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21.
Oliver Pretzel 《Order》1995,12(2):135-147
We prove generalizations to chain groups, of Minty's Arc Colouring Lemma and its extension, the well-known Farkas Lemma. In these the orientation of the edges is replaced by an arbitrary chain.A function on a chain groupN isrepresentable if there exists a chainR such that (X)=R·X for allXN. Anorientation is a chain with values ±1. We prove that for a regular chain group a linear function that is representable by an orientation for each chainXN locally, is representable by an orientation globally. 相似文献
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Flögel O Dash J Brüdgam I Hartl H Reissig HU 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(17):4283-4290
Addition of lithiated methoxyallene to pivalonitrile afforded after aqueous workup the expected iminoallene 1 in excellent yield. Treatment of this intermediate with silver nitrate accomplished the desired cyclization to the electron-rich pyrrole derivative 2 in moderate yield. Surprisingly, trifluoroacetic acid converted iminoallene 1 to a mixture of enamide 3 and trifluoromethyl-substituted pyridinol 4 (together with its tautomer 5). A plausible mechanism proposed for this intriguing transformation involves addition of trifluoroacetate to the central allene carbon atom of an allenyl iminium intermediate as crucial step. Enamide 3 is converted to pyridinol 4 by an intramolecular aldol-type process. A practical direct synthesis of trifluoromethyl-substituted pyridinols 4, 10, 11, and 12 starting from typical nitriles and methoxyallene was established. Pyridinol 10 shows an interesting crystal packing with three molecules in the elementary cell and a remarkable helical supramolecular arrangement. Trifluoromethyl-substituted pyridinol 4 was converted to the corresponding pyridyl nonaflate 13, which is an excellent precursor for palladium-catalyzed reactions leading to pyridine derivatives 14-16 in good to excellent yields. The new synthesis of trifluoromethyl-substituted pyridines disclosed here demonstrates a novel reactivity pattern of lithiated methoxyallene which is incorporated into the products as the unusual tripolar synthon B. 相似文献
25.
Direct calculation of interconversion barriers in dynamic chromatography and electrophoresis: Isomerization of captopril 总被引:1,自引:0,他引:1
Trapp O 《Electrophoresis》2005,26(2):487-493
Dynamic capillary electrophoresis (DCE) and direct calculation of the rate constants of isomerization has been applied to determine the cis-trans isomerization barriers of the angiotensin-converting enzyme inhibitor captopril. The separation of the rotational cis-trans isomeric drug has been performed in an aqueous 50 mM borate buffer at pH 9.3. Interconversion profiles featuring plateau formation, peak-broadening, and peak coalescence were observed. To determine the rate constants of the forward and backward reaction (k(cis-->trans) and k(trans-->cis)) of the isomerization process in dynamic capillary electrophoresis, a novel straightforward calculation method using the experimental parameters plateau height, h(plateau), peak width at half height w(h), the total migration times of the cis-trans isomers t(R) and the electroosmotic break-through time t(0) as well as the peak ratio of the cis-trans isomers is presented for the first time. From temperature dependent measurements the rate constants k(cis-->trans) and k(trans-->cis) and the kinetic activation parameters DeltaG( not equal), DeltaH( not equal), and DeltaS( not equal) of the cis-trans isomerization of captopril were obtained. From the activation parameters the isomerization barriers of captopril at 37 degrees C under basic conditions were calculated to be DeltaG( not equal) (cis-->trans) = 90.3 kJ.mol(-1)and DeltaG( not equal) (trans-->cis) = 90.0 kJ.mol(-1*). 相似文献
26.
The attachment of single ions to putative adsorption sites in the tails of collagen fibers is investigated by means of molecular dynamics simulations and discussed with respect to the very early steps of apatite/collagen biomineral formation. Our studies clearly demonstrate an increased flexibility of the tails of the triple‐helical collagen protein. Apart from the termini of the backbone, several side chains were also observed to be freely accessible to ion attachment from aqueous solution. The teleopeptide was systematically scanned for suitable adsorption sites for calcium, phosphate and fluoride ions. Association of these ions was then explored from potential of mean force calculations. The resulting energy profiles reveal a variety of favorable protein‐ion bonds and hint at the suitability of the collagen tails to promote apatite aggregation. 相似文献
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Joachim Angelkort Sander van Smaalen Prof. Dr. Sven Oliver Hauber Mark Niemeyer 《无机化学与普通化学杂志》2007,633(7):1031-1035
Single crystal X‐ray diffraction of Eu(SC36H49)2 has revealed a first order phase transition at a temperature of 119 K, that involves a reduction of the specific volume by 1 %. The transition corresponds to a doubling of the unit cell, as it is the result from reorientations of isopropyl groups that appear at peripheral sites of the organic ligands. It is argued that a denser packing is achieved at the expense of a less favourable conformation of one of the two crystallographically‐independent complexes in the low‐temperature phase. The Bond‐Valence method is used to show that interactions of equal strengths are present between europium and both sulphur atoms and both coordinating phenyl rings. 相似文献
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The creation and use of unnatural molecules to control cellular function is a long standing goal of the chemical community, but in general, these efforts have been directed at finding molecules to inhibit or activate a particular molecular target or function, or to elicit a particular phenotype. Here we show that multiple unnatural molecules (orthogonal ribosomes) can be used combinatorially, in a single cell, to program Boolean logic functions. These experiments show how attention to the molecular specificity of noncovalent interactions between unnatural macromolecules allows the synthesis of complex function from the "bottom-up" in living matter. 相似文献
30.
Extraction of capsaicins in aerosol defense sprays from fabrics 总被引:2,自引:0,他引:2
The use of aerosol defense sprays has increased as a means of self-defense and as a weapon in the commission of a crime. The residue of these sprays is often left behind as physical evidence on a victim's clothing or personal belongings. As the popularity of self-defense weaponry increases, so does the likelihood that it will be encountered in forensic casework. The extraction, recovery from fabrics, and identification of residue from defense sprays is described. The commonly used extraction method of liquid-liquid extraction is compared to solid phase microextraction (SPME) to recover capsaicin and dihydrocapsaicin from cotton swabs. The use of SPME resulted in lower limits of detection and greater recovery efficiency when compared to solvent extraction. SPME also provided more consistent recovery and less variability when compared to solvent extraction. The effect of use of various types of evidence packages on the preservation of this type of evidence is also reported. The collection and analysis of hand swabs after normal discharge of pepper spray canisters was studied indicating the low persistence of these compounds on the hands of the person conducting the spraying. Finally, the results of a real case whereby solvent-solvent extraction did not provide the necessary sensitivity for extracting the capsaicin compounds on the garments of a victim of an alleged spraying and the SPME extraction provided the recovery and identification of the compounds is also presented. 相似文献