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1.
Sina Escher Wolfgang Giersch Yvan Niclass Grald Bernardinelli Günther Ohloff 《Helvetica chimica acta》1990,73(7):1935-1947
The four possible A/B cis-fused diastereoisomers of Ambrox® have been synthesized and their configurations and conformations established by X-ray and NMR analysis. Only 5β-ambrox (= 1,2,3a,4,5,5β,6,7,8,9,9a,9bα-dodecahydro-3aβ,6,6,9aβ-tetramethylnaphtho[2,1-b]furan; 5 ) has an odor quality comparable to Ambrox®. The 1,3-synperiplanar/diaxial conformation of the substituents at C(8) ( = C(3a)) and C(10) (= C(9a)) has thus been confirmed to be a compulsory structure element for the particular odor. 相似文献
2.
Becattini B Sareth S Zhai D Crowell KJ Leone M Reed JC Pellecchia M 《Chemistry & biology》2004,11(8):1107-1117
Bid is a key member of the Bcl-2 family proteins involved in the control of the apoptotic cascade in cells, leading to cell death. Uncontrolled cell death is associated with several human pathologies, such as neurodegenerative diseases and ischemic injuries. Therefore, Bid represents a potential yet unexplored and challenging target for strategies aimed at the development of therapeutic agents. Here we show that a multidisciplinary NMR-based approach that we named SAR by ILOEs (structure activity relationships by interligand nuclear Overhauser effect) allowed us to rationally design a series of 4-phenylsulfanyl-phenylamine derivatives that are capable of occupying a deep hydrophobic crevice on the surface of Bid. These compounds represent the first antiapoptotic small molecules targeting a Bcl-2 protein as shown by their ability to inhibit tBid-induced SMAC release, caspase-3 activation, and cell death. 相似文献
3.
Possibility of imide structure formation under microwave irradiation of molecules containing anhydride and isocyanate functional groups was investigated. The microwave-assisted polycondensation of aromatic diisocyanates and dianhydrides for preparation of polyimides was studied. The effect of microwave irradiation time and power, solvent nature, solid content of monomers, effect of catalyst, effect of polymerization reactor material and possibility of pressure development during polymerization, on the inherent viscosity of prepared polyimides were discussed. Experimental results showed that polymers obtained via this method had superior inherent viscosity and yield in comparison to the polymers obtained via conventional solution method. 相似文献
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6.
Powell KD Ghaemmaghami S Wang MZ Ma L Oas TG Fitzgerald MC 《Journal of the American Chemical Society》2002,124(35):10256-10257
A new method that utilizes matrix-assisted laser desorption/ionization (MALDI) mass spectrometry and exploits the hydrogen/deuterium (H/D) exchange properties of proteins was developed for measuring the thermodynamic properties of protein-ligand complexes in solution. Dissociation constants (Kd values) determined by the method for five model protein-ligand complexes that included those with small molecules, nucleic acids, peptides, and other proteins were generally in good agreement with Kd values measured by conventional methods. Important experimental advantages of the described method over existing methods include: the ability to make measurements in a high-throughput and automated fashion, the ability to make measurements using only picomole quantitities of protein, and the ability to analyze either purified or unpurified protein-ligand complexes. 相似文献
7.
Rangwalla H Schwab AD Yurdumakan B Yablon DG Yeganeh MS Dhinojwala A 《Langmuir : the ACS journal of surfaces and colloids》2004,20(20):8625-8633
A new and direct approach to verify surface heterogeneity as the microscopic origin of contact-angle hysteresis is demonstrated. IR-visible sum-frequency-generation spectroscopy (SFG) was used to selectively probe the molecules at the interface of an alkyl-side-chain polymer [poly(vinyl n-octadecyl carbamate-co-vinyl acetate)] with water. The spectra indicate that in contact with water, the polymer surface is heterogeneous (having areas of differing surface energies). This evidence of surface heterogeneity supports the hysteresis observed in the advancing and receding contact angles of the polymer surface with water. The same measurements made for the chemically and structurally similar surface of an octadecyltrichlorosilane self-assembled monolayer indicates a homogeneous surface at the water interface. In this case, contact-angle hysteresis measurements implicate surface roughness as the cause of hysteresis. Atomic force microscopy measurements of roughness for these surfaces further support our conclusions. The polymer-water interface was probed using SFG at above-ambient temperatures, and an order-to-disorder transition (ODT) of alkyl side chains at the interface was observed, which closely follows the melting of crystalline side chains in the bulk. This transition explains the increased wettability of the polymer, by water, when the temperature is raised above the bulk melting temperature. Furthermore, the irreversibility of this ODT suggests that the disordered polymer-water interface is the thermodynamic equilibrium state, whereas the before-heating structure of this interface is a kinetically hindered metastable state. 相似文献
8.
Harp GP Rangwalla H Yeganeh MS Dhinojwala A 《Journal of the American Chemical Society》2003,125(37):11283-11290
Surface-sensitive infrared-visible sum frequency generation spectroscopy (SFG) in total internal reflection geometry has been used to study the structure of poly(vinyl n-octadecyl carbamate-co-vinyl acetate) (PVNODC) or poly(octadecyl acrylate) (PA-18) in contact with a deuterated or hydrogenated polystyrene (dPS or hPS) layer. SFG spectra from the PVNODC (or PA-18)/hPS interface show methyl and methylene peaks corresponding to PVNODC (or PA-18) and phenyl peaks corresponding to the PS. Analysis suggests that the methyl groups are tilted at angles less than 30 degrees with respect to the surface normal. The presence of a strong methylene peak suggests the PVNODC alkyl side chains contain more gauche defects at the PS/PVNODC interface in comparison to PVNODC (or PA-18)/air interfaces. On heating, the SFG intensity from the PS/PA-18 interface drops sharply near the bulk melting temperature (T(m)) of PA-18. Interestingly, a similar drop in SFG signal is also observed for the PS phenyl groups. This demonstrates the ability of the phenyl group at the PS/PA-18 interface to rearrange itself upon the solid-to-liquid transition of the PA-18 alkyl side chain, at a temperature well below the bulk PS glass transition temperature. For PS/PVNODC interfaces, the drop in SFG intensity is gradual and in agreement with the three broad transitions of PVNODC observed in the bulk. 相似文献
9.
Biodegradable polyurethane elastomers with potential for applications in medical implants with tunable degradation rate and physical properties were synthesized from reaction of epoxy terminated polyurethanes (EUP) with 1,6-hexamethylene diamine (HMDA) as curing agent. Poly(ε-caprolactone) (PCL) and poly(ethylene glycol) (PEG) as well as 1,6-hexamethylene diisocyanate (HDI) were used for preparation of isocyanate terminated polyurethanes which were subsequently blocked with glycidol to prepare EUPs. All materials were characterized by conventional methods, and their properties were studied fully. Results showed that elastomers based on PEG exhibit superior degradation rate and inferior mechanical properties in comparison to elastomers based on PCL. Optimum degradation rate and mechanical properties were obtained from elastomers made from mixture of PCL and PEG base EUPs. 相似文献
10.
New Phellandrene Derivatives from the Root Oil of Angelica archangelica L . 2-Nitro-1,5-p-menthadiene ( 5 ), trans- and cis-6-nitro-1(7), 2-p-menthadiene ( 6 and 7 ), trans-1(7), 5-p-menthadien-2-yl acetate ( 9 ) and a formal phellandrene derivative, 7-isopropyl-5-methyl-5-bicyclo [2.2.2]octen-2-one ( 16 ), have been identified in the root oil of Angelica archangelica L . Starting from (?)-(R)-α-phellandrene ( 1 ) (R)- 5 , (4R, 6S)- 6 /(4R, 6R)- 7 , (2S, 4R)- 9 and (1R, 4R, 7R)- 16 as well as (2S, 4R)- 11 , (2R, 4R)- 12 and (2R, 4R)- 10 have been prepared. 相似文献