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61.
Codée JD Litjens RE den Heeten R Overkleeft HS van Boom JH van der Marel GA 《Organic letters》2003,5(9):1519-1522
Diphenylsulfoxide in combination with triflic anhydride provides a very potent thiophilic glycosylation promotor system, capable of activating disarmed thioglycosides. The usefulness of this novel thiophilic activator is illustrated in a successful chemoselective glycosylation sequence in which the donor thioglycoside in the first condensation step may be either armed or disarmed. [reaction: see text] 相似文献
62.
Connolly J van Duijneveldt JS Klein S Pizzey C Richardson RM 《Langmuir : the ACS journal of surfaces and colloids》2006,22(15):6531-6538
Montmorillonite clay was treated with quaternary ammonium surfactants with 1-3 long chains of 10-18 carbons to form organoclays which can be suspended in non-aqueous solvents. The effects of surfactant chain length, number of long chains, and the properties of the solvent on the colloidal behavior of the surfactant coated clay plates were studied using small-angle X-ray scattering. The scattering data were modeled using a one-dimensional aggregation theory to describe the stacking of the clay plates. The plates self-organize into stacks with a reproducible basal spacing in the range of 30-50 A, and for each surfactant, the basal spacing falls into one of two preferred distances. We interpret this by considering that the surfactant layer on the clay has two strata, one being the polar near-clay headgroup region and the other the nonpolar alkane chain region. Polar solvents will swell the polar stratum preferentially while nonpolar solvents will swell the nonpolar stratum of the surfactant. As the nonpolar stratum is larger than the polar one, the nonpolar solvents increase the basal spacing between the clay plates more than the polar solvents. The number of long chains on the surfactant does not have an effect on the basal spacing, as the density of surfactant molecules on the surface is low enough to allow the unimpeded swelling of the chains. The one-dimensional aggregation theory can be used to determine the number of plates in a stack, but the effect of changing clay particle size or concentration is not as great as would be expected from this theory. This may be due to the formation of large-scale structures in the suspensions which prevent a true equilibrium stack size being attained. 相似文献
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We describe the development and validation of a high-resolution screening (HRS) platform which couples gradient reversed-phase
high-performance liquid chromatography (RP-HPLC) on-line to estrogen receptor α (ERα) affinity detection using fluorescence
polarization (FP). FP, which allows detection at high wavelengths, limits the occurrence of interference from the autofluorescence
of test compounds in the bioassay. A fluorescein-labeled estradiol derivative (E2-F) was synthesized and a binding assay was
optimized in platereader format. After subsequent optimization in flow-injection analysis (FIA) mode, the optimized parameters
were translated to the on-line HRS bioassay. Proof of principle was demonstrated by separating a mixture of five compounds
known to be estrogenic (17β-estradiol, 17α-ethinylestradiol and the phytoestrogens coumestrol, coumarol and zearalenone),
followed by post-column bioaffinity screening of the individual affinities for ERα. Using the HRS-based FP setup, we were
able to screen affinities of off-line-generated metabolites of zearalenone for ERα. It is concluded that the on-line FP-based
bioassay can be used to screen for the affinity of compounds without the disturbing occurrence of autofluorescence. 相似文献
66.
Structural Revision and Elucidation of the Biosynthesis of Hypodoratoxide by 13C,13C COSY NMR Spectroscopy 下载免费PDF全文
Lena Barra Dr. Kerstin Ibrom Prof. Dr. Jeroen S. Dickschat 《Angewandte Chemie (International ed. in English)》2015,54(22):6637-6640
Feeding of (2,3,4,5,6‐13C5)mevalonolactone to the fungus Hypomyces odoratus resulted in a completely labeled sesquiterpene ether. The connectivity of the carbon atoms was easily deduced from a 13C,13C COSY spectrum, revealing a structure that was different from the previously reported structure of hypodoratoxide, even though the reported 13C NMR data matched. A structural revision of hypodoratoxide is thus presented. Its absolute configuration was tentatively assigned from its co‐metabolite cis‐dihydroagarofuran. Its biosynthesis was investigated by feeding of (3‐13C)‐ and (4,6‐13C2)mevalonolactone, which gave insights into the complex rearrangement of the carbon skeleton during terpene cyclization by analysis of the 13C,13C couplings. 相似文献
67.
Crystalline porous materials are extremely important for developing catalytic systems with high scientific and industrial impact. Metal-organic frameworks (MOFs) show unique potential that still has to be fully exploited. This perspective summarizes the properties of MOFs with the aim to understand what are possible approaches to catalysis with these materials. We categorize three classes of MOF catalysts: (1) those with active site on the framework, (2) those with encapsulated active species, and (3) those with active sites attached through post-synthetic modification. We identify the tunable porosity, the ability to fine tune the structure of the active site and its environment, the presence of multiple active sites, and the opportunity to synthesize structures in which key-lock bonding of substrates occurs as the characteristics that distinguish MOFs from other materials. We experience a unique opportunity to imagine and design heterogeneous catalysts, which might catalyze reactions previously thought impossible. 相似文献
68.
Brasch M de la Escosura A Ma Y Uetrecht C Heck AJ Torres T Cornelissen JJ 《Journal of the American Chemical Society》2011,133(18):6878-6881
We report herein the encapsulation of a water-soluble phthalocyanine (Pc) into virus-like particles (VLPs) of two different sizes, depending on the conditions. At neutral pH, the cooperative encapsulation/templated assembly of the particles induces the formation of Pc stacks instead of Pc dimers, due to an increased confinement concentration. The Pc-containing VLPs may potentially be used as photosensitizer/vehicle systems for biomedical applications such as photodynamic therapy. 相似文献
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Jonker N Kool J Krabbe JG Retra K Lingeman H Irth H 《Journal of chromatography. A》2008,1205(1-2):71-77
A novel methodology is shown enabling the screening of mixtures of compounds for their affinity to a receptor protein. The system presented, dynamic protein-affinity chromatography solid-phase extraction (DPAC-SPE), overcomes the limitations of the existing methods by performing an incubation of the His-tagged protein with a mixture of possible ligands, which are still in their native conditions. This is followed by a fully automated affinity trapping step, coupled on-line to an LC-MS system in order to detect and identify the bound ligands. The system has been optimized using a commercially available on-line SPE system, using the estrogen receptor alpha (ERalpha) as model protein. A representative range of ligands with sub-nanomolar to millimolar affinities has been identified successfully from a mixture. The weakest binder that can be identified is norethindrone (approximately K(d)=0.1-1mM). The same setup also provides the possibilities to measure EC50 curves of both weak and strong binders. 相似文献