Structural characterization of MAO and related aluminum complexes. 1. Solid-state (27)Al NMR with comparison to EFG tensors from ab initio molecular orbital calculations.

Experimental and ab initio molecular orbital techniques are developed for study of aluminum species with large quadrupole coupling constants to test structural models for methylaluminoxanes (MAO). The techniques are applied to nitrogen- and oxygen-containing complexes of aluminum and to solid MAO isolated from active commercial MAO preparations. (Aminato)- and (propanolato)aluminum clusters with 3-, 4-, and 6-coordinate aluminum sites are studied with three (27)Al NMR techniques optimized for large (27)Al quadrupole coupling constants: field-swept, frequency-stepped, and high-field MAS NMR. Four-membered (aminato)aluminum complexes with AlN(4) coordination yield slightly smaller C(q) values than similar AlN(2)C(2) sites: 12.2 vs 15.8 MHz. Planar 3-coordinate AlN(2)C sites have the largest C(q) values, 37 MHz. In all cases, molecular orbital calculations of the electric field gradient tensors yields C(q) and eta values that match with experiment, even for a large hexameric (aminato)aluminum cage. A D(3d) symmetry hexaaluminum oxane cluster, postulated as a model for MAO, yields a calculated C(q) of -23.7 MHz, eta = 0.7474, and predicts a spectrum that is too broad to match the field-swept NMR of methylaluminoxane, which shows at least three sites, all with C(q) values greater than 15 MHz but less than 21 MHz. Thus, the proposed hexaaluminum cluster, with its strained four-membered rings, is not a major component of MAO. However, calculations for dimers of the cage complex, either edge-bridged or face-bridged, show a much closer match to experiment. Also, MAO preparations differ, with a gel form of MAO having significantly larger (27)Al C(q) values than a nongel form, a conclusion reached on the basis of (27)Al NMR line widths in field-swept NMR spectra acquired from 13 to 24 T.     

Spatially-resolved analysis of nanoparticle nucleation and growth in a microfluidic reactor

Microfluidic systems provide a unique platform for investigation of fundamental reaction processes, which is critical to understanding how to control nanostructure synthesis on a production scale. We have examined the synthesis of cysteine-capped CdS quantum dot nanocrystals (CdS-Cys) between two interdiffusing reagent streams in a continuous-flow microfluidic reactor. Using spatially resolved photoluminescence imaging and spectroscopy of the microreactor, we have acquired kinetic and mechanistic data on the CdS-Cys nanoparticle nucleation and growth, and observed a binary shift in the particle emission spectrum from a higher (2.9 eV) to lower (2.5 eV) energy emission peak within the first second of residence time. Several reactor models have been tested against the spatially and spectrally resolved signals, which suggest that homogeneous reaction and particle nucleation are diffusion-limited and occur only at the boundary between the two laminar streams, while a slower activation process occurs on a longer (seconds) time scale. The results provide direct insight into the rapid processes that occur during crystallization in microfluidic mixing channels, and demonstrate the potential of using controlled microfluidic environments with spatially resolved monitoring to conduct fundamental studies of nanocrystal nucleation and growth.     

Polymer “threads” and drag reduction

A number of different polymer fluids were ejected on the centerline of a water pipe-flow facility. Two distinct flow regions were identified: Reynolds numbers above 25000, where centerline injection acted as a rather efficient mixing device for water-soluble polymer — and no drag-reduction resulted from non water-soluble materials; and Reynolds numbers from 10000 to 25000, where strong evidence exists that under certain conditions, a viscoelastic fluid thread can interact with turbulence eddies and reduce the overall flow friction in the pipe.On Sabbatical leave from San Diego State University.     

RHIC束流能量扫描实验中正反粒子椭圆流的平均场势效应（英文）

最近,STAR合作体在相对论重离子对撞机的束流能量扫描实验中观测到了正反粒子的椭圆流劈裂。基于输运模型,发现丰重子介质中正反粒子平均场势的不同可以解释其椭圆流的劈裂。利用Nambu-Jona-Lasinio模型描述相对论重离子碰撞的部分子相,发现实验中正反粒子的相对椭圆流劈裂可以用来约束该模型中夸克矢量相互作用的耦合系数。这一发现对确定QCD相图的临界点位置和理解整个QCD的相结构有重要意义。     

Determination of streptomycin in pharmaceutical preparations by gas chromatography

The antibiotic streptomycin can be reliably quantitated in injectable pharmaceuticals by GC. The manipulations are not difficult, and total analysis time for duplicate samples is less than twenty minutes. Reaction of the drug with aqueous sodium hydroxide solution generates maltol, which is extracted into chloroform prior to silylation. The silyl ether of maltol is then assayed, using naphthalene as internal standard. Duplicate analyses of twenty pharmaceutical samples showed a relative standard deviation of ±1.3%.     

相对论带电费密子Liouville方程

作为密度矩阵一种形式的Wigner函数是量子相空间里的分布。用它描述相对论费密子时,它的通常表达形式为4×4矩阵函数。本文得到相对论带电费密子的2×2矩阵形式的Wigner函数以及它所满足的Liouville方程。这一方程与量子电动力学里带电费密子满足的Dirac方程完全等价。在描述中能核碰撞的Walecka模型里,当只有矢量介子(或标量介于取平均场近似)时,核子满足一定形式的Dirac方程。本文的方程也与之等价。还证明了(2×2)Wigner函数与相对论费密子的波函数在描述量子体系上起着同样的作用。量子体系的可观察量的全部知识都可以通过这里的Wigner函数得到。 关键词：     

High-pressure magic angle spinning nuclear magnetic resonance

A high-pressure magic angle spinning (MAS) NMR capability, consisting of a reusable high-pressure MAS rotor, a high-pressure rotor loading/reaction chamber for in situ sealing and re-opening of the high-pressure MAS rotor, and a MAS probe with a localized RF coil for background signal suppression, is reported. The unusual technical challenges associated with development of a reusable high-pressure MAS rotor are addressed in part by modifying standard ceramics for the rotor sleeve by abrading the internal surface at both ends of the cylinder. In this way, not only is the advantage of ceramic cylinders for withstanding very high-pressure utilized, but also plastic bushings can be glued tightly in place so that other removable plastic sealing mechanisms/components and O-rings can be mounted to create the desired high-pressure seal. Using this strategy, sealed internal pressures exceeding 150 bars have been achieved and sustained under ambient external pressure with minimal loss of pressure for 72 h. As an application example, in situ¹³C MAS NMR studies of mineral carbonation reaction intermediates and final products of forsterite (Mg₂SiO₄) reacted with supercritical CO₂ and H₂O at 150 bar and 50 °C are reported, with relevance to geological sequestration of carbon dioxide.