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101.
102.
The hydrogen-abstracted radicals from the adenine-uracil (AU) base pair have been studied at the B3LYP/DZP++ level of theory. The A(N9)-U and A-U(N1) radicals, which correspond to hydrogen-atom abstraction at the adenine N9 and uracil N1 atoms, respectively, were predicted to be the two lowest-lying among the nine (AU-H) radicals studied in this study. The removal of the amino hydrogen of the adenine moiety that forms a hydrogen bond with the uracil O4 atom in the AU pair resulted in radical A(N6a)-U, which has the smallest base-pair dissociation energy, 5.9 kcal mol(-1). This radical is more likely to dissociate into the two isolated bases than to recover the hydrogen bond with the O4 atom through N6-H bond rotation along the C6-N6 bond. In general, the radicals generated by C-H bond breaking were higher in energy than those arising from N-H bond cleavage, because the unpaired electrons in the carbon-centered radicals were mainly localized on the carbon atom from which the hydrogen atom was removed. However, the highest-lying radical was found to arise from removal of the N3 hydrogen of uracil. The most remarkable structural feature of this radical is a very short C-H...O distance of 2.094 A, consistent with a substantial hydrogen bond. Although this radical lost the N1...H-N3 hydrogen bond between the two bases, its dissociation energy was predicted to be 12.9 kcal mol(-1), similar to that of the intact AU base pair. This is due to the transfer of electron density from the adenine N1 atom to the uracil N3 atom. 相似文献
103.
Liddle BJ Silva RM Morin TJ Macedo FP Shukla R Lindeman SV Gardinier JR 《The Journal of organic chemistry》2007,72(15):5637-5646
The reaction between 2-pyrazolyl-4-X-anilines, H(pzAnX), (X = para-OMe (L1), Me (L2), H (L3), Cl (L4), CO2Et (L5), CF3 (L6), CN (L7)) and triphenylboron in boiling toluene affords the respective, highly emissive N,N'-boron chelate complexes, BPh2(pzAnX) (X = para-OMe (1), Me (2), H (3), Cl (4), CO2Et (5), CF3 (6), CN (7)) in high yield. The structural, electrochemical, and photophysical properties of the new boron complexes can be fine-tuned by varying the electron-withdrawing or -donating power of the para-aniline substituent (delineated by the substituent's Hammett parameter). Those complexes with electron-withdrawing para-aniline substituents such as CO2Et (5), CF3 (6), and CN (7) have more planar chelate rings, more 'quinoidal' distortion in the aniline rings, greater chemical stability, higher oxidation potentials, and more intense (phiF = 0.81 for 7 in toluene), higher-energy (blue) fluorescent emission compared to those with electron-donating substituents. Thus, for 1 the oxidation potential is 0.53 V versus Ag/AgCl (compared to 1.12 V for 7), and the emission is tuned to the yellow-green but at an expense in terms of lower quantum yields (phiF = 0.07 for 1 in toluene) and increased chemical reactivity. Density functional calculations (B3LYP/6-31G*) on PM3 energy-minimized structures of the ligands and boron complexes reproduced experimentally observed data and trends and provided further insight into the nature of the electronic transitions. 相似文献
104.
105.
Willi A. Brand Tyler B. Coplen Anita T. Aerts‐Bijma J. K. Böhlke Matthias Gehre Heike Geilmann Manfred Gröning Henk G. Jansen Harro A. J. Meijer Stanley J. Mroczkowski Haiping Qi Karin Soergel Hilary Stuart‐Williams Stephan M. Weise Roland A. Werner 《Rapid communications in mass spectrometry : RCM》2009,23(7):999-1019
Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high‐temperature conversion techniques (HTC) a in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125‰, an artificially enriched reference water (δ18O of +78.91‰) and two barium sulfates (one depleted and one enriched in 18O) were prepared and calibrated relative to VSMOW2 b and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded:
The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3‐fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for δ18O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen‐isotope ratios (δ18O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ18O values of two or more internationally distributed nitrates (USGS34, IAEA‐NO‐3, and USGS35), sulfates (IAEA‐SO‐5, IAEA‐SO‐6, and NBS 127), or organic material (IAEA‐601 benzoic acid, IAEA‐602 benzoic acid, and IAEA‐600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the δ18O values at a later time should it become necessary. The high‐temperature reduction technique for analyzing δ18O and δ2H is not as widely applicable as the well‐established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
Reference material | δ18O and estimated combined uncertainty c |
---|---|
IAEA‐602 benzoic acid | +71.28 ± 0.36‰ |
USGS35 sodium nitrate | +56.81 ± 0.31‰ |
IAEA‐NO‐3 potassium nitrate | +25.32 ± 0.29‰ |
IAEA‐601 benzoic acid | +23.14 ± 0.19‰ |
IAEA‐SO‐5 barium sulfate | +12.13 ± 0.33‰ |
NBS 127 barium sulfate | +8.59 ± 0.26‰ |
VSMOW2 water | 0‰ |
IAEA‐600 caffeine | ?3.48 ± 0.53‰ |
IAEA‐SO‐6 barium sulfate | ?11.35 ± 0.31‰ |
USGS34 potassium nitrate | ?27.78 ± 0.37‰ |
SLAP water | ?55.5‰ |
106.
We estimate d-dimensional least squares approximations of an arbitrary d-regular measure μ via discrete curvatures of d+2 variables. The main result bounds the least squares error of approximating μ (or its restrictions to balls) with a d-plane by an average of the discrete Menger-type curvature over a restricted set of simplices. Its proof is constructive and even suggests an algorithm for an approximate least squares d-plane. A consequent result bounds a multiscale error term (used for quantifying the approximation of μ with a sufficiently regular surface) by an integral of the discrete Menger-type curvature over all simplices. The preceding paper (part I) provided the opposite inequalities of these two results. This paper also demonstrates the use of a few other discrete curvatures which are different from the Menger-type curvature. Furthermore, it shows that a curvature suggested by Léger (Ann. Math. 149(3), pp. 831–869, 1999) does not fit within our framework. 相似文献
107.
Taylor Ringia EA Tyler PC Evans GB Furneaux RH Murkin AS Schramm VL 《Journal of the American Chemical Society》2006,128(22):7126-7127
Transition state analogues of PNP, the Immucillins and DADMe-Immucillins, were designed to match transition state features of bovine and human PNPs, respectively. The inhibitors with or without the hydroxyl and hydroxymethyl groups of the substrate demonstrate that inhibitor geometry mimicking that of the transition state confers binding affinity discrimination. This finding is remarkable since crystallographic analysis indicates complete conservation of active site residues and contacts to ligands in human and bovine PNPs. 相似文献
108.
Burnham CJ Petersen MK Day TJ Iyengar SS Voth GA 《The Journal of chemical physics》2006,124(2):024327
Ion-water-cluster properties are investigated both through the multistate empirical valence bond potential and a polarizable model. Equilibrium properties of the ion-water clusters H+(H2O)100, Na+(H2O)100, Na+(H2O)20, and Cl-(H2O)17 in the temperature region 100-450 K are explored using a hybrid parallel basin-hopping and tempering algorithm. The effect of the solid-liquid phase transition in both caloric curves and structural distribution functions is investigated. It is found that sodium and chloride ions largely reside on the surface of water clusters below the cluster melting temperature but are solvated into the interior of the cluster above the melting temperature, while the solvated proton was found to have significant propensity to reside on or near the surface in both the liquid- and solid-state clusters. 相似文献
109.
Chau Le Tyler E. Bruns Daniel A. Tortorelli 《Journal of the mechanics and physics of solids》2012,60(2):351-378
We describe a systematic approach to design material microstructures to achieve desired energy propagation in a two-phase composite plate. To generate a well-posed topology optimization problem we use the relaxation approach which requires homogenization theory to relate the macroscopic material properties to the microstructure, here a sequentially ranked laminate. We introduce an algorithm whereby the laminate layer volume fractions and orientations are optimized at each material point. To resolve numerical instabilities associated with the dynamic simulation and constrained optimization problem, we filter the laminate parameters. This also has the effect of generating smoothly varying microstructures which are easier to manufacture. To demonstrate our algorithm we design microstructure layouts for tailored energy propagation, i.e. energy focus, energy redirection, energy dispersion and energy spread. 相似文献
110.