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951.
952.
Chiral BINOL-derived diols catalyze the enantioselective asymmetric allylboration of acyl imines. The reaction requires 15 mol % (S)-3,3'-Ph2-BINOL as the catalyst and allyldiisopropoxyborane as the nucleophile. The reaction products are obtained in good yields (75-94%) and high enantiomeric ratios (95:5-99.5:0.5) for aromatic and aliphatic imines. High diastereoselectivities (diastereomeric ratio > 98:2) and enantioselectivities (enantiomeric ratio > 98:2) are obtained in the reactions of acyl imines with crotyldiisopropoxyboranes. This asymmetric transformation is directly applied to the synthesis of Maraviroc, the selective CCR5 antagonist with potent activity against HIV-1 infection. Mechanistic investigations of the allylboration reaction including IR, NMR, and mass spectrometry studies indicate that acyclic boronates are activated by chiral diols via exchange of one of the boronate alkoxy groups with activation of the acyl imine via hydrogen bonding. 相似文献
953.
954.
Dempsey CE Mason PE Brady JW Neilson GW 《Journal of the American Chemical Society》2007,129(51):15895-15902
Guanidinium (Gdm+) chloride is a powerful protein denaturant, whereas the sulfate dianion (SO42-) is a strong stabilizer of folded protein states; Gdm2SO4 is effectively neutral in its effects on protein stability. While the "neutralizing" effects of protein-stabilizing solutes on the activity of denaturants can be broadly interpreted in terms of additive effects of the solutes, recent experimental and simulation studies support a role for hetero-ion interactions in the effect of sulfate on Gdm+ denaturation [Mason, P. E.; et al. J. Phys. Chem. B 2005, 109, 24185-24196]. Here we describe an experimental strategy for testing this mechanism that involves spectroscopic analysis of the separate effects of alkali metal sulfates (Na2SO4, Rb2SO4), GdmCl, and Gdm2SO4 on the folded populations of several peptides chosen to dissect specific noncovalent contributions to the conformational stability of proteins [alanine-based helical peptides stabilized by hydrogen bonds, tryptophan zipper (trpzip) peptides stabilized largely by cross-strand indole-indole interactions]. While the trpzip peptides are highly sensitive to GdmCl denaturation, they are unaffected by NaCl, Na2SO4, or Gdm2SO4, indicating that the reversal of the denaturant activity of Gdm+ by sulfate in this case is not due to competing stabilizing (sulfate) and destabilizing (Gdm+) interactions. Gdm2SO4 was found to retain considerable denaturant activity against alanine-based alpha-helical peptides. The differences in the effects of Gdm2SO4 on the two peptide types can be understood in terms of the different mechanisms of Gdm+ denaturation of trpzip peptides and helical peptides, respectively, and the specific nature of Gdm+ and SO42- ionic "clustering" that differentially affects the ability of Gdm+ to make the molecular interactions with the peptides that underlie its denaturant activity. 相似文献
955.
Cheung CM Goldberg FW Magnus P Russell CJ Turnbull R Lynch V 《Journal of the American Chemical Society》2007,129(40):12320-12327
During the course of studies on the synthesis of diazonamide A 1, an unusual O-aryl into C-aryl rearrangement was discovered that allows partial control of the absolute stereochemistry of the C-10 quaternary stereogenic center. Treatment of 30 with TBAF/THF gave the O-tyrosine ethers 31 and 32 (1:1), which on heating each separately in chloroform at reflux rearranged to 33 and 34 in ratios of 84:16 and 56:44, respectively. This corresponds to a 70% yield of the correct C-10 stereoisomer 33 and a 30% yield of the wrong C-10 stereoisomer 34. Attempts to convert 34 into 33 by ipso-protonation and equilibration were unsuccessful. Confirmation of the stereochemical outcome of the rearrangement was obtained by converting 33 into 37, an advanced intermediate in the first synthesis of diazonamide A by Nicolaou et al. It was also found that the success of the above rearrangement is sensitive to the protecting group on both the tryptophan nitrogen atom and the tyrosine nitrogen atom. 相似文献
956.
Abdelsalam ME Mahajan S Bartlett PN Baumberg JJ Russell AE 《Journal of the American Chemical Society》2007,129(23):7399-7406
Palladium and platinum are important catalytic metals, and it would be highly advantageous to be able to use surface enhanced Raman spectroscopy (SERS) to study reactive species and intermediates on their surfaces. In this paper we describe the use of templated electrodeposition through colloidal templates to produce thin (<1 microm) films of palladium and platinum containing close packed hexagonal arrays of uniform sphere segment voids. We show that, even though these films are not rough, when the appropriate film thickness and sphere diameter are employed these surfaces give stable, reproducible surface enhancements for Raman scattering from molecules adsorbed at the metal surface. We report SERS spectra for benzenethiol adsorbed on the structured palladium and platinum surfaces of different thicknesses and void diameters and show that, for 633 nm radiation, enhancements of 1800 and 550 can be obtained for palladium and platinum, respectively. 相似文献
957.
Hantash J Bartlett A Oldfield P Dénès G O'Rielly R David F 《Analytical and bioanalytical chemistry》2007,387(1):351-357
A flow-injection biosensor-like system based on a nonenzymatic approach has been developed to determine the carbamate pesticide
carbaryl in complex biological samples without lengthy and expensive extraction steps. Molecularly imprinted polymeric beads
were used to immobilize carbaryl from biological samples. pH variation permitted the elution of carbaryl from the binding
cavity to the flow cell. A pH electrode was used to detect changes in the charge of carbaryl in the sample solution resulting
from the protonation and deprotonation of the molecule over different pH ranges. At pH 2.0, the secondary amine group is protonated,
giving a (+1) charge to the carbaryl molecule. At pH 8.0, the ionized carbaryl loses a proton to become neutral, changing
the local pH of the flow cell. The pH change at the flow cell generated by the deprotonation of carbaryl ion in alkaline medium
was used to determine the carbaryl concentration. Parameters influencing the performance of the system were optimized for
use in the detection procedure. The validated biosensor-like system had a carbaryl detection limit of 10.0 μg/mL and a response
that was linear (r
2 > 0.98) over the concentration range of 10.0–00 μg/mL. 相似文献
958.
Suci PA Berglund DL Liepold L Brumfield S Pitts B Davison W Oltrogge L Hoyt KO Codd S Stewart PS Young M Douglas T 《Chemistry & biology》2007,14(4):387-398
Nanomedicine directed at diagnosis and treatment of infections can benefit from innovations that have substantially increased the variety of available multifunctional nanoplatforms. Here, we targeted a spherical, icosahedral viral nanoplatform to a pathogenic, biofilm-forming bacterium, Staphylococcus aureus. Density of binding mediated through specific protein-ligand interactions exceeded the density expected for a planar, hexagonally close-packed array. A multifunctionalized viral protein cage was used to load imaging agents (fluorophore and MRI contrast agent) onto cells. The fluorescence-imaging capability allowed for direct observation of penetration of the nanoplatform into an S. aureus biofilm. These results demonstrate that multifunctional nanoplatforms based on protein cage architectures have significant potential as tools for both diagnosis and targeted treatment of recalcitrant bacterial infections. 相似文献
959.
Neoglycolipid probes prepared via oxime ligation for microarray analysis of oligosaccharide-protein interactions 总被引:1,自引:0,他引:1
Liu Y Feizi T Campanero-Rhodes MA Childs RA Zhang Y Mulloy B Evans PG Osborn HM Otto D Crocker PR Chai W 《Chemistry & biology》2007,14(7):847-859
Neoglycolipid technology is the basis of a microarray platform for assigning oligosaccharide ligands for carbohydrate-binding proteins. The strategy for generating the neoglycolipid probes by reductive amination results in ring opening of the core monosaccharides. This often limits applicability to short-chain saccharides, although the majority of recognition motifs are satisfactorily presented with neoglycolipids of longer oligosaccharides. Here, we describe neoglycolipids prepared by oxime ligation. We provide evidence from NMR studies that a significant proportion of the oxime-linked core monosaccharide is in the ring-closed form, and this form selectively interacts with a carbohydrate-binding protein. By microarray analyses we demonstrate the effective presentation with oxime-linked neoglycolipids of (1) Lewis(x) trisaccharide to antibodies to Lewis(x), (2) sialyllactose analogs to the sialic acid-binding receptors, siglecs, and (3) N-glycans to a plant lectin that requires an intact N-acetylglucosamine core. 相似文献
960.
Glycosaminoglycans are sulfated in complex and changing patterns that affect neural development. These sugars mediate interactions between macromolecules, and their biological contributions are of high interest. In this issue of Chemistry & Biology, Shipp and Hsieh-Wilson describe microarrays to probe these complex modifications. 相似文献