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181.
Okamura WH Zhu GD Hill DK Thomas RJ Ringe K Borchardt DB Norman AW Mueller LJ 《The Journal of organic chemistry》2002,67(5):1637-1650
Isotope-labeled drug molecules may be useful for probing by NMR spectroscopy the conformation of ligand associated with biological hosts such as membranes and proteins. Triple-labeled [7,9,19-(13)C(3)]-vitamin D(3) (56), its 25-hydroxylated and 1 alpha,25-dihydroxylated metabolites (58 and 68, respectively), and other labeled materials have been synthesized via coupling of [9-(13)C]-Grundmann's ketone 39 or its protected 25-hydroxy derivative 43 with labeled A ring enyne fragments 25 or 26. The labeled CD-ring fragment 39 was prepared by a sequence involving Grignard addition of [(13)C]-methylmagnesium iodide to Grundmann's enone 28, oxidative cleavage, functional group modifications leading to seco-iodide 38, and finally a kinetic enolate S(N)2 cycloalkylation. The C-7,19 double labeling of the A-ring enyne was achieved by the Corey-Fuchs/Wittig processes on keto aldehyde 11. By employing these labeled fragments in the Wilson-Mazur route, the C-7,9,19 triple-(13)C-labeled metabolites 56, 58, and 68 as well as other (13)C-labeled metabolites have been prepared. In an initial NMR investigation of one of the labeled metabolites prepared in this study, namely [7,9,19-(13)C(3)]-25-hydroxyvitamin D(3) (58), the three (13)C-labeled carbons of the otherwise water insoluble steroid could be clearly detected by (13)C NMR analysis at 0.1 mM in a mixture of CD(3)OD/D(2)O (60/40) or in aqueous dimethylcyclodextrin solution and at 2 mM in 20 mM sodium dodecyl sulfate (SDS) aqueous micellar solution. In the SDS micellar solution, a double half-filter NOESY experiment revealed that the distance between the H(19Z) and H(7) protons is significantly shorter than that of the corresponding distance calculated from the solid state (X-ray) structure of the free ligand. The NMR data in micelles reveals that 58 exists essentially completely in the alpha-conformer with the 3 beta-hydroxyl equatorially oriented, just as in the solid state. The shortened distance (H(19Z))-H(7)) in micellar solutions as compared to that in the solid state is most easily rationalized on the basis that the 5(10)-torsion angle in 58 is decreased in micellar solutions as compared to that in the solid state. 相似文献
182.
Thomas F. Jenny Jennifer Horlacher Nicoletta Previsani Steven A. Benner 《Helvetica chimica acta》1992,75(6):1944-1954
A set of derivatives of cyclopentaneacetic acid cis-substituted at position 3 by nucleoside bases (both purines and pyrimidines) were prepared and characterized (see 11, 14 , and 23a, b; Schemes 2–4). These molecules are carbocyclic analogs of 2′,3′-dideoxy-5′-homonucleosides. In this synthesis, the skeleton was constructed from norbornanone and a novel method based on Mitsunobu chemistry used for the introduction of nucleoside-base substituents. The scope of this method was further explored via the preparation of a cyclobutyl analog of dideoxyguanosine (see 17 , Scheme 3). 相似文献
183.
Haberichter T Roux E Marhl M Mazat JP 《Bioelectrochemistry (Amsterdam, Netherlands)》2002,57(2):129-138
In airway myocytes, like in many cells, Ca(2+) signaling is controlled by inositol 1,4,5-trisphosphate (InsP(3)) via InsP(3) receptors (InsP(3)R) located in the sarco-endoplasmic reticulum. Three types of InsP(3)R exist, labeled Types 1, 2, and 3, which differ in their gating kinetics. We analyze a possible impact of the different gating kinetics of Type 1 and Type 3 InsP(3)R on the time course of cytosolic Ca(2+) concentration in tracheal smooth muscle cells upon agonist stimulation. Previous experimental data in rat tracheal myocytes showed that upon gradually increased stimulation with acetylcholine (ACh), a contractile agonist that acts via InsP(3) production, signal spikes, several spikes with declining maxima, and sustained oscillations appear. Our model reproduces the time courses of cytosolic Ca(2+) measured in tracheal myocytes. Moreover, by postulating slight variations in the model parameters which determine the total number of receptors expressed and the ratio between Type 1 and Type 3 InsP(3)R, it offers an explanation to the experimental observation of qualitatively different responses of cells within a presumably homogeneous tissue. 相似文献
184.
The impact of spilled explosives, their by-products and degradation products on human beings and the environment has been
recognised as a serious problem at areas of existing and former ammunition plants. In nature, aerobic and anaerobic degradation
processes of explosives and their accompanying compounds yield polar contaminants with relatively high water solubilities.
Most are potentially carcinogenic and mutagenic. An HPLC method applying UV-detection for nitroaromatic compounds and amperometric
detection for aminoaromatic and phenolic compounds was used for monitoring the degradation of explosives in a polluted groundwater
sample under natural conditions. Analysis was performed by direct injection of aliquots of the sample after exposition to
daylight for different periods of time.
Received: 6 January 1996/Revised: 7 March 1996/Accepted: 13 March 1996 相似文献
185.
Iron-silicon thin films have been characterized by means of analytical transmission electron microscopic methods. Under certain conditions — composition and annealing temperature — these films exhibit thermoelectric behavior. In particular, the morphology and phase formation which results from annealing of these films, and doping with oxygen and nitrogen, are of interest. The thermoelectric phase -FeSi2 is formed at temperatures above 500°C. This phase is transformed into electrically conducting phases at about 1000°C. A small oxygen content does not influence this crystallization process. If the oxygen content is higher than 15 atom-% the electrically conducting phases exist even at 500°C. The presence of a small nitrogen content inhibits the formation of the -FeSi2 phase. The development of silicon and iron nitrides is possible. 相似文献
186.
Reinhard Haase Dorit S. Meinhold Berthold Thomas Edwin Weber Gerd Rheinwald 《Structural chemistry》2002,13(5-6):471-477
The crystal structures of inclusion compounds of 3,3-bis(9-hydroxy-9-fluorenyl)-2,2-binaphthyl host (1) and its chloro (2) or bromo (3) derivatives substituted in 2,7-positions of the fluorene units with acetone guests (1A–3A) were determined by X-ray studies as well as by 1H-CRAMPS solid-state NMR. Using this NMR technique allows identification of differently bound guest molecules due to their different chemical shifts caused by the influence of the ring current effects of the host aryl units. 相似文献
187.
Both RhH(CO)PPh3)3 and a catalyst made in situ from RhCl3·3H2O, PPh3 and Na2CO3 catalyse the reaction of a range of aldehydes with simple primary alcohols to give esters together with alcohols formed by reduction of the aldehydes. The proportion of ester can be increased by adding an efficient hydrogen acceptor. The reaction can also be used to produce 5- and 7-membered lactones from aromatic dialdehydes. Propan-2-ol and the in situ catalyst reduce some aromatic aldehydes to the corresponding alcohols without concomitant ester formation. 相似文献
188.
189.
190.
MM2 Exploration of the conformational space for methylcyclopentane, in contrast to cyclopentanone yields more and flatter minima than known previously. Calculations of cyclopentanes with substituents X = F, Cl, CHMe2, and CMe3 with two stable conformations indicate <2° torsional angle changes with the different substituents. Cyclopentanes bearing not more than 2 substituents can accommodate all groups in pseudoequatorial positions without changing the basic envelope and twist chair geometries significantly. A model for 13C-shift calculation is proposed in which shift increments for the different torsional arrangements are obtained by linear interpolation between corresponding cyclohexane values. After correction for the nonequivalent carbon shifts in the hydrocarbon itself, again using the linear interpolation, a significant improvement of the shift correlations is observed. For disubstituted cyclopentanes these predict the shifts within ± 1.7 ppm with Me, CHMe2, CMe3, Cl, Br and OH as substituents. Configurational assignments are difficult with 1,3-di-substituted cyclopentanes, but straightforward with 1,2-di- and trisubstituted compounds. Thus, due to the presence of smaller torsional angles between, e.g. diequatorial vicinal substituents in the 1,2- cis series as compared to the trans compounds, the latter show deshielding, particularly at C2, by 1–4 ppm. Several epimers are stereo-selectively prepared by suitable ketone reduction and displacement methods. 相似文献