity, and stability were evaluated. The intra- and inter-day precision and accuracy of the quality control samples at low, medium, and high concentration levels were RSD 相似文献
6.
Cannon JS Kirsch SF Overman LE Sneddon HF 《Journal of the American Chemical Society》2010,132(43):15192-15203
The catalytic enantioselective S(N)2' displacement of (Z)-allylic trichloroacetimidates catalyzed by the palladium(II) complex [COP-OAc](2) is a broadly useful method for the asymmetric synthesis of chiral branched allylic esters. A variety of experiments aimed at elucidating the nature of the catalytic mechanism and its rate- and enantiodetermining steps are reported. Key findings include the following: (a) the demonstration that a variety of bridged-dipalladium complexes are present and constitute resting states of the COP catalyst (however, monomeric palladium(II) complexes are likely involved in the catalytic cycle); (b) labeling experiments establishing that the reaction proceeds in an overall antarafacial fashion; (c) secondary deuterium kinetic isotope effects that suggest substantial rehybridization at both C1 and C3 in the rate-limiting step; and (d) DFT computational studies (B3-LYP/def2-TZVP) that provide evidence for bidentate substrate-bound intermediates and an anti-oxypalladation/syn-deoxypalladation pathway. These results are consistent with a novel mechanism in which chelation of the imidate nitrogen to form a cationic palladium(II) intermediate activates the alkene for attack by external carboxylate in the enantiodetermining step. Computational modeling of the transition-state structure for the acyloxy palladation step provides a model for enantioinduction. 相似文献
7.
Ann M. Schmiedekamp Anthony Ginnetti Brian Piccione Kevin Cannon M. Dominic Ryan 《International journal of quantum chemistry》2007,107(6):1415-1429
Octahedral, six‐coordinate Co2+ can exist in two spin states: S = 3/2 and S = 1/2. The difference in energy between high spin (S = 3/2) and low spin (S = 1/2) is dependent on both the ligand mix and coordination stereochemistry. B3LYP calculations on combinations of neutral imidazole, NH3, and H2O ligands show that low‐spin isomers are stabilized by axial H2O ligands and in structures that also include trans pairs of equatorial NH3 and protonated imidazole ligands, spin crossover structures are predicted from spin state energy differences. Occupied Co d orbitals from the DFT calculations provide a means of estimating effective ligand strength for homoleptic and mixed ligand combinations. These calculations suggest that in a labile biological system, a spin crossover environment can be created. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
8.
This paper considers the time dependent stefan problem with convection in the fluid phase governed by the Stokes equation, and with adherence of the fluid on the lateral boundaries: The existence of a weak solution is obtained via the introduction of a temperature dependent penalty term in the fluid flow equation, together with the application of various compactness arguments. 相似文献
9.
Summary
Existence and unicity for the solution of the one-dimensional two-phase Stefan problem with energy specification
in the liquid phase is established via potential theoretic arguments employing the Schauder fixed point theorem and a contracting map.This work was supported in part by NSF Grant MCS-7801687.This work was carried out at UT-Austin while on sabbatical from the University of Adelaide. 相似文献
10.
There are few techniques available to numerically solve sixth-order boundary-value problems with two-point boundary conditions. In this paper we show that the Sinc-Galerkin method is a very effective tool in numerically solving such problems. The method is then tested on examples with homogeneous and nonhomogeneous boundary conditions and a comparison with the modified decomposition method is made. It is shown that the Sinc-Galerkin method yields better results.