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41.
Beevers AP Fettes KJ Sabbagh G Murad FK Arnold JR Cosstick R Fisher J 《Organic & biomolecular chemistry》2004,2(1):114-119
High-resolution NMR spectroscopy has been used to establish the conformational consequences of the introduction of a single 3[prime or minute]-S-phosphorothiolate link in the DNA strand of a DNA : RNA hybrid. These systems are of interest as potential antisense therapeutic agents. Previous studies on similarly modified dinucleotides have shown that the conformation of the sugar to which the sulfur is attached shifts to the north (C(3[prime or minute])-endo/C(2[prime or minute])-exo). Comparisons made between NOESY cross-peak intensities, and coupling constants from PE-COSY spectra, for both non-modified and modified duplexes confirm that this conformational shift is also present in the double helical oligonucleotide system. In addition it is noted that in both the dinucleotides and the modified duplex, the conformation of the sugar ring 3[prime or minute] to the site of modification is also shifted to the north. That this pattern is observed in the small monomeric system as well as the larger double helix is suggestive of some pre-ordering of the sequences. The conclusion is supported by consideration of the (1)H chemical shifts of the heterocyclic bases near the site of the modification. The enhanced stability that these conformational changes should bring was confirmed by UV thermal melting studies. Subsequently a series of singly and doubly 3[prime or minute]-S-phosphorothiolate-modified duplexes were investigated by UV. The results are indicative of an additive effect of the modification with thermodynamic benefit being derived from alternate spacing of two modified linkers. 相似文献
42.
Probing the water coordination of protein-targeted MRI contrast agents by pulsed ENDOR spectroscopy.
Stephan G Zech Wei-Chuan Sun Vincent Jacques Peter Caravan Andrei V Astashkin Arnold M Raitsimring 《Chemphyschem》2005,6(12):2570-2577
A novel methodology based on electron-nuclear double resonance (ENDOR) spectroscopy is used for the direct determination of the water coordination number (q) of gadolinium-based magnetic resonance imaging (MRI) contrast agents. Proton ENDOR spectra can be obtained at approximately physiological concentrations for metal complexes in frozen aqueous solutions either in the presence or absence of protein targets. It is shown that, depending on the structure of the co-ligand, the water hydration number of a complex in aqueous solution can be significantly different to when the complex is noncovalently bound to a protein. From the ENDOR spectra of the exchangeable protons, precise information on the metal-proton distance can be derived as well. These essential parameters directly correlate with the efficacy of MRI contrast agents and should therefore aid the development of novel, highly efficient compounds targeted to various proteins. 相似文献
43.
Grotjahn DB Van S Combs D Lev DA Schneider C Incarvito CD Lam KC Rossi G Rheingold AL Rideout M Meyer C Hernandez G Mejorado L 《Inorganic chemistry》2003,42(10):3347-3355
Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions. 相似文献
44.
The Ramanujan Journal - We study fixed points in integer partitions viewed, respectively, as weakly increasing or weakly decreasing structures. A fixed point is a point with value i in position i.... 相似文献
45.
Hans-Joachim Arnold 《Results in Mathematics》1995,28(3-4):195-208
To characterize E. D. Sontag’s system of axioms for control-systems in a more operative manner we consider an equivalent algebraic structure, which we name Regel- Relative. 相似文献
46.
Makins NC Ent R Chapman MS Hansen J Lee K Milner RG Nelson J Arnold RG Bosted PE Keppel CE Lung A Rock SE Spengos M Szalata ZM Tao LH White JL Coulter KP Geesaman DF Holt RJ Jackson HE Papavassiliou V Potterveld DH Zeidman B Arrington J Beise EJ Belz E Filippone BW Gao H Lorenzon W Mueller B McKeown RD O'Neill TG Epstein M Margaziotis DJ Napolitano J Kinney E Anthony PL van Bibber K Dietrich FS Gearhart RA Patratos GG Kuhn SE van den Brand JF Bulten H Jones CE 《Physical review letters》1994,72(13):1986-1989
47.
48.
Richard Ley D. Hagena D. Weil G. Werth W. Arnold H. Schneider 《Hyperfine Interactions》1994,89(1):327-341
Electric dipole transitions in the microwave range have been induced between the fine-structure levels of positronium in the excited staten=2. As an indication of the transitions, we used the increase in Lyman- radiation when the metastable 23S1-level is depopulated. The results for the transitions 23S123P0,1,2 are
0=18499.65±1.20±4.00 MHz,
1=13012.42 ±0.65±1.54 MHz and
2=8624.38±0.54±1.40 MHz. The first error is statistical and the second systematic. The precision of the present measurement has improved by a factor of 3, compared to previous data. Recent bound state QED-calculations have been extended to the orderR
t8
4ln
–1. The not yet completely calculated orderR
t8
4 is estimated to contribute less than 1 MHz. Our experimental results are in good agreement with theory. By applying a weak magnetic field, we were able to observe the transition 23S121P1 which is strictly forbidden byC-invariance in zero field. Our result, corrected for Zeeman- and motional Starkeffect, is
3=11180.0±5.0±4.0 MHz. An upper limit for theC-violating matrix element of
MHz could be deduced. Our experiment used moderated slow positrons from the bremsstrahlung and pair production of a pulsed electron linear accelerator (TEPOS facility at the university of Giessen). 相似文献
49.
50.