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991.
Michael Sax 《Tetrahedron》2005,61(1):205-211
A novel solid phase synthesis of 2-substituted 2,3-dihydropyridin-4(1H)-ones using Rinkamide-polystyrene-resin is described. The key step involves a hetero-Diels-Alder reaction of Danishefsky's diene with solid phase bound imines, which was carefully optimized. Using this method even ketones are transformed into 2,2-disubstituted dihydropyridones. 相似文献
992.
Obrecht D Altorfer M Lehmann C Schönholzer P Müller K 《The Journal of organic chemistry》1996,61(12):4080-4086
A novel strategy for the synthesis of (R)- and (S)-alpha-methyl(alkyl)serine-containing peptides is presented. Using (S)-phenylalanine cyclohexylamide 6 as chiral auxiliary, the optically pure azlactones (R)- and (S)-2 were synthesized via a novel azlactone/oxazoline interconversion reaction (Figures 3 and 6). These azlactones constitute fully protected and activated synthetic equivalents of (R)- and (S)-alpha-methylserine and can be directly incorporated into peptides without further protective group manipulations. Like other alpha,alpha-dialkylated glycines, optically pure alpha-alkylserines can be used to stabilize beta-turn and alpha-helical conformations in short peptides. 相似文献
993.
994.
Herbst K Zanello P Corsini M D'Amelio N Dahlenburg L Brorson M 《Inorganic chemistry》2003,42(4):974-981
By reaction of the geometrically incomplete cubane-like clusters [(eta(5)-Cp')(3)Mo(3)S(4))][pts] and [(eta(5)-Cp')(3)W(3)S(4)][pts] (Cp' = methylcyclopentadienyl; pts = p-toluenesulfonate) with group 10 alkene complexes, three new heterobimetallic clusters with cubane-like cluster cores were isolated: [(eta(5)-Cp')(3)W(3)S(4)M'(PPh(3))][pts] ([5][pts], M' = Pd; [6][pts], M' = Pt); [(eta(5)-Cp')(3)Mo(3)S(4)Ni(AsPh(3))][pts] ([7][pts]). The compounds [5][pts]-[7][pts] are completing the extensive series of clusters [(eta(5)-Cp')(3)M(3)S(4)M'(EPh(3))][pts] (M = Mo, W; M' = Ni, Pd, Pt; E = P, As) which allows the consequences of replacing a single type of atom on structural and NMR and UV/vis spectroscopic as well as electrochemical properties to be determined. Single-crystal X-ray structure determinations of [5][pts]-[7][pts] revealed that [5][pts] was not isomorphous to the other members of the series [(eta(5)-Cp')(3)M(3)S(4)M'(EPh(3))][pts] due to distinctly different cell parameters, which in the molecular structure of [5](+) is reflected in a slightly different orientation of the PPh(3) ligand. Electrochemical measurements on the series showed that the Mo-based clusters were more difficult to oxidize than their W-based analogues. The Pd-containing clusters underwent two-electron oxidation processes, whereas the Ni- and Pt-containing clusters underwent two separated one-electron oxidation processes. 相似文献
995.
Allison M. Mills Daniel Brunling Michael Ruck 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(8):i70-i72
A redetermination of the structure of `La32.66Fe11S60' in the trigonal space group Rm led to the new formula La52Fe12S90 and to a redefinition of the structure type. In the structure, the Fe2+ cations occur in Fe2S9 dimers of face‐sharing octahedra (with 3m symmetry). The dimers are linked by face‐ and vertex‐sharing bi‐ and tricapped LaS6 trigonal prisms (with m symmetry) to form a three‐dimensional network containing two types of cuboctahedral cavities. The larger cavities remain empty, while the smaller ones accommodate alternative sites for disordered La3+ cations. 相似文献
996.
The metal binding properties of the dinucleotide duplex, dCG x dCG, were analyzed in the gas phase with ion mobility mass spectrometry. Both MALDI and ESI were used to generate [M(dCG x dCG)]+ complexes. The collision cross section of each complex was measured in helium using ion mobility based methods and compared to calculated cross sections of theoretical structures. When metal cations classified as hard acids were combined with dCG x dCG, the [M(dCG x dCG)]+ complex organized into a globular structure. However, when soft acid metal cations were examined, a structure was observed where the two C-G base pairs were Watson-Crick bound. 相似文献
997.
Vibrational relaxation cross sections of the H(2)O(upsilon(2) = 1) bending mode by H(2) molecules are calculated on a recent high-accuracy ab initio potential-energy surface using quasiclassical trajectory calculations. The role of molecular rotation is investigated at a collisional energy of 3500 cm(-1) and it is shown that initial rotational excitation significantly enhances the total (rotationally summed) vibrational relaxation cross sections. A strong and complex dependence on the orientation of the water angular momentum is also observed, suggesting the key role played by the asymmetry of water. Despite the intrinsic limitations of classical mechanics, these exploratory results suggest that quantum approximations based on a complete decoupling of rotation and vibration, such as the widely used vibrational close-coupling (rotational) infinite-order-sudden method, would significantly underestimate rovibrationally inelastic cross sections. We also present some rationale for the absence of dynamical chaos in the scattering process. 相似文献
998.
Frank W. Crow Michael L. Gross Maurice M. Bursey 《Journal of mass spectrometry : JMS》1981,16(7):309-311
Collisional activation of the molecular ions of 1-propanol, 2-propanol and methyl ethyl ether, and of the m/z 60 ion from 1,2-dimethoxyethane provides evidence for four distinct forms of [C3H8O]+˙. Collision induced decompositions may be explained either by simple cleavages, by cyclic processes involving adjacent substituents, or by bicyclic processes of adjacent substituents. Evidence for a form of [C3H8O]+˙ in which charge and radical site are separate is assembled from the spectra. 相似文献
999.
Crystal Structures of Acid Hydrates and Oxonium Salts. XX. Oxonium Tetrafluoroborates H3OBF4, [H5O2]BF4, and [H(CH3OH)2]BF4 The crystal structures of three oxonium tetrafluoroborates were determined. H3OBF4, oxonium tetrafluoroborate proper, is triclinic with space group P1 , Z = 2 and the unit cell dimensions a = 4.758, b = 6.047, c = 6.352 Å and α = 80.40, β = 79.48, γ = 88.25° at ?26°C. Cations H3O+ and anions BF4? are linked by hydrogen bonds O? H…?F into ribbons of condensed rings. In [H5O2]BF4 (diaquohydrogen tetrafluoroborate, monoclinic, P21/c, Z = 4, a = 6.584, b = 9.725, c = 7.084 Å, β = 95.15° at ?100°C) the hydrogen bond in the cation H5O2+ is 2.412 Å short, asymmetric and approximately centered and the linking of cations and anions three-dimensional. In [H(CH3OH)2]BF4 (Bis(methanol)hydrogen tetrafluoroborate, monoclinic, P21/c, Z = 4, a = 5.197, b = 14.458, c = 9.318 Å, β = 94.61° at ?50°C) the cation [H(CH3OH)2]+ is characterized for the first time in a crystal structure with an again very short (2.394 Å), asymmetric and effectively centered hydrogen bond. By further hydrogen bonds cations and anions form only dimers of the formula unit of centrosymmetric cyclic structure. 相似文献
1000.
Haplotype studies support slippage as the mechanism of germline mutations in short tandem repeats 总被引:1,自引:0,他引:1
Klintschar M Dauber EM Ricci U Cerri N Immel UD Kleiber M Mayr WR 《Electrophoresis》2004,25(20):3344-3348
Germline mutations of human short tandem repeat (STR) loci are expansions or contractions of repeat arrays which are not well understood in terms of the mechanism(s) underlying such mutations. Although polymerase slippage is generally accepted as a mechanism capable to explain most features of such mutations, it is still possible that unequal crossing over plays some role in those events, as most studies in humans could not exclude unequal crossing over (UCO). Crossing over can be studied by analyzing haplotypes using flanking markers. To check for UCO in mutations, we have analyzed 150 paternity cases for which more than the usual trio (mother, child, and father) were available for testing by analyzing 16 STR loci. In a total of 4900 parent-child allele transfers four mutations were observed at different loci (D8S1179, D18S51, D21S11, and SE33/ACTBP2). To identify the mutated allele and to check for UCO, we typed at least four informative loci flanking the mutated locus and used the pedigree data to establish haplotypes. By doing so we were able to exclude UCO in each case. Moreover, we were able to identify the mutations as one-repeat contractions/expansions. Our data thus support slippage as the mechanism of germline mutations in STRs. 相似文献