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1.
Blackwell HE Sadowsky JD Howard RJ Sampson JN Chao JA Steinmetz WE O'Leary DJ Grubbs RH 《The Journal of organic chemistry》2001,66(16):5291-5302
Heptapeptides containing residues with terminal olefin-derivatized side chains (3 and 4) have been treated with ruthenium alkylidene 1 and undergone facile ring-closing olefin metathesis (RCM) to give 21- and 23-membered macrocyclic peptides (5 and 6). The primary structures of peptides 3 and 4 were based upon a previously studied heptapeptide (2), which was shown to adopt a predominantly 3(10)-helical conformation in CDCl(3) solution and an alpha-helical conformation in the solid state. Circular dichroism, IR, and solution-phase (1)H NMR studies strongly suggested that acyclic precursors 3 and 4 and the fully saturated macrocyclic products 7 and 8 also adopted helical conformations in apolar organic solvents. Single-crystal X-ray diffraction of cyclic peptide 8 showed it to exist as a right-handed 3(10)-helix up to the fifth residue. Solution-phase NMR structures of both acyclic peptide 4 and cyclic peptide 8 in CD(2)Cl(2) indicated that the acyclic diene assumes a loosely 3(10)-helical conformation, which is considerably rigidified upon macrocyclization. The relative ease of introducing carbon-carbon bonds into peptide secondary structures by RCM and the predicted metabolic stability of these bonds renders olefin metathesis an exceptional methodology for the synthesis of rigidified peptide architectures. 相似文献
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In this work we devise efficient algorithms for finding the search directions for interior point methods applied to linear programming problems. There are two innovations. The first is the use of updating of preconditioners computed for previous barrier parameters. The second is an adaptive automated procedure for determining whether to use a direct or iterative solver, whether to reinitialize or update the preconditioner, and how many updates to apply. These decisions are based on predictions of the cost of using the different solvers to determine the next search direction, given costs in determining earlier directions. We summarize earlier results using a modified version of the OB1-R code of Lustig, Marsten, and Shanno, and we present results from a predictor–corrector code PCx modified to use adaptive iteration. If a direct method is appropriate for the problem, then our procedure chooses it, but when an iterative procedure is helpful, substantial gains in efficiency can be obtained. 相似文献
5.
Mulholland AJ O'Leary RL Ramadas N Parr A Troge A Pethrick RA Hayward G 《Ultrasonics》2007,47(1-4):102-110
This paper investigates the use of magnetically active materials in the matching layer of a piezoelectric transducer. This then allows the performance of the device to be dynamically altered by applying an external field. The effect that this new matching layer has on the performance of a typical device is theoretically investigated here. It transpires that the additional flexibility of an active matching layer can be used to maintain the efficiency of the device as the external load is varied. 相似文献
6.
The solutions of elliptic regularizations of the heat equation converge to the solutions of the corresponding evolution equation in weak energy norms. The technique is of relevance in control theory as well as variational inequalities. We show that the convergence actually takes place in some Hölder space. The result holds for a class of parabolic equations in divergence form and sufficiently integrable forcing terms.
Sommario Le soluzioni delle regolarizzanti ellittiche dell'equazione del calore, convergono alle soluzioni della corrispondente equazione di evoluzione in norme deboli dell'energia. Questa tecnica trova applicazione nelle teoric dei controlli e disuguaglianze variazionali. Si dimostra che la convergenza é forte ed ha luogo in norme Hölderiane. Il risultato si estende ad una classe di equazioni paraboliche in forma di divergenza con termini forzanti sufficientemente integrabili.相似文献
7.
Triacylglycerol profiling of microalgae strains for biofuel feedstock by liquid chromatography-high-resolution mass spectrometry 总被引:2,自引:0,他引:2
MacDougall KM McNichol J McGinn PJ O'Leary SJ Melanson JE 《Analytical and bioanalytical chemistry》2011,401(8):2609-2616
Biofuels from photosynthetic microalgae are quickly gaining interest as a viable carbon-neutral energy source. Typically,
characterization of algal feedstock involves breaking down triacylglycerols (TAG) and other intact lipids, followed by derivatization
of the fatty acids to fatty acid methyl esters prior to analysis by gas chromatography (GC). However, knowledge of the intact
lipid profile could offer significant advantages for discovery stage biofuel research such as the selection of an algal strain
or the optimization of growth and extraction conditions. Herein, lipid extracts from microalgae were directly analyzed by
ultra-high pressure liquid chromatography–mass spectrometry (UHPLC-MS) using a benchtop Orbitrap mass spectrometer. Phospholipids,
glycolipids, and TAGs were analyzed in the same chromatographic run, using a combination of accurate mass and diagnostic fragment
ions for identification. Using this approach, greater than 100 unique TAGs were identified over the six algal strains studied
and TAG profiles were obtained to assess their potential for biofuel applications. Under the growth conditions employed, Botryococcus braunii and Scenedesmus obliquus yielded the most comprehensive TAG profile with a high abundance of TAGs containing oleic acid. 相似文献
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The layered double hydroxide Mg2Al(OH)6(C12H25SO4) was delaminated to give high levels of inclusion in acrylate monomers; subsequent polymerisation of the monomers containing the LDH dispersion gave polyacrylates with the inorganic component still in the delaminated form. 相似文献
10.
Mizoguchi has very recently cast London's theory of magnetic susceptibilities of conjugated molecules in terms of the Coulson contour-integral formulation of Hückel molecular-orbital theory. Since interest in this approach has been thus revived, we present here a previously unpublished document, dated May 16th, 1953, by the late Professor C.A. Coulson, FRS, in which he formulates the London theory in terms of his own contour-integral method. Coulson's treatment is based on bond-bond polarisabilities and it therefore provides an interesting parallel to certain aspects of the now-classic McWeeny polarisability method, advanced five years later. The Coulson polarisability formalism does not, however, provide for explicit computation of individual ring-current intensities, nor — since it preceded the experimental observations — for the direct calculation of ring-current secondary fields (and, hence,1H-NMR chemical shifts). 相似文献