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151.
Wu WJ Vidugiris G Mooberry ES Westler WM Markley JL 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2003,164(1):84-91
The size limit for protein NMR spectroscopy in solution arises in large part from line broadening caused by slow molecular tumbling. One way to alleviate this problem is to increase the effective tumbling rate by reducing the viscosity of the solvent. Because proteins generally require an aqueous environment to remain folded, one approach has been to encapsulate hydrated proteins in reverse micelles formed by a detergent and to dissolve the encapsulated protein in a low-viscosity fluid. The high volatility of suitable low-viscosity fluids requires that the samples be prepared and maintained under pressure. We describe a novel apparatus used for the preparation of such samples. The apparatus includes a chamber for mixing the detergent with the low-viscosity solvent, a second chamber for mixing this with hydrated protein, and a 5-mm (o.d.) zirconium oxide NMR sample tube with shut-off valves designed to contain pressures on the order of 10 bar, sufficient for liquid propane. Liquids are moved from one location to another by introducing minor pressure differentials between two pressurization vessels. We discuss the operation of this apparatus and illustrate this with data on a 30-kDa protein complex (chymotrypsin:turkey ovomucoid third domain) encapsulated in reverse micelles of the detergent, sodium bis (2-ethylhexyl) sulfosuccinate, aerosol-ot (AOT), dissolved in liquid propane. 相似文献
152.
153.
A review is given of the today available adequate information in the field of low-energy (? 30keV) ion reflection from metal surfaces. Considerable attention is paid to the so-called binary collision approach and its ranges of validity. In addition, the different existing models describing the scattering from a surface, and recent results of experimental verification of them are discussed. 相似文献
154.
155.
Radiation-induced long-chain branching for the purpose of improving melt strength and hence the processability of polypropylene (PP) and polyethylene (PE) is reviewed. Long-chain branching without significant gel content can be created by low dose irradiation of PP or PE under different atmospheres, with or without multifunctional branching promoters. The creation of long-chain branching generally leads to improvement of melt strength, which in turn may be translated into processability improvement for specific applications in which melt strength plays an important role. In this paper, the changes of the melt flow rate and the melt strength of the irradiated polymer and the relationship between long-chain branching and melt strength are reviewed. The effects of the atmosphere and the branching promoter on long-chain branching vs. degradation are discussed. The benefits of improved melt strength on the processability, e.g., sag resistance and strain hardening, are illustrated. The implications on practical polymer processing applications such as foams and films are also discussed. 相似文献
156.
Mathew R Gunawidjaja PN Izquierdo-Barba I Jansson K García A Arcos D Vallet-Regí M Edén M 《The journal of physical chemistry. C, Nanomaterials and interfaces》2011,115(42):20572-20582
By exploiting (1)H and (31)P magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy, we explore the proton and orthophosphate environments in biomimetic amorphous calcium phosphate (ACP) and hydroxy-apatite (HA), as grown in vitro at the surface of a 10CaO-85SiO(2)-5P(2)O(5) mesoporous bioactive glass (MBG) in either a simulated body fluid or buffered water. Transmission electron microscopy confirmed the presence of a calcium phosphate layer comprising nanocrystalline HA. Two-dimensional (1)H-(31)P heteronuclear correlation NMR established predominantly (1)H(2)O?(31)PO(4) (3-) and O(1)H?(31)PO(4) (3-) contacts in the amorphous and crystalline component, respectively, of the MBG surface-layer; these two pairs exhibit distinctly different (1)H→(31)P cross-polarization dynamics, revealing a twice as large squared effective (1)H-(31)P dipolar coupling constant in ACP compared with HA. These respective observations are mirrored in synthetic (well-crystalline) HA, and the amorphous calcium orthophosphate (CaP) clusters that are present in the pristine MBG pore walls: besides highlighting very similar local (1)H and (31)P environments in synthetic and biomimetic HA, our findings evidence closely related NMR characteristics, and thereby similar local structures, of the CaP clusters in the pristine MBG relative to biomimetic ACP. 相似文献
157.
Pierce ME Harris GD Islam Q Radesca LA Storace L Waltermire RE Wat E Jadhav PK Emmett GC 《The Journal of organic chemistry》1996,61(2):444-450
DMP 323, a potent HIV-1 protease inhibitor, has been synthesized by an efficient stereoselective process, amenable to large scale preparations. The core C(2) symmetric diol was synthesized by a stereoselective pinacol coupling of CBZ protected D-phenylalanine. Judicious selection of protecting groups allowed cyclic urea formation under mild conditions, enhanced the ease of bis-alkylation, and led to intermediates which were easily purified without chromatography. Additionally, a one-pot, high yield process was developed to prepare the alkylating agent, 4-[(triphenylmethoxy)methyl]benzyl chloride from 1,4-benzenedimethanol. 相似文献
158.
Attempts to prepare tris(ligand) metal complexes of technetium in intermediate oxidation states with potentially bidentate oxazoline- and thiazoline-containing ligands were unsuccessful; when pertechnetate was reduced in the presence of excess ligand, TcO(2).xH(2)O was produced. Instead, by reaction with preformed M.O cores, a series of oxotechnetium(V) and oxorhenium(V) complexes of the formula MOXL(2) (M = Re, X = Br; M = Tc, X = Cl) and HL = 2-(2'-hydroxyphenyl)-2-oxazoline (Hoz), 2-(2'-hydroxy-3'-methylphenyl)-2-oxazoline (Hmoz), 2-(2'-hydroxyphenyl)-2-thiazoline (Hthoz), and 2-(2'-hydroxyphenyl)-2-benzoxazoline (Hhbo) have been prepared. These compounds have been characterized by a variety of techniques including single-crystal X-ray diffraction. Crystals of Hthoz (C(9)H(9)NOS) are monoclinic, with space group P2(1)/n, a = 7.5342(6) ?, b = 12.2187(6) ?, c = 9.3942(8) ?, beta = 94.233(7) degrees, and Z = 4; those of TcOCl(thoz)(2) (C(18)H(16)ClN(2)O(3)S(2)Tc) are monoclinic, with space group P2(1)/n, a = 16.506(1) ?, b = 7.664(1) ?, c = 16.3216(6) ?, beta = 111.154(4) degrees, and Z = 4; those of ReOBr(oz)(2) (C(18)H(16)BrN(2)O(5)Re) are orthorhombic, with space group Pbca, a = 12.864(2) ?, b = 25.369(2) ?, c = 11.025(2) ?, and Z = 8. The structures were solved by direct (Hthoz) or Patterson (metal complexes) methods and were refined by full-matrix least-squares procedures to R = 0.033, 0.032, and 0.028 for 1600, 3152, and 2651 reflections with I >/= 3sigma(I), respectively. In the two complexes, the geometry around the metals is distorted octahedral with the halide ligands in each bound cis, and one phenolate oxygen from one ligand in each bound trans to the metal-oxo linkage. In ReOBr(oz)(2), the two oxazoline nitrogens are coordinated trans to one another; in TcOCl(thoz)(2), the two thiazoline nitrogens are found cis to one another. 相似文献
159.
160.
Dr. Shanmugam Thiyagarajan Dr. Homer C. Genuino Dr. Jan C. van der Waal Dr. Ed de Jong Prof. Dr. Bert M. Weckhuysen Dr. Jacco van Haveren Dr. Pieter C. A. Bruijnincx Dr. Daan S. van Es 《Angewandte Chemie (International ed. in English)》2016,55(4):1368-1371
Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels–Alder (DA) aromatization route, to effectively block retro‐DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal‐based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80 % selectivity in a solid‐phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H‐Y was found to perform the best and can be easily reused after calcination. 相似文献