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951.
Chen Q Schweitzer D Kane J Davisson VJ Helquist P 《The Journal of organic chemistry》2011,76(13):5157-5169
Iejimalide B, a structurally unique 24-membered polyene macrolide having a previously underutilized mode of anticancer activity, was synthesized according to a strategy employing Julia-Kocienski olefinations, a palladium-catalyzed Heck reaction, a palladium-catalyzed Marshall propargylation, a Keck-type esterification, and a palladium-catalyzed macrolide-forming, intramolecular Stille coupling of a highly complex cyclization substrate. The overall synthesis is efficient (19.5% overall yield for 15 linear steps) and allows for more practical scaled-up synthesis than previously reported strategies that differed in the order of assembly of key subunits and in the method of macrocyclization. The present synthesis paves the way for efficient preparation of analogues for drug development efforts. 相似文献
952.
Xuan J Hamblin MN Stout JM Tolley HD Maynes RD Woolley AT Hawkins AR Lee ML 《Journal of chromatography. A》2011,1218(50):9102-9110
An array of parallel planar nanochannels containing two or three segments with varying inner heights was fabricated and used for size fractionation of inorganic and biological nanoparticles. A liquid suspension of the particles was simply drawn through the nanochannels via capillary action. Using fluorescently labeled 30 nm polyacrylonitrile beads, different trapping behaviors were compared using nanochannels with 200-45 nm and 208-54-30 nm height segments. Addition of sodium dodecyl sulfate (SDS) surfactant to the liquid suspension and application of an AC electric field were shown to aid in the prevention of channel clogging. After initial particle trapping at the segment interfaces, significant particle redistribution occurred when applying a sinusoidal 8V peak-to-peak oscillating voltage with a frequency of 150 Hz and DC offset of 4V. Using the 208-54-30 nm channels, 30 nm hepatitis B virus (HBV) capsids were divided into three fractions. When the AC electric field was applied to this trapped sample, all of the virus particles passed through the interfaces and accumulated at the channel ends. 相似文献
953.
John CJ Amalanathan M Sajan D Lakshmi KU Joe IH 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(1):264-272
FT-Raman and FT-IR spectra of the nonlinear optical crystal 1-(4-N,N-dimethylaminopyridinium) acetic acid bromide monohydrate have been recorded and analyzed. The equilibrium geometry, vibrational wavenumbers and the first order hyperpolarizability of the crystal have been calculated with the help of density functional theory computations. The assignments of the vibrational spectra have been carried out with the help of Scaled Quantum Mechanic force field theory. Optimized geometry gives the charge transfer interaction of the pyridine ring and the amino group in the electron-donor side of the nonlinear optic chromophore. Electron–phonon coupling and O–H?O interactions in making the molecule nonlinear optical active have been analyzed based on the vibrational spectral features. The Natural Bond Orbital analysis confirms the occurrence of strong intermolecular O–H?O hydrogen bonding. 相似文献
954.
Tandon SS Dul MC Lee JL Dawe LN Anwar MU Thompson LK 《Dalton transactions (Cambridge, England : 2003)》2011,40(14):3466-3475
Ligands based on carbo- and thio-carbohydrazone cores, modified with pyridine, carboxylate and oxime ends, have been examined. They display a tautomeric versatility based on the flexible nature of the hydrazone linkages, leading to varied coordination motifs. Examples of mononuclear (Co(II), Ni(II)), dinuclear (Co(III)), 1D chain (Cu(II)) and square [2 × 2] grid (Ni(II)) complexes are obtained. Ferromagnetic (Cu(II)) and antiferromagnetic (Ni(II)) exchange is observed, with spin coupling in the Ni(II)(4) square grids propagated through the μ-O and μ-S bridges. Weak antiferromagnetic exchange (J = -6.0 cm(-1)) is observed for the μ-O bridged grid, despite the large Ni-O-Ni angles (137-141°), while for the μ-S bridged grids much stronger exchange is observed (J = -148 cm(-1), -198 cm(-1)). This is much larger than expected based on the Ni-S-Ni bridge angles (151-169°), and is associated with the soft (less polarizing than oxygen) nature of the sulfur bridge, which would allow for much more efficient transmission of spin exchange than observed in the μ-O bridged case. Structures and variable temperature magnetic data are included, and spin exchange is analyzed using normal Heisenberg exchange models. No examples involving oxime (NO) bridging are reported, which reflects the positioning of the N,O and N,S donor combinations in each ligand, and the preferred coordination through these donor atoms. 相似文献
955.
When used as solvent, chloroform was found to act as a hydrogen atom donor in Barton reductive decarboxylation reactions. Chloroform offers a substantial practical advantage over pre-existing hydrogen atom donors. 相似文献
956.
957.
Jean d’Angelo Georges Morgant Nour Eddine Ghermani Didier Desmaële Bernard Fraisse François Bonhomme Emma Dichi Mehrez Sghaier Yanling Li Yves Journaux John R.J. Sorenson 《Polyhedron》2008
Purposes of these studies were to synthesize Zn(II) and Co(II) complexes of 3-nitro-4-hydroxybenzoic acid, determine their structures through X-ray crystallography, and obtain their anticonvulsant activities. Thermogravimetric, differential scanning calorimetry, impedance of aqueous solutions and magnetic properties analyses were also determined. Anticonvulsant and related activities of these complexes as well as Zn(II), Co(II), Ni(II) and Mg(II) (5-nitrosalicylato) complexes were determined by the National Institutes of Health, Antiepileptic Development Program. Results of these analyses are presented to document unique bonding features and physical properties of these compounds and their anticonvulsant activities. It is concluded that these compounds have chemical and physical properties that can be used to account for their anticonvulsant activities. 相似文献
958.
959.
Croley TR White KD Callahan JH Musser SM 《Journal of the American Society for Mass Spectrometry》2012,23(9):1569-1578
Resolution improvements in time-of-flight instrumentation and the emergence of the Orbitrap mass spectrometer have researchers using high resolution mass spectrometry to determine elemental compositions and performing screening methods based on the full-scan data from these instruments. This work is focused on examining instrument performance of both a QTOF and a bench-top Orbitrap. In this study, the impact of chromatographic resolution on mass measurement accuracy, mass measurement precision, and ion suppression is examined at a fundamental level. This work was extended to a mixture of over 200 pesticides to determine how well two different software algorithms componentized and correctly identified these compounds under different sets of chromatographic conditions, where co-elution was expected to vary markedly. 相似文献
960.
Gandon LA Russell AG Güveli T Brodwolf AE Kariuki BM Spencer N Snaith JS 《The Journal of organic chemistry》2006,71(14):5198-5207
A novel approach to 2,4-disubstituted piperidines is reported, involving the radical cyclization of 7-substituted-6-aza-8-bromooct-2-enoates. Cyclization with tributyltin hydride affords the trans piperidines with trans/cis diastereomeric ratios ranging typically from 3:1 to 6:1. Cyclization with tris(trimethylsilyl)silane affords the same products with diastereomeric ratios of up to 99:1 in certain cases. The enhancement in diastereoselectivity results from the selective rearrangement of the minor stereoisomer through a cascade process involving radical cyclization to the piperidine radical, 1,5-radical translocation, and attack of the translocated radical onto the sulfonamide with extrusion of SO2 in a Smiles-type rearrangement. Slower trapping of the piperidine radical by tris(trimethylsilyl)silane compared to tributyltin hydride accounts for the occurrence of the rearrangement cascade in the former case. 相似文献