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991.
We recently reported a beta-peptide foldamer, beta53-1, that folds into a 14-helix in aqueous solution, binds the oncoprotein hDM2 with submicromolar affinity, and potently inhibits the interaction of hDM2 with a peptide derived from the activation domain of p53 (p53AD). Here, we present the solution structure of beta53-1 in methanol. Details of the structure illustrate fundamental and novel elements of beta-peptide folding and recognition. These elements include the detailed arrangement of a complex, 14-helix-stabilizing salt bridge on one helical face, and a unique "wedge into cleft" packing interaction along a second. The structure also reveals how a subtle distortion in the beta53-1 14-helix geometry alters the presentation of its recognition epitope, rendering it particularly well suited for alpha-helix mimicry. The solution structure of beta53-1 demonstrates that well folded beta-peptide oligomers can effectively present an extended, highly variable surface that could be used as a general platform for targeting critical protein-protein interfaces. 相似文献
992.
Lutetium(III) forms an association compound with a new synthetic reagent, 1,6-bi(1-phenyl-3-methyl-5-pyrazolone-4)hexandione (BPMPHD), and cetyltrimethylammonium bromide (CTMAB). The compound enhances the natural fluorescence of BPMPHD remarkably, upon which a new fluorescence method was developed for determining lutetium in rare earth (RE) samples. The determination range was 1.80 × 10–7–8.8 × 10–6 g/ml. The determination limit was 29 ng/ml. The composition of the ion associate was [Lu(BPMPHD)2]–CTMAB+. 相似文献
993.
A series of 2-benzyl-1,3-dicabonyl derivatives was synthesized.Their insulin-sensitizing activity was evaluated in 3T3-L1 preadipocyte cells.Compounds3,26 and 27 were found to possess strong insulin-sensitizing activity in vitro and were selected for further hypoglycemic evaluation in vivo. 相似文献
994.
Single p-toluic acid pendant groups were attached to 1,4,7,10,13-pentaazacyclopentadecane (15aneN5) and 1,4,8,11-tetraazacyclotetradecane (cyclam) to prepare bifunctional reagents for radiolabeling monoclonal antibodies with (64,67)Cu. The ligands are 1,4,7,10,13-pentaazacyclopentadecane-1-(alpha-1,4-toluic acid) (PCBA) and 1,4,8,11-tetraazacyclotetradecane-1-(alpha-1,4-toluic acid) (CPTA). For the parent macrocycles and their pendant arm derivatives, the 1:1 Cu(2+) complexes dissociate only below pH 2. At pH 0.0 and 25 degrees C the CPTA-Cu complex has a half-life toward complete dissociation of 24 days. A new approach was developed for the estimation of the Cu(2+) stability constant for the kinetically robust CPTA. All other formation constants were determined at 25.0 degrees C with batch spectrophotometric techniques. Potentiometric titrations were used to determine the protonation constants of the macrocyclic ligands as well as of the metal chelates. The protonation constants, stability constants, and pM's are discussed in terms of both molecular mechanics calculations and the ligands' potential applicability as copper(II) radiopharmaceuticals. 相似文献
995.
Michael J. Costanzo Harold R. AlmondJr. A. Diane Gauthier Bruce E. Maryanoff 《Tetrahedron: Asymmetry》1994,5(12)
The conformational preferences for 2,3-O-isopropylidene-α-
-sorbopyranose derivatives 3–6 were determined by using 1H NMR data and empirical force field calculations. Proton NMR studies of 3–6 indicate that a twist-boat (or skew) conformation (3S0) prevails over possible chair forms for each compound. Force-field calculations (MM2, MNDO, AM1) on a model 2,3-O-isopropylidene-α-
-sorbopyranose system (18) indicate that the 3S0 conformation is among the low-energy structures. X-Ray crystallographic analysis of α-
-sorbopyranose sulfamate 3, a compound with potent anticonvulsant activity, demonstrates that the 3S0 skew conformation is manifested in the solid state, as well. 相似文献
996.
尼龙1010/尼龙6共聚物的表观相图研究 总被引:2,自引:0,他引:2
采用显微熔点法和DSC测定了尼龙1010/尼龙6共聚物的表观相图;分析了投料比与链节结构单元含量的关系。最低熔点时尼龙1010/尼龙6的理论重量投料比为60/40,摩尔比为33.3/66.7,实验结果与此相近。 相似文献
997.
Direct trimethylsilylation1) of phenanthrene in different molar ratio of phenanthrene/sodium/trimethylchlorosilane is reported and discussed. Instead of the aromatic silyl compounds, such as 9-trimethylsilylphenanthrene (V), the hydroaromatic silyl compounds, such as 9, 10–bis (trimethylsilyl)-9, 10-dihydrophenanthrene (I) were obtained preferentially. Structure of these compounds are characterized and discussed. These silylated products have a general trend to change their properties during long time storage in the atmosphere under exposure to light. A significant difference of chemical shifts between silylated aromatic compound (V) and silylated hydroaromatic compound (I-IV) was observed. 相似文献
998.
L. Mandelkern J. Michael Price M. Gopalan J. G. Fatou 《Journal of Polymer Science.Polymer Physics》1966,4(3):385-400
Replicas of fracture surfaces of fractions of linear polyethylene, which were crystallized at elevated temperatures for extended time periods, were examined by electron microscopy. Striated. lamella-type crystallites were observed for all molecular weights over the range 3.2 × 103?5.7 × 105. In agreement with Anderson's previous report, for molecular weights of 12,000 or less, the crystallite thicknesses were comparable to the extended chain length. As the molecular weight increased above this level, however, the crystallite sizes increased only slightly and hence at high molecular weights were very much smaller than the extended chain length. From the measured melting temperatures, crystallite interfacial free energies were calculated from the theory for the melting of finite size crystals comprised of chains of finite length. The crystallite interfacial free energy was found to increase with molecular weight. Based on these results, a crystallization process is outlined which allows for the formation of either extended chain crystallites, or crystallites whose size is much smaller than the extended chain length without any change in nucleation mechanism or arbitrary adjustment in growth mechanism with molecular weight. 相似文献
999.
Yang L Mayr M Wurst K Buchmeiser MR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5761-5770
The synthesis of novel ruthenium-based metathesis catalysts containing the saturated 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene ligand, that is, [RuCl2(NHC)[=CH-2-(2-PrO)-5-NO(2)-C6H3]] (1) and [Ru(CF3COO)2(NHC)[=CH-2-(2-PrO)-5-NO2-C6H3]] (2) (NHC=1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) is described. Both catalysts are highly active in ring-closing metathesis (RCM) and ring-opening cross-metathesis (ROCM). Compound 1 shows moderate activity in enyne metathesis. Compound 2 is not applicable to enyne metathesis since it shows high activity in the cyclopolymerization of diethyl dipropargylmalonate (DEDPM). Poly(DEDPM) prepared by the action of 2 consists of 95% five-membered rings, that is, poly(cyclopent-1-enevinylene)s, and 5 % of six-membered rings, that is, poly(cyclohex-1-ene-3-methylidene)s. The polymerization proceeds in a nonliving manner and results in polyenes with broad polydispersities (1.9< or =PDI< or =2.3). Supported analogues of 2 were prepared by immobilization on hydroxymethyl-Merrifield resin and a monolithic support derived from ring-opening-metathesis polymerization (ROMP). Catalyst loadings of 1 and 2.5%, respectively, were obtained. Both supported versions of 2 showed excellent reactivity. With 0.24-2% of the supported catalysts, yields in RCM and ROCM were in the range of 76-100%. Leaching of ruthenium was low and resulted in Ru contaminations of the products of less than 0.000014% (0.14 ppm). 相似文献
1000.
Burford N Ragogna PJ McDonald R Ferguson MJ 《Chemical communications (Cambridge, England)》2003,(16):2066-2067
Polyphosphorus dications have been synthesised and comprehensively characterised as diphosphine (dppe, dmpe and dpph) linked Ar2P+ Lewis acids (Ar = C6H5); this application of unique homoatomic coordination chemistry provides important building blocks for extended systems. 相似文献