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151.
The formal synthesis of the marine natural product (-)-cyanolide A is presented. The synthetic strategy is centered on two acyclic diastereoselective reactions and a single cyclic reaction with modest to excellent dr based on an initial stereocenter. Most notable is a highly stereoselective oxocarbenium reduction based on a "mismatched" reactive conformer to afford the β-C-glycoside subunit leading to an efficient synthesis of the diolide aglycon in 12 overall steps. 相似文献
152.
Improving reagent performance in immunoassays both to enhance assay sensitivity and to minimize interference are ongoing challenges in clinical diagnostics. We describe herein the syntheses of a new class of hydrophilic reagents containing sulfobetaine zwitterions and their applications. These zwitterionic reagents are potentially useful for improving the properties of immunoassay reagents. We demonstrate for the first time that zwitterion labeling is a general and viable strategy for reducing the non-specific binding of proteins to microparticles and, to improve the aqueous solubility of hydrophobic peptides. We also describe the synthesis of zwitterionic cross-linking reagents and demonstrate their utility for peptide conjugation. In automated, chemiluminescent immunoassays, improved assay performance was observed for a hydrophobic, small analyte (theophylline) using an acridinium ester conjugate with a zwitterionic sulfobetaine linker compared to a hexa(ethylene)glycol linker. Sandwich assay performance for a large analyte (thyroid stimulating hormone) was similar for the two acridinium ester labels. These results indicate that zwitterions are complementary to poly(ethylene)glycol in improving the aqueous solubility and reducing the non-specific binding of chemiluminescent acridinium ester conjugates. 相似文献
153.
Sharpe RB Burdinski D van der Marel C Jansen JA Huskens J Zandvliet HJ Reinhoudt DN Poelsema B 《Langmuir : the ACS journal of surfaces and colloids》2006,22(13):5945-5951
Poly(dimethylsiloxane) (PDMS) is the most widely used stamp material in microcontact printing. It has excellent properties with respect to versatility, chemical inertness, and mechanical stability. However, it has an inclination to contaminate printed substrates with low molecular weight siloxane fragments. In this study, it is shown, by a combination of lateral force microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, that the extent of the PDMS-induced contamination is dependent on the nature of the ink used. The highest degree of contamination was found for relatively polar inks, whereas apolar alkanethiol inks were found to shield the substrate from contamination. This is interpreted in terms of the contaminating species being polar in nature. 相似文献
154.
Sharpe RB Burdinski D Huskens J Zandvliet HJ Reinhoudt DN Poelsema B 《Journal of the American Chemical Society》2006,128(49):15560-15561
In this report it is described how a gold surface can be treated with an oxygen plasma to become an effective etch mask, with its etch resistive properties based upon electrostatic repulsion. Such a treated gold layer is only temporarily stable and may therefore be employed as a temporary etch barrier that introduces no contaminating species. Deterioration of the barrier properties can be locally expedited in a scheme that is compatible with microcontact printing. This has been achieved by the microcontact printing of a reductant on a fully oxidized gold substrate. 相似文献