Model Calculations of Radiation-Induced Damage in Thymine Derivatives

When the thymine base is oxidized, the resulting cation may deprotonate reversibly at N3, or irreversibly at >C5-CH₃. In all thymine derivatives studied so far in the solid state, there is always a significant concentration of a radical formed by net H-abstraction from the >C5-CH₃. DFT calculations on this allyl-like radical are in good agreement with the experimental results for both the isotropic and anisotropic hyperfine couplings. There is a tendency for the thymine cation to deprotonate at N3 in solution. Calculations on the N3 deprotonated thymine cation yield two structures, one planar radical with an unusually large N1-C2 bond length, and one nonplanar radical with the N3 more than 25° out of the molecular plane. Calculations show that the structure with the lowest energy is the allyl-like radical.     

多类型过程的耦合问题

本文阐述了多类型过程的定义及反应到实践中的具体模型 ,并且证明最优耦合的充要条件 .     

Noncommutative integrable coupling system of TC equation hierarchy

A noncommutative version of the TC soliton equation hierarchy is presented, which possesses the zero curvature representation. Then, we show that noncommutative (NC) TC equation can be derived from the noncommutative (anti-)self-dual Yang-Mills equation by reduction. Finally, an integrable coupling system of the NC TC equation hierarchy is constructed by using of the enlarged Lax pairs.     

1H NMR spectra. Part 29§: proton chemical shifts and couplings in esters—the conformational analysis of methyl γ‐butyrolactones

The ¹H NMR spectra of 35 cyclic and acyclic esters are analysed to give the ¹H chemical shifts and couplings. The substituent chemical shifts of the ester group were analysed using three‐bond (γ) effects for near protons and the electric field, magnetic anisotropy and steric effect of the ester group for more distant protons. The electric field is calculated from the partial atomic charges on the O?C = O atoms, and the asymmetric magnetic anisotropy of the carbonyl group acts at the midpoint of the C = O bond. The values of the anisotropies Δχ_parl and Δχ_perp were for the aliphatic esters 10.35 and ?18.84 and for the conjugated esters 7.33 and ?15.75 (×10^?6 ų/molecule). The oxygen steric coefficients found were 104.4 (aliphatic C = O), 45.5 (aromatic C = O) and 16.0 (C–O) (×10^?6 Å⁶/molecule). After parameterisation, the overall RMS error for the data set of 280 entries was 0.079 ppm. The strongly coupled ¹H NMR spectra of the 2‐methyl, 3‐methyl and 4‐methyl γ‐butyrolactones were analysed and the methyl conformational equilibrium obtained from the observed couplings. The observed versus calculated density functional theory (DFT) ΔG(ax‐eq) was 1.0 (1.01), 0.34 (0.54) and 0.65 (0.71) kcal/mol res. The shielding effect of a methyl cis to a proton in the five‐membered lactone rings is ?0.40 ±0.05 ppm and deshielding trans effect 0.12 ±0.05 ppm, which is common to both five and six membered rings. The cis/trans isomerism in the vinyl esters methyl acrylate, crotonate and methacrylate and methyl furoate was examined using the ¹H chemical shifts. The calculated shifts of both the cis and trans isomers were in good agreement with the observed shifts. Copyright © 2012 John Wiley & Sons, Ltd.     

利用李代数构造非线性可积及双可积哈密顿耦合

With the help of a Lie algebra,two kinds of Lie algebras with the forms of blocks are introduced for generating nonlinear integrable and bi-integrable couplings.For illustrating the application of the Lie algebras,an integrable Hamiltonian system is obtained,from which some reduced evolution equations are presented.Finally,Hamiltonian structures of nonlinear integrable and bi-integrable couplings of the integrable Hamiltonian system are furnished by applying the variational identity.The approach presented in the paper can also provide nonlinear integrable and bi-integrable couplings of other integrable system.     

UC Pd: A New Form of Pd/C for Sonogashira Couplings

Screening of different sources of Pd/C shows reagents of highly variable nanoparticle sizes and oxidation states of the metal. Typically, catalysts with higher surface area are viewed as likely to be the more reactive. In this paper a new form of Pd/C, “UC Pd” is described that is shown to contain larger nanoparticles yet it is the most reactive catalyst of those sold commercially for Sonogashira coupling reactions. UC Pd functions efficiently in the absence of a copper co‐catalyst, under very mild and “green” conditions using inexpensive 95 % EtOH at 50 °C. It is also the only form of Pd/C that can be recycled. In side‐by‐side reactions with several commercially available forms of Pd/C, none compete successfully with UC Pd under standardized conditions. Physical data obtained from extensive surface analysis using TEM, XRD, XPS, and CO‐TPD measurements lead to an explanation behind the unique reactivity of this new recyclable form of Pd/C.     

Optimized 1D double quantum filter NMR experiments

We propose and demonstrate a 1D pulse sequence to convert double quantum coherence (DQC) of y phase with optimal efficiency, relying on single transition selection. Our sequence has a larger high-sensitivity bandwidth with respect to the coupling, compared to other reconversion strategies. A modified version of the new pulse sequence provides the missing chemical shift and coupling information, at minor cost in sensitivity. Application to 1D 13C INADEQUATE is demonstrated.Our new sequence is also applied to quadrupole coupled spin-1 systems, such as 2H in lyotropic phase. Performance of the sequence may be fine-tuned by pulse flip angle optimization, taking into account relaxation effects.     

An integrable coupling hierarchy of the Mkdv_integrable systems, its Hamiltonian structure and corresponding nonisospectral integrable hierarchy

A four-by-four matrix spectral problem is introduced, locality of solution of the related stationary zero curvature equation is proved. An integrable coupling hierarchy of the Mkdv_integrable systems is presented. The Hamiltonian structure of the resulting integrable coupling hierarchy is established by means of the variational identity. It is shown that the resulting integrable couplings are all Liouville integrable Hamiltonian systems. Ultimately, through the nonisospectral zero curvature representation, a nonisospectral integrable hierarchy associated with the resulting integrable couplings is constructed.