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1.
2.
Polymers such as poly(ethylene glycol) (PEG) have proven use in a variety of applications including organic synthesis. We now disclose our investigations into the recently disputed report that PEG tartrate esters can reverse the enantioselectivity of the Sharpless asymmetric epoxidation reaction. The results presented herein have clarified that the enantioselectivity of this reaction can be reproducibly reversed solely as a function of the molecular weight of the appended PEG. By preparing a range of tartrate ligands with varying PEG chains lengths, the reversal was found to occur within a molecular weight change of only 800. As the PEG chain did not affect the inherent chirality of the ligand, the enantioreversal was proposed to occur as a result of two Ti-ligand complexes which differ in their molecularity of ligand, one monomeric in ligand and the other dimeric. Support for this hypothesis was given through equilibrium measurements which revealed that the predominant species in Ti/PEG tartrate ester mixtures is a distinct 2:1 Ti-ligand complex, as opposed to the 2:2 Ti-ligand complex of traditional Sharpless asymmetric epoxidations. In total, these data represent an unrecognized property of PEG-supported catalysts that could open up new venues in the control of asymmetric reactions by means of achiral appended polymers. 相似文献
3.
Dickerson CA Fisher MJ Sykora RE Albrecht-Schmitt TE Cody JA 《Inorganic chemistry》2002,41(4):640-642
The compound K(3)PSe(4).2Se(6) was synthesized at 110 degrees C via solventothermal techniques from binary starting materials and Se in acetonitrile. The compound crystallizes in the space group Fd macro 3 of the cubic system with eight formula units in a cell with a dimension of a = 16.415(2) A at T = 193 K. The structure contains an unusual intermixing of ionic and uncharged species. The selenophosphate tetrahedral trianions PSe(4)(3-) are surrounded by potassium cations; other potassium cations in the structure are coordinated to 12 selenium atoms from four Se(6) rings in a tetrahedral arrangement. There are no short contacts between adjacent selenium rings. Heating the same reaction mixture to 160 degrees C results in the formation of only needles of trigonal selenium. 相似文献
4.
Dickerson MB Naik RR Stone MO Cai Y Sandhage KH 《Chemical communications (Cambridge, England)》2004,(15):1776-1777
Peptides that promote the rapid, room-temperature precipitation of amorphous germania nanoparticle networks from solution have been identified via use of a combinatorial peptide display library. 相似文献
5.
We have coupled CIEF with an LIF detector that is based on a post‐column sheath flow cuvette. We employed Chromeo P503 as a fluorogenic reagent to label proteins before analysis. This reagent reacts with the ε‐amine of lysine residues, preserving the cationic nature of the residue; labeled proteins generate extremely sharp peaks in CIEF. A set of four standard proteins generated a linear relationship between migration time and pI. A protein homogenate prepared from a Barrett's esophagus cell line resolved over 100 components in a 40 min separation. Detection limits for Chromeo P503‐labeled β‐lactoglobulin were 5 amol injected into the capillary. Fluorescent impurities present in the ampholytes generated a large background signal that degraded the detection limit by four orders of magnitude compared with other forms of capillary electrophoresis with this detector. 相似文献
6.
Oluwatosin O. Dada Lauren M. Ramsay Jane A. Dickerson Nathan Cermak Rong Jiang Cuiru Zhu Norman J. Dovichi 《Analytical and bioanalytical chemistry》2010,397(8):3305-3310
We report a multiplexed capillary electrophoresis system employing an array of 32 capillaries with a micromachined sheath-flow
cuvette as the detection chamber. The sample streams were simultaneously excited with a 473-nm laser beam, and the fluorescence
emission was imaged on a CCD camera with a pair of doublet achromat lens. The instrument produced mass detection limits of
380 ± 120 yoctomoles for fluorescein in zone electrophoresis. Capillary isoelectric focusing of fluorescent standards produced
peaks with an average width of 0.0029 ± 0.0008 pH. Capillary coating stability limits the reproducibility of the analysis. 相似文献
7.
8.
We discuss the notion of spin squeezing considering two mutually exclusive classes of spin-s states, namely, oriented and non-oriented states. Our analysis shows that the oriented states are not squeezed while non-oriented
states exhibit squeezing. We also present a new scheme for construction of spin-s states using 2s spinors oriented along different axes. Taking the case of s=1, we show that the ‘non-oriented’ nature and hence squeezing arise from the intrinsic quantum correlations that exist among
the spinors in the coupled state. 相似文献
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10.
Rogers CJ Mee JM Kaufmann GF Dickerson TJ Janda KD 《Journal of the American Chemical Society》2005,127(28):10016-10017
Cocaine is among the most reinforcing of all drugs of abuse, yet no effective pharmacotherapy is available. Herein, we report the development and characterization of phage-displayed cocaine esterases with pharmacologically relevant kinetic parameters (kcat/Km approximately 104 M-1 s-1). 相似文献