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991.
Neumann H Strübing D Lalk M Klaus S Hübner S Spannenberg A Lindequist U Beller M 《Organic & biomolecular chemistry》2006,4(7):1365-1375
Corollosporine is an antimicrobial metabolite, which was isolated from the marine fungus Corollospora maritima. Owing to its basic 4-hydroxyphthalic acid anhydride structure, it has become an attractive target for a structure/activity relationship modelling of derived compounds with potential antibiotic activity. In this regard we report on the straightforward synthesis of hetero analogous corollosporines, which were easily prepared by a three-step reaction sequence, taking advantage of a novel multicomponent reaction (AAD-reaction) and a subsequent aromatization/Grignard reaction protocol. Furthermore, the obtained products were tested in several biological assays to evaluate their antimicrobial activity. 相似文献
992.
Hayer A de Halleux V Köhler A El-Garoughy A Meijer EW Barberá J Tant J Levin J Lehmann M Gierschner J Cornil J Geerts YH 《The journal of physical chemistry. B》2006,110(15):7653-7659
A concept for highly ordered solid-state structures with bright fluorescence is proposed: liquid crystals based on tetraethynylpyrene chromophores, where the rigid core is functionalized with flexible, promesogenic alkoxy chains. The synthesis of this novel material is presented. The thermotropic properties are studied by means of differential scanning calorimetry (DSC), cross-polarized optical microscopy (POM), and X-ray diffraction. The mesogen possesses an enantiotropic Col(h) phase over a large temperature range before clearing. The material is highly fluorescent in solution and, most remarkably, in the condensed state, with a broad, strongly red shifted emission. Fluorescence quantum yields (Phi(F)) have been determined to be 70% in dichloromethane solution and 62% in the solid state. Concentration- and temperature-dependent absorption and emission studies as well as quantum-chemical calculations on isolated molecules and dimers are used to clarify the type of intermolecular interactions present as well as their influence on the fluorescence quantum yield and spectral properties of the material. The high luminescence efficiency in the solid state is ascribed to rotated chromophores, leading to an optically allowed lowest optical transition. 相似文献
993.
[reaction: see text] The first total synthesis of an N,C-coupled naphthylisoquinoline alkaloid-ancisheynine-was achieved by condensing a monocyclic diketone or the respective benzopyrylium salt with an aminonaphthalene. The presence of a rotationally hindered axis in ancisheynine was demonstrated by resolution of its two atropo-enantiomers by HPLC on a chiral phase with LC-CD coupling. The assignment of their axial configurations succeeded by quantum chemical CD calculations. 相似文献
994.
Wienkoop S Larrainzar E Niemann M Gonzalez EM Lehmann U Weckwerth W 《Journal of separation science》2006,29(18):2793-2801
Mass spectrometry (MS) has become a powerful tool for the quantitative analysis of complex protein samples. A high-throughput strategy for the comparative analysis of multiple protein samples with high complexity becomes more and more important. Two strategies, spectral count and peak intensity, for label-free MS analysis of prefractionated complex mixtures have been described recently to be useful for quantitation. Here we compare both strategies for rapid and quantitative 1-D shotgun LC/MS/MS analyses of highly complex protein mixtures using silica-based monolithic columns. First, we validated linearity and sensitivity of these methods by spiking varying amounts of an internal standard protein in a complex plant protein extract. Secondly, quantitative data of proteins of Medicago truncatula nodules were visualized with independent components analysis using data either obtained from spectral count or peak integration performed with commercial software. Spectral count showed apparent advantages over peak integration because several peptides per protein are automatically averaged, the linear dynamic range of quantitation increases in complex matrices and the number of quantified proteins surpasses the number of proteins using peak integration. Thus, for the need of rapid comparative analysis of highly complex protein samples, spectral count enables sample pattern recognition and identification of biomarkers in nongel based proteomic studies. 相似文献
995.
Sin KK Chan CP Pang TH Seydack M Renneberg R 《Analytical and bioanalytical chemistry》2006,384(3):638-644
Nanocrystals of the fluorogenic precursor fluorescein diacetate (FDA) were applied as labels in order to improve on the assay
sensitivity achieved in our previous studies. Each FDA nanocrystal can be converted into ∼2.6×106 fluorescein molecules, which is useful for improving immunoassay sensitivity and limits of detection. NeutrAvidin was simply
adsorbed onto the surface of the FDA nanocrystals, which were coated with distearoylglycerophosphoethanolamine (DSPE) modified
with amino(poly(ethylene glycol))(PEG(2000)-Amine) as an interface for coupling biomolecules. This can be applied to detect
different kinds of analytes that are captured by corresponding biotinylated biomolecules in different bioanalytical applications.
The applicability of the NeutrAvidin-labeled nanocrystals was demonstrated in an immunoassay using the labeled avidin–biotin
technique. Biotinylated antibody and FDA-labeled avidin were applied to the assay sequentially. The performance was compared
with the traditional sandwich-type assay for mouse immunoglobulin G detection. Following the immunoreaction, the nanocrystals
were released by hydrolysis and dissolution instigated by adding a large volume of organic solvent/sodium hydroxide mixture.
The limit of detection was lower (by a factor of 2.5–21) and the sensitivity was (3.5–30-fold) higher than immunoassays using
commercial labeling systems (FITC and peroxidase). This study shows that using fluorescent nanocrystals in combination with
the avidin–biotin technique can enhance assay sensitivity and provide a lower limit of detection without requiring long incubation
times as in enzyme-based labels. 相似文献
996.
D'hooghe M Van Speybroeck V Waroquier M De Kimpe N 《Chemical communications (Cambridge, England)》2006,(14):1554-1556
Enantiomerically pure 2-(aryloxymethyl)aziridines are efficiently transformed into chiral N-(2-bromo-3-aryloxypropyl)amines via a regio- and stereospecific ring opening of the intermediate aziridinium salts, and the experimental results are rationalized on the basis of some high level ab initio calculations. 相似文献
997.
Tong H Dong Y Häussler M Lam JW Sung HH Williams ID Sun J Tang BZ 《Chemical communications (Cambridge, England)》2006,(10):1133-1135
Nonemissive fulvenes can be induced to luminesce by aggregate formation, with the crystalline aggregates emitting bluer lights more intensely than their amorphous counterparts. 相似文献
998.
Reetz MT Peyralans JJ Maichele A Fu Y Maywald M 《Chemical communications (Cambridge, England)》2006,(41):4318-4320
The concept of utilizing the methods of directed evolution for tuning the enantioselectivity of synthetic achiral metal-ligand centers anchored to proteins has been implemented experimentally for the first time. 相似文献
999.
Chin KK Chuang SC Hernandez B Selke M Foote CS Garcia-Garibay MA 《The journal of physical chemistry. A》2006,110(51):13662-13666
The photophysical properties of a novel 1,2,3,4,5,6-hexasubstituted fullerene derivative (1) are examined in this study. In addition to the ground state absorption spectrum of 1, we report its triplet-triplet absorption spectrum and molar extinction coefficient (Deltae(T-T)), as well as the triplet quantum yield (PhiT), lifetime (tauT), and energy (ET). The saturation of a single six-member ring on the fullerene cage results in significant changes in the triplet state properties as compared to that of pristine C60. The triplet-triplet absorption spectrum shows a hypsochromic shift in long wavelength absorption, and both the triplet state lifetime and the triplet quantum yield are decreased. The triplet energy was found to be similar to that of C60. In addition, the quantum yield (PHI(delta)) of singlet oxygen generated by 1 was calculated and is found to be significantly less than in the case of C60. 相似文献
1000.
Hoyermann K Nothdurft J Olzmann M Wehmeyer J Zeuch T 《The journal of physical chemistry. A》2006,110(9):3165-3173
The formation and the decomposition of chemically activated cyclopentoxy radicals from the c-C5H9 + O reaction have been studied in the gas phase at room temperature. Two different experimental arrangements have been used. Arrangement A consisted of a laser-flash photolysis set up combined with quantitative Fourier transform infrared spectroscopy and allowed the determination of the stable products at 4 mbar. The c-C5H9 radicals were produced via the reaction c-C5H10 + Cl with chlorine atoms from the photolysis of CFCl3; the O atoms were generated by photolysis of SO2. Arrangement B, a conventional discharge flow-reactor with molecular beam sampling, was used to determine the rate coefficient. Here, the hydrocarbon radicals (c-C5H9, C2H5, CH2OCH3) were produced via the reaction of atomic fluorine with c-C5H10, C2H6, and CH3OCH3, respectively, and detected by mass spectrometry after laser photoionization. For the c-C5H9 + O reaction, the relative contributions of intermediate formation (c-C5H9O) and direct abstraction (c-C5H8 + OH) were found to be 68 +/- 5 and 32 +/- 4%, respectively. The decomposition products of the chemically activated intermediate could be identified, and the following relative branching fractions were obtained: c-C5H8O + H (31 +/- 2%), CH2CH(CH2)2CHO + H (40 +/- 5%), 2 C2H4 + H + CO (17 +/- 5%), and C3H4O + C2H4 + H (12 +/- 5%). Additionally, the product formation of the c-C5H8 + O reaction was studied, and the following relative yields were obtained (mol %): C2H4, 24%; C3H4O, 18%; c-C5H8O, 30%; c-C5H8O, 23%; 4-pentenal, 5%. The rate coefficient of the c-C5H9 + O reaction was determined relative to the reactions C2H5 + O and CH3OCH2 + O leading to k = (1.73 +/- 0.05) x 10(14) cm3 mol(-1) s(-1). The experimental branching fractions are analyzed in terms of statistical rate theory with molecular and transition-state data from quantum chemical calculations, and high-pressure limiting Arrhenius parameters for the unimolecular decomposition reactions of C5H9O species are derived. 相似文献