Strategies for organic impurity quantification by H NMR spectroscopy: Constrained total-line-shape fitting

A constrained total-line-shape (CTLS) fitting strategy for organic impurity analysis from ¹H NMR spectra was developed and assessed by studying two examples. In general, total-line-shape fitting allows integration of overlapping lines without suffering from baseline artifacts as much as traditional integration methods. It is shown here that the constrained total-line-shape fitting, where the spectral structures of the multiplets to be fitted are taken into account in form of constraints, allows quantification of seriously overlapping lines and when the signals are close to the root of major signals. Also, a method for removal of ¹³C satellite signals is described. The results indicate that our approach significantly improves the usefulness of qNMR in impurity analysis and that impurity levels of 0.1 mol%, which in some cases means down to 0.01 wt%, can be easily determined with relative standard error smaller than 10%.     

Cu（OAc）2/Pyrimidines-Catalyzed Cross-coupling Reactions of Aryl Iodides and Activated Aryl Bromides with Alkynes under Aerobic, Solvent-free and Palladium-free Conditions

Excellent results have been achieved in the Cu（OAc）2-catalyzed Sonogashira cross-couplings of aryl iodides and activated aryl bromides utilizing TBAF （tetrabutylammonium fluoride） as the base and 4,6-dimethoxypyrimidin-2-amine as the ligand. It is noteworthy that the reaction is conducted under aerobic, solvent-free and palladium-free conditions.     

Analysis of positron diffusion data

In this paper we present and discuss experimental methods to determine the positron diffusion coefficient from slow positron beam measurements. We also evaluate the use of the annihilation line Doppler-broadening technique in positron diffusion measurements, as compared on the more commonly used method of positronium fraction. The effects of incomplete positron thermalization and uncertainties of the positron implantation profile at low-positron incident energies to the measured data are discussed. We apply the presented methods to the model case of A1(110) system in the temperature range from 20 to 500 K. This data shows that Doppler-broadening and positronium fraction measurements give consistent results for the positron diffusion coefficient in A1(110), where D₊(300 K) = 1.7(2) cm²/s with the temperature dependence D₊ T ^–0.62(3).     

1H NMR spectral analysis and conformational behavior of n‐alkanes in different chemical environments

Alkyl chains are common structural units, for example in lipids, and their ¹H NMR spectral parameters offer valuable information about their conformational behavior in solvent environment. Even the spectra of short n‐alkanes are complex, which is obviously a reason why their accurate spectral analyses have not been reported before. The present study reports the quantum mechanical analysis of ¹H NMR spectra of n‐butane, n‐pentane, n‐hexane, and n‐heptane. The spectral parameters were used to characterize the conformational behavior of n‐alkanes. The temperature dependence analysis of coupling constants suggests that the enthalpy difference between the gauche (g) and trans (t) conformations (ΔH_g) of n‐butane in chloroform is 2.55–2.85 kJ mol^?1. The difference between the trans–gauche (tg) and all‐trans (tt) conformers of n‐pentane (ΔH_tg) seems to be 0.1–0.2 kJ mol^?1 higher. The coupling constant information shows that the t_n conformations become more favored with longer chains, although not only for energetic reasons but also partly because the g⁺g^‐ arrangements become sterically unfavorable, which decreases the number of favorable g_n‐type conformations. The analysis of the ¹H NMR spectra of n‐pentane and n‐hexane in solvents representing different chemical environments indicates that polar and spherical dimethyl sulfoxide favors clearly the g conformations, whereas n‐hexane‐d₁₄ favors slightly the extended t_n conformation. In addition to the intrinsic scientific importance for NMR spectral parameter prediction and molecular modeling in solution, the results provide some insights to behavior of hydrocarbon chains and their spectra in different chemical environments. Copyright © 2012 John Wiley & Sons, Ltd.     

AC Alternating-Current Loss Analyses of a Thin High-Temperature Superconducting Tube Carrying AC Transport Current in AC External Magnetic Field

Numerical simulations on the AC loss characteristics in a thin high-temperature superconducting （HTS） tube are presented. Geometry of the HTS conductor is modeled as a tube with negligible thickness, and assumed to carry a transport current with the same phase as an AC externally applied magnetic field perpendicular to the axis. Based on the classical theory of AC loss with the Bean critical current model, the distribution of critical current density jc and AC loss Q are obtained by means of numerical analysis. The results are in very good agreement with experiments. A double-peak profile is observed in the curve of the critical current density distribution along the azimuth angle. This numerical simulation method is suitable for a thin HTS tube, which may be applicable on a thin tube configuration consisting of coated superconductors.     

C_2H_2,C_2H_4与K在Ru(100)表面上共吸附的UPS研究

利用紫外光电子谱 (UPS)对乙烯 (C2 H4)和乙炔 (C2 H2 )气体在Ru(10 10 )表面的吸附及与K的共吸附进行了研究 ,实验结果表明 :当衬底温度超过 2 0 0K ,乙烯即发生脱氢反应后 ,σCH 和σCC 能级均向高结合能方向移动 .在室温下 ,σCH和σCC 能级位置与乙炔在Ru(10 10 )表面的吸附时的分子能级完全一致 .乙烯发生脱氢反应后的主要产物为乙炔 .衬底温度从 12 0K升到室温 ,Ru(10 10 )表面上乙炔的σCH 和σCC 能级均未发现变化 .室温下乙炔仍然可以在Ru(10 10 )表面以分子状态稳定吸附 .在有K的Ru(10 10 )表面上 ,室温时σCC谱峰几乎消失 .碱金属K的存在促进了乙炔的分解 .     

单体对聚乙烯醇乳化行为的影响及大孔材料的制备

以聚乙烯醇-1788(PVA-1788)为表面活性剂,研究了3种甲基丙烯酸酯系列水溶性单体对水包二氧化碳(C/W)型高内相乳液(HIPE)的形成及稳定性的影响,然后采用HIPE模板法制备了两种大孔材料.结果表明,甲基丙烯酰氧乙基三甲基氯化铵的存在对C/W型HIPE的形成及稳定影响较小,所得乳液最高能稳定48 h;而甲基...