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191.
Peyre V Lair V André V le Maire G Kragh-Hansen U le Maire M Møller JV 《Langmuir : the ACS journal of surfaces and colloids》2005,21(19):8865-8875
To evaluate the role of hydrophobic and electrostatic or other polar interactions for protein-ligand binding, we studied the interaction of human serum albumin (HSA) and beta-lactoglobulin with various aliphatic (C10-C14) cationic and zwitterionic detergents. We find that cationic detergents, at levels that do not cause unfolding, interact with a single site on beta-lactoglobulin and with two primary and five to six secondary sites on HSA with an affinity that is approximately the same as that with which zwitterionic (dimethylamineoxide) detergents interact, suggesting the absence of significant electrostatic interactions in the high-affinity binding of these compounds. The binding affinity for all of the groups of compounds was dependent upon hydrocarbon chain length, suggesting the predominant role of hydrophobic forces, supported by polar interactions at the protein surface. A distinct correlation between the binding energy and the propensity for micelle formation within the group of cationic or noncharged (nonionic and zwitterionic) detergents indicated that the critical micellar concentration (CMC) for each of these detergent groups, rather than the absolute length of the hydrocarbon chain, can be used to compare their hydrophobicities during their interaction with protein. Intrinsic fluorescence data suggest that the two primary binding sites on serum albumin for the zwitterionic and cationic compounds are located in the C-terminal part of the albumin molecule, possibly in the Sudlow II binding region. Comparisons with previous binding data on anionic amphiphiles emphasize the important contribution of ion bond formation and other polar interactions in the binding of fatty acids and dodecyl sulfate (SDS) by HSA but not by beta-lactoglobulin. Electrostatic interactions by cationic detergents played a significant role in destabilizing the protein structure at high binding levels, with beta-lactoglobulin being more susceptible to unfolding than HSA. Zwitterionic detergents, in contrast to the cationic detergents, had no tendency to unfold the proteins at high concentrations. 相似文献
192.
Mo-catalyzed asymmetric ring-closing metathesis (ARCM) reactions are used to synthesize cyclic allylboronates of high optical purity (89% ee to >98% ee). A one-pot procedure involving formation of allylboronates, Mo-catalyzed ARCM and functionalization of the optically enriched cyclic allylboronates constitutes net asymmetric cross metathesis (ACM). Structural modification of ARCM products include reactions with aldehydes to afford optically enriched compounds that bear quaternary carbon centers with excellent diastereoselectivity. These studies emphasize the significance of the availability of chiral Mo-based complex as a class of chiral metathesis catalysts that frequently complement one another in terms of reactivity and selectivity. 相似文献
193.
Krzysztof Walczak Jesper Wengel Erik B. Pedersen 《Monatshefte für Chemie / Chemical Monthly》1992,123(4):349-354
Summary Mercuric catalyzed hydrolysis of acetylatedL-rhamnal1 gave the ,-unsaturated aldehyde2. 1,2,4-Triazole was coupled, in a Michael type addition reaction, to2 at C-3 in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to give, after acetylation at the anomeric center, an anomeric mixture of 1,5-di-O-acetyl-3-(1,2,4-triazol-1-yl)-2,3,6-trideoxy-L-arabino-hexofuranose (3). Reaction of3 with silylated 2,4-dihydroxypyrimidines4 in the presence of trimethylsilyl triflate as catalyst followed by deprotection with 33% methylamine in absolute ethanol afforded the corresponding nucleosides7 and8.
Synthese von 1-(3-(1,2,4-Triazol-1-yl)-2,3,6-trideoxy-L-arabino-hexofuranosyl)uracilen über eine ,-ungesättigte Aldohexose
Zusammenfassung Die quecksilberkatalysierte Hydrolyse von acetyliertemL-Rhamnal1 ergab die ,-ungesättigten Aldehyde2. 1,2,3-Triazol wurde in Gegenwart von 1,8-Diazabicyclo[5.4.0]-7-undecen mittels einer Addition vom Michael-Typ an C-3 von2 gekoppelt und ergab dann nach Acetylierung am anomeren Zentrum eine anomere Mischung von 1,5-Di-O-acetyl-3-(1,2,4-triazol-1-yl)-2,3,6-trideoxy-L-arabino-hexofuranose (3). Die Reaktion von3 mit silyliertem 2,4-Di-hydroxypyrimidinen4 in Gegenwart von Trimethylsilyltriflat in absolutem Ethanol ergab die entsprechenden Nucleoside7 und8.相似文献
194.
Construction of Insulin 18‐mer Nanoassemblies Driven by Coordination to Iron(II) and Zinc(II) Ions at Distinct Sites
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Dr. Henrik K. Munch Jesper Nygaard Dr. Niels Johan Christensen Dr. Christian Engelbrekt Mads Østergaard Dr. Trine Porsgaard Dr. Thomas Hoeg‐Jensen Prof. Dr. Jingdong Zhang Prof. Dr. Lise Arleth Prof. Dr. Peter W. Thulstrup Prof. Dr. Knud J. Jensen 《Angewandte Chemie (International ed. in English)》2016,55(7):2378-2381
Controlled self‐assembly (SA) of proteins offers the possibility to tune their properties or to create new materials. Herein, we present the synthesis of a modified human insulin (HI) with two distinct metal‐ion binding sites, one native, the other abiotic, enabling hierarchical SA through coordination with two different metal ions. Selective attachment of an abiotic 2,2′‐bipyridine (bipy) ligand to HI, yielding HI–bipy, enabled ZnII‐binding hexamers to SA into trimers of hexamers, [[HI–bipy]6]3, driven by octahedral coordination to a FeII ion. The structures were studied in solution by small‐angle X‐ray scattering and on surfaces with AFM. The abiotic metal ligand had a higher affinity for FeII than ZnII ions, enabling control of the hexamer formation with ZnII and the formation of trimers of hexamers with FeII ions. This precise control of protein SA to give oligomers of oligomers provides nanoscale structures with potential applications in nanomedicine. 相似文献
195.
Prof. Jesper Bendix Dr. Kensha Marie Clark 《Angewandte Chemie (International ed. in English)》2016,55(8):2748-2752
To survey the noninnocence of bis(arylimino) acenaphthene (BIAN) ligands (L) in complexes with early metals, the homoleptic vanadium complex, [V(L)3] ( 1 ), and its monocation, [V(L)3]PF6 ( 2 ), were synthesized. These complexes were found to have a very rich electronic behavior, whereby 1 displays strong electronic delocalization and 2 can be observed in unprecedented valence tautomeric forms. The oxidation states of the metal and ligand components in these complexes were assigned by using spectroscopic, crystallographic, and magnetic analyses. Complex 1 was identified as [VIV(Lred)(L.)2] (Lred=N,N′‐bis(3,5‐dimethylphenylamido)acenaphthylene; L.=N,N′‐bis(3,5‐dimethylphenylimino)acenaphthenesemiquinonate). Complex 2 was determined to be [VV(Lred)(L.)2]+ at T<150 K and [VIV(L.)3]+ at T>150 K. Cyclic voltammetry experiments reveal six quasi‐reversible processes, thus indicating the potential of this metal–ligand combination in catalysis or materials applications. 相似文献
196.
Kalek M Benediktson P Vester B Wengel J 《Chemical communications (Cambridge, England)》2008,(6):762-764
Chemically modified nucleotide monomers were incorporated into adjacent terminal positions of two separate oligonucleotides complementary to an RNA target; all possible combinations of the catalytic units were tested, resulting in an artificial nuclease that showed high activity and catalytic turnover. 相似文献
197.
Stergios Piligkos Jesper Bendix H?gni Weihe Constantinos J Milios Euan K Brechin 《Dalton transactions (Cambridge, England : 2003)》2008,(17):2277-2284
A ligand field analysis of two structurally related hexanuclear Mn(iii) coordination complexes reveals that the observed difference in their ground spin-state anisotropy originates from the difference in projection coefficients of the single-ion anisotropy to spin states of different total spin quantum-number, S, rather than the geometrical distortions of the metal ions. Furthermore we show that the single-ion second order anisotropy induces fourth and higher order anisotropy terms to the ground spin states of the studied systems, as a consequence of spin-state mixing effects due to the comparable magnitude of the single-ion second order anisotropy and the isotropic exchange parameters. 相似文献
198.
199.
Kumar TS Madsen AS Østergaard ME Wengel J Hrdlicka PJ 《The Journal of organic chemistry》2008,73(18):7060-7066
Oligonucleotides (ONs) modified with a 2'-N-(pyren-1-yl)acetyl-2'-amino-alpha-L-LNA thymine monomer Y flanked on the 3'-side by an abasic site Phi (i.e., YPhi-unit) exhibit unprecedented increases in thermal affinity (DeltaT(m) values) toward target strands containing abasic sites (DeltaT(m) per YPhi unit >+33.0 degrees C in 9-mer duplexes relative to unmodified ONs). Biophysical studies along with force field calculations suggest that the conformationally locked 2-oxo-5-azabicyclo[2.2.1]heptane skeleton of monomer Y, in concert with the short rigid acetyl linker, efficiently forces the thymine and pyrene moieties to adopt an interplanar distance of approximately 3.4 A. This precisely positions the pyrene moiety in the duplex core void formed by abasic sites (Phi:Phi pair) for optimal pi-pi overlap. Duplexes with multiple YPhi: APhi units separated by one base pair are tolerated extraordinarily well, as exemplified by a 13-mer duplex containing four separated YPhi: APhi units (8 abasic sites distributed over 13 "base pairs"), which exhibit a thermal denaturation temperature of 60.5 degrees C. The YPhi probes display up to 16-fold increases in fluorescence intensity at 380 nm upon hybridization with abasic target strands, whereby self-assembly of these complex architectures can be easily monitored. This study underlines the potential of N2'-functionalized 2'-amino-alpha-L-LNA as building blocks in nucleic acid based diagnostics and nanomaterial engineering. 相似文献
200.
Søndergaard K Kristensen JL Palner M Gillings N Knudsen GM Roth BL Begtrup M 《Organic & biomolecular chemistry》2005,3(22):4077-4081
From codeine, four different 2-aryl substituted apomorphines were synthesised in 6 steps each. Oxidation of codeine with IBX followed by acid catalysed rearrangement gave morphothebaine, which was selectively triflylated at the 2-position and subsequently O-acetylated at the 11-position. The resulting triflate was coupled in a Suzuki-Miyaura type reaction with a series of 4-substituted arylboronic esters which, after deprotection, gave the desired 2-aryl apomorphines. The analogues were tested for affinity towards a range of dopaminergic, serotonergic and adrenergic receptors. 2-(4-Hydroxyphenyl)-apomorphine exhibited high affinity for the dopamine D2 receptor. A putative ligand-receptor interaction was put forward. 相似文献