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81.
NMR methods are widely used to probe the structure and fluid dynamics of porous materials, as they are uniquely suited to these studies since NMR records the correlation of changing local magnetic fields over a time scale of ns to seconds. The local magnetic fields are established by local variations in the bulk magnetic susceptibility of the sample (and so are directly tied to the sample's local structure). The fluctuation in field that a spin sees is due to molecular transport (including molecular diffusion) through these local fields, and so reports on the length scales of structures and impediments to transport. We have developed a new set of methods DIFFUSIVE-MASS to provide a means of systematically varying the effective time scale of the measurement and thus the effective length scale. This new handle permits a detailed, microscopic picture of the structure and dynamics. Diffusive MASS NMR methods will permit a systematic set of methods and analysis for characterizing the chemistry, structure and fluid dynamics of the mobile phase in porous materials. The approach will be applicable to any diamagnetic material. In particular, the industry of oil discovery depends on understanding heterogeneous porous media.  相似文献   
82.
Pulsed gradient spin echo (PGSE) experiments can be used to measure the probability distribution of molecular displacements. In homogeneous samples this reports on the molecular diffusion coefficient, and in heterogeneous samples, such as porous media and biological tissue, such measurements provide information about the sample's morphology. In heterogeneous samples however background gradients are also present and prevent an accurate measurement of molecular displacements. The interference of time independent background gradients with the applied magnetic field gradients can be removed through the use of bipolar gradient pulses. However, when the background gradients are spatially non-uniform molecular diffusion introduces a temporal modulation of the background gradients. This defeats simple bipolar gradient suppression of background gradients in diffusion related measurements. Here we introduce a new method that requires the background gradients to be constant over coding intervals only. Since the coding intervals are typically at least an order of magnitude shorter than the storage time, this new method succeeds in suppressing cross-terms for a much wider range of heterogeneous samples.  相似文献   
83.
Li P  Evans CD  Joullié MM 《Organic letters》2005,7(23):5325-5327
[reaction: see text] The ustiloxins are a family of heterodetic cyclopeptides that have been isolated from the water extracts of false smut balls on the panicles of rice plants caused by the fungus Ustilaginoidea virens. A concise total synthesis of ustiloxin D has been achieved via an unprecedented ethynyl aziridine ring-opening of phenol derivatives. The longest linear sequence of the synthesis is 15 steps from commercially available compounds.  相似文献   
84.
[chemical reaction: see text]. A simple, one-pot method for the alpha-acyloxylation of carbonyl compounds that proceeds at room temperature in the presence of both moisture and air has been developed. Treatment of a variety of aldehydes and both cyclic and acyclic ketones with N-methyl-O-benzoylhydroxylamine hydrochloride provides the alpha-functionalized product in 69-92% isolated yield. The transformation is tolerant of a wide range of functional groups and, significantly, is regiospecific in the discrimination of secondary over primary centers in the case of nonsymmetrical substrates.  相似文献   
85.
A novel dimer, tetraethyl 2,2′,3,3′‐tetramethyl‐1,1′,2,2′‐tetrahydro‐4H,4′H‐2,2′‐bipyrrolyl‐5,5,5′,5′‐tetracarboxylate, has been isolated as an impurity (0.4% yield) from a Knorr reaction for the synthesis of ethyl 3,5‐dimethylpyrrole‐2‐carboxylate from 2,4‐pentanedione and diethyl oximinomalonate in a dissolving zinc reduction. The solid‐state structure of this novel dimer was determined by X‐ray crystallography. Knorr reactions typically rely upon the requisite pyrrole being the only water‐insoluble crystalline material present in the reaction mixture, and so work‐up and purification procedures for Knorr reactions should be monitored carefully given the water‐insolubility of this dimer. Investigations regarding mechanistic implications and reductive dimerization are underway.  相似文献   
86.
The 13C spectra of tricyclo[3.2.1.02,7]octane, its 1,5-dimethyl derivative and ten tricyclo[3.2.1.02,7]octan-6-ones have been recorded as model compounds to aid the interpretation of the spectra of the naturally occurring polycyclic terpenes, ishwarane, ishwarone, ishwarol and methyl trachylobanate. The assignments for specific carbons in this series are based on the internal consistency of the observed shielding trends together with the effects of shift reagent on the shieldings of some of these derivatives.  相似文献   
87.
This Letter reports on the experimental implementation of the quantum baker's map via a three bit nuclear magnetic resonance quantum information processor. The experiments tested the sensitivity of the quantum chaotic map to perturbations. In the first experiment, the map was iterated forward and then backward to provide benchmarks for intrinsic errors and decoherence. In the second set of experiments, the least significant qubit was perturbed in between the iterations to test the sensitivity of the quantum chaotic map to controlled perturbations. These experiments can be used to investigate existing theoretical predictions for quantum chaotic dynamics.  相似文献   
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The synthesis of new molecular complexes of U2+ has been pursued to make comparisons in structure, physical properties, and reactivity with the first U2+ complex, [K(2.2.2‐cryptand)][Cp′3U], 1 (Cp′=C5H4SiMe3). Reduction of Cp′′3U [Cp′′=C5H3(SiMe3)2] with KC8 in the presence of 2.2.2‐cryptand or 18‐crown‐6 generates [K(2.2.2‐cryptand)][Cp′′3U], 2‐K(crypt) , or [K(18‐crown‐6)(THF)2][Cp′′3U], 2‐K(18c6) , respectively. The UV/Vis spectra of 2‐K and 1 are similar, and they are much more intense than those of U3+ analogues. Variable temperature magnetic susceptibility data for 1 and 2‐K(crypt) reveal lower room temperature χMT values relative to the experimental values for the 5f3 U3+ precursors. Stability studies monitored by UV/Vis spectroscopy show that 2‐K(crypt) and 2‐K(18c6) have t1/2 values of 20 and 15 h at room temperature, respectively, vs. 1.5 h for 1 . Complex 2‐K(18c6) reacts with H2 or PhSiH3 to form the uranium hydride, [K(18‐crown‐6)(THF)2][Cp′′3UH], 3 . Complexes 1 and 2‐K(18c6) both reduce cyclooctatetraene to form uranocene, (C8H8)2U, as well as the U3+ byproducts [K(2.2.2‐cryptand)][Cp′4U], 4 , and Cp′′3U, respectively.  相似文献   
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