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S.W. Downey G.L. Keaton N.S. Nogar 《Spectrochimica Acta Part B: Atomic Spectroscopy》1985,40(7):927-932
Continuous wave intracavity absorption provides a sensitive method for probing the distribution of absorbing species in a plasma flame. There exists considerable potential for plasma mechanistic studies using this method both as a spatial diagnostic for selected species, and as a spectral diagnostic for the detection of low concentration or low oscillator strength species. 相似文献
24.
We discuss problems related to in silico studies of enzymes and show that accurate and converged free energy changes for complex chemical reactions can be computed if a method based on a thermodynamic cycle is employed. The method combines the sampling speed of molecular mechanics with the accuracy of a high-level quantum mechanics method. We use the method to compute the free energy barrier for a methyl transfer reaction catalyzed by the enzyme catechol O-methyltransferase at the level of density functional theory. The surrounding protein and solvent are found to have a profound effect on the reaction, and we show that energies can be extrapolated easily from one basis set and exchange-correlation functional to another. Using this procedure we calculate a barrier of 69 kJ/mol, in excellent agreement with the experimental value of 75 kJ/mol. 相似文献
25.
Marble AE Mastikhin IV MacGregor RP Akl M LaPlante G Colpitts BG Lee-Sullivan P Balcom BJ 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,168(1):164-174
The results of a magnetic resonance imaging (MRI) investigation concerning the effects of an aluminum honeycomb sandwich panel on the B1 and B0 fields and on subsequent image quality are presented. Although the sandwich panel structure, representative of an aircraft composite material, distorts B0 and attenuates B1, distortion-free imaging is possible using single point (constant time) imaging techniques. A new expression is derived for the error caused by gradient field distortion due to the heterogeneous magnetic susceptibility within a sample and this error is shown not to cause geometric distortion in the image. The origin of the B0 distortion in the sample under investigation was also examined. The graphite-epoxy 'skin' of the panel is the principal source of the B0 distortion. Successful imaging of these structures sets the stage for the development of methods for detecting moisture ingress and degradation within composite sandwich structures. 相似文献
26.
We show that on conformal manifolds of even dimension there is no conformally invariant natural differential operator between density bundles with leading part a power of the Laplacian for n/2$">. This shows that a large class of invariant operators on conformally flat manifolds do not generalise to arbitrarily curved manifolds and that the theorem of Graham, Jenne, Mason and Sparling, asserting the existence of curved version of for , is sharp.
27.
3D ultrasound guided breast biopsy system 总被引:2,自引:0,他引:2
Stereotactic X-ray mammography (SM) and ultrasound (US) guidance are commonly used techniques for breast biopsy. While SM provides 3D targeting information and US provides real-time guidance, both techniques have limitations. SM is a long and uncomfortable procedure and the US guided procedure is inherently 2D, requiring a skilled physician for both safety and accuracy. We have developed a 3D US-guided biopsy system to integrate with SM. The dual modality breast biopsy system combines the advantages of both approaches with 3D US and SM targeting, near real-time 3D and real-time 2D US guidance, breast stabilisation and a confined needle trajectory. Our goal is to be able to biopsy a larger percentage of suspicious masses using ultrasound, by clarifying ambiguous structures with mammographic imaging. Using breast phantoms, we have shown that our ultrasound guided biopsy system was capable of targeting artificial lesions that were 3.2 mm in diameter, with a 96% success rate. Through this study, we also demonstrated that our system was equivalent to current clinical practice, for an in vitro biopsy task. Metal beads in known relative positions allowed us to determine the geometry of the SM system, so that stereotactic mammography could be registered to 3D US images. The target registration error was found to be 1.6 mm. This error was dominated by positioning error in the vertical direction (perpendicular to the film surface). As an adjunct to SM, we propose that 3D US could provide more complete imaging information for target identification and real-time monitoring of needle insertion, as well as providing a means for rapid confirmation of biopsy success. 相似文献
28.
Mass spectrometry and non-covalent protein-ligand complexes: confirmation of binding sites and changes in tertiary structure 总被引:2,自引:0,他引:2
Shields SJ Oyeyemi O Lightstone FC Balhorn R 《Journal of the American Society for Mass Spectrometry》2003,14(5):460-470
An experimental approach is described for determining protein-small molecule non-covalent ligand binding sites and protein conformational changes induced by ligand binding. The methodology utilizes time resolved limited proteolysis and the high throughput analysis capability of MALDI TOF MS to determine the binding site in a tetanus toxin C-fragment (51 kDa)-doxorubicin (543 Da) non-covalent complex. Comparing relative ion abundances of peptides released from the time resolved limited proteolysis of tetanus toxin C-fragment (TetC) and the TetC-doxorubicin complex every 10 min from 10 to 120 min of digestion revealed that the binding of doxorubicin induced a significant change in surface topology of TetC. Four of the twenty-nine peptides observed by MALDI MS, including amino acids 351-360, 299-304, 305-311 and 312-316, had a lower abundance in the TetC-doxorubicin complex relative to TetC from 10 to 100 min of digestion. A decrease in ion abundance suggests doxorubicin obstructs the access of the protease to one or both termini of these peptides, identifying doxorubicin binding site(s). Conversely, five peptide ions, including amino acids 335-350, 364-375, 364-376, 281-298, and 316-328, all had a greater abundance in the digest of the complex, indicating an increase in accessibility to these sites. These five peptides flank regions of decreased ion abundance, suggesting that doxorubicin not only binds to the surface, but also induces a conformational change in TetC. 相似文献
29.
Evans DA Seidel D Rueping M Lam HW Shaw JT Downey CW 《Journal of the American Chemical Society》2003,125(42):12692-12693
A highly enantioselective, nitroaldol reaction catalyzed by a chiral Cu(II) bis(oxazoline) complex has been developed. The reaction scope includes both aromatic and aliphatic aldehydes (15 examples) affording products in good yields and enantioselectivities (87-94% ee). An X-ray structure of the catalyst has been provided along with a rationalization of the sense of asymmetric induction. 相似文献
30.
The synthesis of (-)-epibatidine has been accomplished utilizing a highly exo-selective asymmetric hetero Diels-Alder reaction. The key steps employed to transform the resulting bicycle into the natural product include a fluoride-promoted fragmentation and a Hofmann rearrangement. Reaction: see text. 相似文献