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21.
[structure: see text] The first total synthesis of rollicosin, a member of a rare subgroup of Annonaceous acetogenins containing two terminal gamma-lactones, is reported. The approach features a highly regio- and stereoselective tandem ring-closing/cross-metathesis reaction for construction of the east-wing lactone and incorporation of the alkyl spacer. Establishment of the C4 stereocenter and addition of the west-wing lactone were achieved by Sharpless asymmetric dihydroxylation and enolate alkylation. 相似文献
22.
Larry G. French 《The Chemical Educator》2002,7(5):270-277
Students obtain, via steam distillation, pennyroyal essential oil that is analyzed by capillary gas chromatography—mass spectrometry. TLC experiments establish conditions for preparative scale purification of the major oil component via flash column chromatography. The terpene obtained, (R)-(+)-pulegone, is characterized spectroscopically, employing at a minimum mass spectral molecular ion and fragmentation patterns, IR, and 300-MHz 1H NMR. Optionally, 13C and 2-D correlation NMR spectra can be utilized to enable unambiguous assignment of all C and H resonances. The project has been successfully incorporated into our upper-level advanced organic chemistry laboratory. The experiment provides opportunities for instruction in and experience with a wide variety of chromatographic and spectroscopic methods. Further, it centers on a plant and natural product well suited for the discussion of contemporary health care issues surrounding nontraditional/alternative medicine and herbal remedies. 相似文献
23.
Jockusch RA Kroemer RT Talbot FO Snoek LC Carçabal P Simons JP Havenith M Bakker JM Compagnon I Meijer G von Helden G 《Journal of the American Chemical Society》2004,126(18):5709-5714
The beta(1-->4) glycosidic linkage found in lactose is a prevalent structural motif in many carbohydrates and glycoconjugates. Using UV and IR ion-dip spectroscopies to probe benzyl lactoside isolated in the gas phase, we find that the disaccharide unit adopts only a single, rigid structure. Its fully resolved infrared ion-dip spectrum is in excellent agreement with that of the global minimum structure computed ab initio. This has glycosidic torsion angles of phi(H) (H1-C1-O-C4') approximately 180 degrees and psi(H) (C1-O-C4'-H4') approximately 0 degrees which correspond to a rotation of approximately 150 degrees about the glycosidic bond compared to the accepted solution-phase conformation. We discuss the biological implications of this discovery and the generality of the strategies employed in making it. 相似文献
24.
J. Stephen Clark Rebecca P. Freeman Andrew W. Thomas Claire Wilson 《Tetrahedron letters》2004,45(47):8639-8642
A concise enantioselective synthesis of the cyclic ether core of the marine natural product (+)-laurenyne has been accomplished using ring-closing metathesis for medium-ring construction. 相似文献
25.
Bertosa B Kojić-Prodić B Wade RC Ramek M Piperaki S Tsantili-Kakoulidou A Tomić S 《Journal of chemical information and computer sciences》2003,43(5):1532-1541
The activity of a biological compound is dependent both on specific binding to a target receptor and its ADME (Absorption, Distribution, Metabolism, Excretion) properties. A challenge to predict biological activity is to consider both contributions simultaneously in deriving quantitative models. We present a novel approach to derive QSAR models combining similarity analysis of molecular interaction fields (MIFs) with prediction of logP and/or logD. This new classification method is applied to a set of about 100 compounds related to the auxin plant hormone. The classification based on similarity of their interaction fields is more successful for the indole than the phenoxy compounds. The classification of the phenoxy compounds is however improved by taking into account the influence of the logP and/or the logD values on biological activity. With the new combined method, the majority (8 out of 10) of the previously misclassified derivatives of phenoxy acetic acid are classified in accord with their bioassays. The recently determined crystal structure of the auxin-binding protein 1 (ABP1) enabled validation of our approach. The results of docking a few auxin related compounds with different biological activity to ABP1 correlate well with the classification based on similarity of MIFs only. Biological activity is, however, better predicted by a combined similarity of MIFs + logP/logD approach. 相似文献
26.
Spatial profiling invertebrate ganglia using MALDI MS 总被引:4,自引:0,他引:4
The ability of MALDI TOF MS to spatially map peptides and proteins directly from a tissue is an exciting advance to imaging mass spectrometry. Recent advances in instrumentation for MS have resulted in instruments capable of achieving several micron spatial resolution while acquiring high-resolution mass spectra. Currently, the ability to obtain high quality mass spectrometric images depends on sample preparation protocols that often result in limited spatial resolution. A number of sample preparation and matrix deposition protocols are evaluated for spatial profiling of Aplysia californica exocrine gland and neuronal tissues. Such samples are different from mammalian tissues, but make good targets for method optimization because of the wealth of biochemical information available on neuropeptide processing and distribution. Electrospray matrix deposition and a variety of freezing methods have been found to be optimum for these invertebrate tissues, with the exact protocols being tissue dependent. 相似文献
27.
Richardson RA Cotton JW Mark Ormerod R 《Dalton transactions (Cambridge, England : 2003)》2004,(19):3110-3115
La(0.6)Sr(0.4)Co(0.2)Fe(0.8)O(3-delta)(LSCF) perovskite powders have been synthesised by solid-state reaction, co-precipitation, drip pyrolysis and citrate gel routes, and characterised using XRF, XRD, SEM and BET. Co-precipitation using oxalic acid or aqueous ammonia as precipitant failed to achieve the correct chemical composition. Perovskite structures were achieved in all other cases. Surface areas ranging from 0.6 to 17.4 m(2) g(-1) were obtained, which was reflected in the different microstructures observed. The citrate gel product exhibited a convoluted network morphology resulting in its large surface area. Thin-walled (approximately 200 microm) tubular membranes have been manufactured from the LSCF powders using viscous plastic processing. The tubes have been characterised using a custom-built gas analysis rig with on-line mass spectrometry. Porosity levels of the membranes were found to be very low (<0.1%). The spontaneous oxygen flux across the tubular membranes was determined as a function of temperature. Oxygen permeation rates ranged from 0.1 to 0.3 micromol cm(-2) s(-1) at 1273 K. The catalytic behaviour of the LSCF tubes towards methane oxidation has been studied using temperature programmed reaction and conventional catalytic measurements. The tubes favoured combustion reactions, with smaller amounts of partial oxidation and oxidative coupling products observed. Powder coatings have been incorporated to establish the effect of increasing surface area. 相似文献
28.
29.
The high frequency acoustic response of liquids is measured in a manner directly analogous to conventional ultrasonic measurements. Two thin metal films act as acoustic transducer and receiver for a liquid layer between them. Pulsed optical excitation generates high bandwidth wave packets in the transducer, and these are detected in the receiver after damping and dispersion by the liquid. This initial measurement probes structural relaxation dynamics of glycerol in the frequency range 2-20 GHz, for temperatures between 235 and 291 K. The analysis presented here demonstrates the presence of excess relaxation, not accounted for by either the alpha or beta relaxation of the mode-coupling theory, and suggests the presence of constant loss in the susceptibility spectrum of supercooled glycerol. 相似文献
30.
Yang Shen Ioanna Kalograiaki Alessio Prunotto Matthew Dunne Samy Boulos Nicholas M. I. Taylor Eric T. Sumrall Marcel R. Eugster Rebecca Martin Alicia Julian-Rodero Benjamin Gerber Petr G. Leiman Margarita Menndez Matteo Dal Peraro Francisco Javier Caada Martin J. Loessner 《Chemical science》2021,12(2):576
Endolysins are bacteriophage-encoded peptidoglycan hydrolases targeting the cell wall of host bacteria via their cell wall-binding domains (CBDs). The molecular basis for selective recognition of surface carbohydrate ligands by CBDs remains elusive. Here, we describe, in atomic detail, the interaction between the Listeria phage endolysin domain CBD500 and its cell wall teichoic acid (WTA) ligands. We show that 3′O-acetylated GlcNAc residues integrated into the WTA polymer chain are the key epitope recognized by a CBD binding cavity located at the interface of tandem copies of beta-barrel, pseudo-symmetric SH3b-like repeats. This cavity consists of multiple aromatic residues making extensive interactions with two GlcNAc acetyl groups via hydrogen bonds and van der Waals contacts, while permitting the docking of the diastereomorphic ligands. Our multidisciplinary approach tackled an extremely challenging protein–glycopolymer complex and delineated a previously unknown recognition mechanism by which a phage endolysin specifically recognizes and targets WTA, suggesting an adaptable model for regulation of endolysin specificity.Combining genetic, biochemical and computational approaches, we elucidated the molecular mechanisms underlying the recognition of Listeria wall teichoic acid by bacteriophage-encoded SH3b repeats. 相似文献