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171.
2,4-Difluorotoluene is unusual among hydrofluorocarbons because it is shaped like the DNA base thymine. It was first synthesised as a nucleotide analogue and incorporated into DNA a decade ago. Although it is a nonpolar molecule, it was found to be replicated by DNA polymerase enzymes as if it were thymine. We concluded that replication of DNA base pairs can occur without Watson-Crick hydrogen bonds, and hypothesised that steric effects, rather than these hydrogen bonds, were the main arbiters of DNA replication fidelity. A debate was initiated then, with claims by some that the molecule is polar and forms hydrogen bonds with adenine, thus supporting the hydrogen bonding theory of DNA replication. Here we discuss the evolution of this debate, and reflect on the relevant data that have since come from hundreds of papers and dozens of laboratories. Although discussion on this topic continues, the steric hypothesis for DNA replication is now widely accepted among biochemists, and the changing paradigm has been reflected in textbooks. 相似文献
172.
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
173.
Mark S. Herman 《Annales Henri Poincare》2010,11(1-2):23-67
We perform a rigorous mathematical analysis of the bending modes of a linear triatomic molecule that exhibits the Renner–Teller effect. Assuming the potentials are smooth, we prove that the wave functions and energy levels have asymptotic expansions in powers of ${\epsilon}$ , where ${\epsilon^4}$ is the ratio of an electron mass to the mass of a nucleus. To prove the validity of the expansion, we must prove various properties of the leading order equations and their solutions. The leading order eigenvalue problem is analyzed in terms of a parameter ${\tilde{b}}$ , which is equivalent to the parameter originally used by Renner. For ${0< \tilde{b}< 1}$ , we prove self-adjointness of the leading order Hamiltonian, that it has purely discrete spectrum, and that its eigenfunctions and their derivatives decay exponentially. Perturbation theory and finite difference calculations suggest that the ground bending vibrational state is involved in a level crossing near ${\tilde{b}=0.925}$ . We also discuss the degeneracy of the eigenvalues. Because of the crossing, the ground state is degenerate for ${0< \tilde{b}< 0.925}$ and non-degenerate for ${0.925< \tilde{b}< }$ . 相似文献
174.
175.
We report results on the geometrical statistics of the vorticity vector obtained from experiments in electromagnetically forced rotating turbulence. A range of rotation rates Ω is considered, from non-rotating to rapidly rotating turbulence with a maximum background rotation rate of Ω = 5 rad/s (with Rossby number much smaller than unity). Typically, the Taylor-scale Reynolds number in our experiments is around Reλ ≈ 100. The measurement volume is located in the centre of the fluid container above the bottom boundary layer, where the turbulent flow can be considered locally statistically isotropic and horizontally homogeneous for the non-rotating case, see L.J.A. van Bokhoven, H.J.H. Clercx, G.J.F. van Heijst, and R.R. Trieling, Experiments on rapidly rotating turbulent flows, Phys. Fluids 21 (2009) 096601. Based on the full set of velocity derivatives, measured in a Lagrangian way by three-dimensional (3D) particle tracking velocimetry, we have been able to quantify statistically the effect of system rotation on several flow properties. For the range of rotation rates considered, the experimental results show how the turbulence evolves from almost isotropic 3D turbulence (Ω ? 0.2 rad/s) to quasi-two-dimensional turbulence (Ω ≈ 5.0 rad/s), and how this is reflected by several statistical quantities. In particular, we have studied the orientation of the vorticity vector with respect to the three eigenvectors of the local strain rate tensor and with respect to the vortex stretching vector. Additionally, we have quantified the role of system rotation on the self-amplification terms of the enstrophy and strain rate equations and the direct contribution of the background rotation on these evolution equations. The main effect of background rotation is the strong reduction of extreme events and related (strong) reduction of the skewness of PDFs of several quantities, for example, the intermediate eigenvalue of the strain rate tensor and the enstrophy self-amplification term. 相似文献
176.
Alexander Lutz Linsey Lapeire Tuan Nguyen-Minh Kim Verbeken Herman Terryn Iris De Graeve 《Surface and interface analysis : SIA》2019,51(12):1251-1259
The occurrence of preferential grain etching (PGE) during alkaline etching of aluminum extrusion alloys from the 6XXX series is often linked to the presence of certain impurity elements such as zinc, causing an undesired etching appearance. In the presented work, an additional culprit in this context is identified, which has not been investigated yet. A clear relation between PGE and the presence of a subsurface shear layer is identified for extruded Al 6060 alloys containing 0.02 and 0.06 wt% Zn. This shear layer can be distinguished from the bulk of the metal by its difference in crystallographic texture as visualized by electron backscatter diffraction (EBSD). For the Zn enriched alloy, the <111>//ND grains are etched away faster than grains with other orientations, resulting in the grainy appearance typical for PGE. Independent of the Zn content in the alloy, once the shear layer is removed and <111>//ND grains are practically absent on the new surface, the depths variations caused by preferential etching disappear. Instead, the surface of the alloy is attacked uniformly by the caustic etch bath. 相似文献
177.
Dr. Stefan van der Vorm Thomas Hansen Dr. Erwin R. van Rijssel Rolf Dekkers Jerre M. Madern Prof. Dr. Herman S. Overkleeft Dr. Dmitri V. Filippov Prof. Dr. Gijsbert A. van der Marel Dr. Jeroen D. C. Codée 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(29):7149-7157
The 3D shape of glycosyl oxocarbenium ions determines their stability and reactivity and the stereochemical course of SN1 reactions taking place on these reactive intermediates is dictated by the conformation of these species. The nature and configuration of functional groups on the carbohydrate ring affect the stability of glycosyl oxocarbenium ions and control the overall shape of the cations. We herein map the stereoelectronic substituent effects of the C2-azide, C2-fluoride and C4-carboxylic acid ester on the stability and reactivity of the complete suite of diastereoisomeric furanoses by using a combined computational and experimental approach. Surprisingly, all furanosyl donors studied react in a highly stereoselective manner to provide the 1,2-cis products, except for the reactions in the xylose series. The 1,2-cis selectivity for the ribo-, arabino- and lyxo-configured furanosides can be traced back to the lowest-energy 3E or E3 conformers of the intermediate oxocarbenium ions. The lack of selectivity for the xylosyl donors is related to the occurrence of oxocarbenium ions adopting other conformations. 相似文献
178.
A. Jolly Y. Benilan E. Cané L. Fusina F. Tamassia A. Fayt S. Robert M. Herman 《Journal of Quantitative Spectroscopy & Radiative Transfer》2008,109(17-18):2846-2856
The global analysis of published high-resolution vibration–rotation spectra of 12C2HD in the bending spectral range is presented, resulting in an extension of the known vibration–rotation assignments, including a new band 2v4+v5←2v4 (IΠ←Δ). Experimental integrated band intensities are reported in the range from 25 to 2.5 μm, and both v4 and v5 bending fundamentals are simulated line by line. An extensive line list is produced in the bending energy range, to supply previously missing information in databases. 相似文献
179.
We show that, in string models with the minimal supersymmetric standard model residing on D-branes, the bino mass can be generated in a geometrically separated hidden sector. Hypercharge mediation thus naturally teams up with anomaly mediation. The mixed scenario predicts a distinctive yet viable superpartner spectrum, provided that the ratio alpha between the bino and gravitino mass lies in the range 0.05 < or = |alpha| < or = 0.25 and m(3/2) > or = 35 TeV. We summarize some of the experimental signatures of this scenario. 相似文献
180.
Jeurissen R de Jong J Reinten H van den Berg M Wijshoff H Versluis M Lohse D 《The Journal of the Acoustical Society of America》2008,123(5):2496-2505
Piezo-driven inkjet systems are very sensitive to air entrapment. The entrapped air bubbles grow by rectified diffusion in the ink channel and finally result in nozzle failure. Experimental results on the dynamics of fully grown air bubbles are presented. It is found that the bubble counteracts the pressure buildup necessary for the droplet formation. The channel acoustics and the air bubble dynamics are modeled. For good agreement with the experimental data it is crucial to include the confined geometry into the model: The air bubble acts back on the acoustic field in the channel and thus on its own dynamics. This two-way coupling limits further bubble growth and thus determines the saturation size of the bubble. 相似文献