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101.
102.
The key construction in the preparation of as-indacene-bridged bis(alpha-amino acid) derivatives was effected by a Ru(II)-catalyzed RCM cascade reaction of appropriately substituted triynes. The latter were available after stepwise and stereocontrolled alkynylations of (2R)-2,5-dihydro-2-isopropyl-3,6-dimethoxypyrazine as chiral auxiliary. The regio- and stereochemical transformations have been verified by a single-crystal X-ray analysis. 相似文献
103.
The relation of the special and the general principle of relativity to the principle of covariance, the principle of equivalence and Mach's principle, is discussed. In particular, the connection between Lorentz covariance and the special principle of relativity is illustrated by giving Lorentz covariant formulations of laws that violate the special principle of relativity: Ohm's law and what we call Aristotle's first and second laws. An Aristotelian universe in which all motion is relative to absolute space is considered. The first law: a free particle is at rest. The second law: force is proportional to velocity. Ohm's law: the current density is proportional to the electrical field strength. Neither of these laws fulfills the principle of relativity. The examples illustrate, in the context of Lorentz covariance and special relativity, Kretschmann's critique of founding Einstein's general principle of relativity on the principle of general covariance. A modification of the principle of covariance is suggested, which may serve as a restricted criterium for a physical law to satisfy Einstein's general principle of relativity. Other objections that have been raised to the validity of Einstein's general principle of relativity are based upon the preferred state of inertial frames in the general, as well as in the special theory, the existence of tidal effects in true gravitational fields, doubts as to the validity of Mach's principle, whether electromagnetic phenomena obey the principle, and, finally, the anisotropy of the cosmic background radiation. These objections are reviewed and discussed. 相似文献
104.
A method for preparation of silica nanowires with dimensions of d = 10-100 nm, l = 5-500 nm, is described. The nanostructured material is an integral part of the inner surface of narrow bore fused-silica capillary tubing. The wire preparation method is based on a decomposition of 2-chloro-1,1,2-trifluoroethyl methyl ether at elevated temperature and pressure. The silica bulk material is rearranged via a sustained silica-hydrogen fluoride chemistry, and reaction mechanisms for this process are proposed. The method is suitable for preparing long lengths of tubing with the modified surface. It is our belief that the texture of the capillary wall with its increased surface area is useful for applications such as microreactions, catalysis, and high-resolution pressure and/or electrodriven open-tubular liquid chromatography. 相似文献
105.
Kjell Rosquist 《General Relativity and Gravitation》1980,12(8):649-664
Global rotation in cosmological models is defined on an observational basis. A theorem is proved saying that, for rigid motion, the global rotation is equal to the ordinary local vorticity. The global rotation is calculated in the space-time homogeneous class III models, with Gödel's model as a special case. It is shown that, with the exception of Gödel's model, the rotation in these models becomes infinite for finite affine parameter values. In some directions the rotation changes sign and becomes infinite in a direction opposite to the local vorticity. The points of infinite rotation are identified as conjugate points along the null geodesies. The physical interpretation of the infinite rotation is discussed, and a comparison with the behavior of the area distance at conjugate points is given. 相似文献
106.
An elementary presentation is given of classical and relativistic collision dynamics based upon the principle of conservation of momentum. The concepts of mass are shown to be implicitly defined and their basic properties are rigorously derived and discussed. Luxons and tachyons are treated on the same footing as material particles. 相似文献
107.
Andrei M Bjørnstad V Langli G Rømming C Klaveness J Taskén K Undheim K 《Organic & biomolecular chemistry》2007,5(13):2070-2080
Cyclic adenosine monophosphate (cAMP) has been converted into its 8-bromo derivative and 2'O-TBDMS protected before activation of the phosphoric acid moiety with a reagent generated in situ from oxalyl chloride and DMF. Further reactions with primary amines furnished corresponding phosphoramidates with high stereoselectivity at the phosphorus atom. Cross-coupling reactions with the 8-bromopurine yielded 8-hetaryl derivatives. X-Ray analyses showed the amidates to possess the (S(P))-configuration. Carbon disulfide effected thiylation under strongly basic conditions stereospecifically provided the (R(P))-phosphorothioic acids. 相似文献
108.
Uhlig S Vikøren T Ivanova L Handeland K 《Rapid communications in mass spectrometry : RCM》2007,21(10):1651-1660
Ergot alkaloids are mycotoxins which are produced among fungi in the family Clavicipitaceae. Poisoning with ergot alkaloids is an important veterinary problem in animal husbandry and has recently also been recognised in wild animals. While the poisoning syndrome observed in domestic animals such as cattle, horses and sheep is usually caused by endophyte-infected grass, the recently observed ergotism among Norwegian cervids is probably due to infection of wild grasses with Claviceps. Mass spectrometry is today the method of choice for the rapid qualitative and quantitative determination of many natural compounds. This study uses tandem quadrupole mass spectrometry as well as ion trap mass spectrometry in connection with electrospray(+) ionisation for the quantification, screening and fragmentation of ergot alkaloids in extracts from Claviceps sclerotia that had been picked from wild grasses from several locations in Norway. Ergotamine, ergovaline, ergonovine and ergocryptine were available as standards and were quantified in the extracts, while ergocrystine, ergocornine, ergonine/ergosine, lysergic acid and lysergol were identified on the basis of their molecular weights and semi-quantified. Ergocrystine dominated the alkaloid spectrum of most extracts. Levels of the quantified alkaloids were in the range 0.2-9300 microg/g. Several unknown ergot alkaloids were found in the extracts. MS(n) experiments identified some as simple lysergic acid amide derivatives, while othes are probably related to ergocrystine and ergocryptine by dehydration, dehydrogenation and/or amino acid substitution at R(1) of the peptide moiety. 相似文献
109.
110.
The reaction between Zn(NO3)2.6H2O and 5-aminoisophthalic acid (aip) in a mixture of diethylformamide (DEF) and ethanol resulted in [Zn(C8H5NO4)(C5H11NO)]n (CPO-8-DEF). This compound is composed of infinite 2D layers with tetrahedral Zn atoms and aip ligands in a triangular topology. The DEF molecules are bonded to Zn, and within each layer, the DEF molecules are oriented in the same direction, while in the subsequent layer, the DEF molecules are oriented in the opposite direction. By introduction of the pillaring ligands 4,4-bipyridine (BPY), 1,2-di-4-pyridylethylene (DPE), 1,2-di-4-pyridylethane (DPA), and 1,3-di-4-pyridylpropane (DPP) into mixtures of N,N'-dimethylformamide and water with Zn(NO3)2 and aip, we have successfully synthesized a series of related pillared bilayer compounds with the same common triangular Zn(aip) layer structural motif as that observed in CPO-8-DEF. The compounds are denoted as CPO-8-BPY ([Zn(C8H5NO4)(C10H8N2)(0.5)]n.3nH2O), CPO-8-DPE ([Zn(C8H5NO4)(C12H10N2)(0.5)]n.2.5nH2O), CPO-8-DPA ([Zn(C8H5NO4)(C12H12N2)(0.5)]n.2.5nH2O), and CPO-8-DPP ([Zn(C8H5NO4)(C13H14N2)(0.5)]n.3nH2O). In all cases, the pillars create spaces inside the bilayers that result in 1D channels running along the [010] directions with dimensions of 3.5 x 6.7 A(2). These channels contain water molecules that can be removed on heating to 150 degrees C, resulting in porous structures. The crystal structures of these porous high-temperature variants have been determined on the basis of powder X-ray diffraction data. All of the compounds show preferential adsorption of H2 over N2 at 77 K. 相似文献