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41.
Intercalation of trioxatriangulenium ion in DNA: binding,electron transfer,x-ray crystallography,and electronic structure 总被引:1,自引:0,他引:1
Reynisson J Schuster GB Howerton SB Williams LD Barnett RN Cleveland CL Landman U Harrit N Chaires JB 《Journal of the American Chemical Society》2003,125(8):2072-2083
Trioxatriangulenium ion (TOTA(+)) is a flat, somewhat hydrophobic compound that has a low-energy unoccupied molecular orbital. It binds to duplex DNA by intercalation with a preference for G-C base pairs. Irradiation of intercalated TOTA(+) causes charge (radical cation) injection that results in strand cleavage (after piperidine treatment) primarily at GG steps. The X-ray crystal structure of TOTA(+) intercalated in the hexameric duplex d[CGATCG](2) described here reveals that intercalation of TOTA(+) results in an unusually large extension of the helical rise of the DNA and that the orientation of TOTA(+) is sensitive to hydrogen-bonding interactions with backbone atoms of the DNA. Electronic structure calculations reveal no meaningful charge transfer from DNA to TOTA(+) because the lowest unoccupied molecular orbital of TOTA(+), (LUMO)(T), falls in the gap between the highest occupied molecular orbital, (HOMO)(D), and the (LUMO)(D) of the DNA bases. These calculations reveal the importance of backbone, water, and counterion interactions, which shift the energy levels of the bases and the intercalated TOTA(+) orbitals significantly. The calculations also show that the inserted TOTA(+) strongly polarizes the intercalation cavity where a sheet of excess electron density surrounds the TOTA(+). 相似文献
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Niels Weidmann Marthe Ketels Prof. Dr. Paul Knochel 《Angewandte Chemie (International ed. in English)》2018,57(33):10748-10751
The first sodiations of (hetero)arenes in continuous flow using NaDA (sodium diisopropylamide) in Me2EtN are reported. This flow procedure enables sodiation of functionalized arenes and heteroarenes that decompose under batch‐sodiation conditions. The resulting sodiated (hetero)arenes react instantly with various electrophiles, such as ketones, aldehydes, isocyanates, alkyl bromides, and disulfides, affording polyfunctionalized (hetero)arenes in high yields. Scale‐up is possible without further optimization. 相似文献
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A simple desalting procedure for the coupling of a polymer microchip injector to mass spectrometry is proposed. The overall process is based on the adsorption of proteins on a poly(vinylidene difluoride) (PVDF) membrane, which are then directly eluted in the spraying solution. This microchip-based approach has been successfully applied to small drugs, peptides and proteins originally diluted in phosphate-buffered saline (PBS). Moreover, when eluting the retained proteins in small volumes, a preconcentration is obtained. The combination of single-use, mass-produceable, low-sample-consumption, easy-to-automate, miniaturized polymer injectors with easy-to-handle solution-exchange membranes makes this system particularly amenable to screening applications. 相似文献
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[reaction: see text] A novel type of tetrathiafulvalene-cage 4 containing three monopyrrolo-tetrathiafulvalene units has been prepared employing a general and efficient synthetic approach. X-ray crystal structure analysis revealed that the cage is able to accommodate solvent molecules within a cavity in the solid state. 相似文献
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Bertram HC Rasmussen M Busk H Oksbjerg N Karlsson AH Andersen HJ 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,157(2):267-276
This study investigates the effects of developmental stage and muscle type on the mobility and distribution of water within skeletal muscles, using low-field (1)H-NMR transverse relaxation measurements in vitro on four different porcine muscles (M. longissimus dorsi, M. semitendinosus, M. biceps femoris, M. vastus intermedius) from a total of 48 pigs slaughtered at various weight classes between 25 kg and 150 kg. Principal component analysis (PCA) revealed effects of both slaughter weight and muscle type on the transverse relaxation decay. Independent of developmental stage and muscle type, distributed exponential analysis of the NMR T(2) relaxation data imparted the existence of three distinct water populations, T(2b), T(21), and T(22), with relaxation times of approximately 1-10, 45-120, and 200-500 ms, respectively. The most profound change during muscle growth was a shift toward faster relaxation in the intermediate time constant, T(21). It decreased by approx. 24% in all four muscle types during the period from 25 to 150 kg live weight. Determination of dry matter, fat, and protein content in the muscles showed that the changes in relaxation time of the intermediate time constant, T(21), during growth should be ascribed mainly to a change in protein content, as the protein content explained 77% of the variation in the T(21) time constant. Partial least squares (PLS) regression revealed validated correlations in the region of 0.58 to 0.77 between NMR transverse relaxation data and muscle development for all the four muscle types, which indicates that NMR relaxation measurements may be used in the prediction of muscle developmental stage. 相似文献
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Niels Vigand Pedersen 《Journal of Functional Analysis》1981,43(3):368-393
For an arbitrary separable locally compact group G we exhibit a canonical Borel subset of the quasi-dual (with the Mackey Borel structure), such that is a standard Borel space in the induced Borel structure, and such that the canonical measure for the left regular representation λGof G is concentrated on . On the basis of this we discuss the (non-unimodular) “Plancherel theorem.” 相似文献
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