NMR and theoretical study on the linking properties of peroxovanadium(V) complexes with the 3-aminomethyl-pyridine derivatives

To understand the substitution effects of 3-aminomethyl-pyridine on the reaction equilibrium, the interactions between a series of 3-aminomethyl-pyridine derivatives and peroxovanadium(V) complex [OV(O₂)₂(D₂O)]^?/[OV(O₂)₂(HOD)]^? in solution were explored by the combined use of multinuclear (¹H, ¹³C, and ⁵¹V) magnetic resonance spectroscopy together with HSQC in 0.15 M NaCl ionic medium for mimicking the physiological conditions. Some direct NMR data are given for the first time. The relative reactivity among the 3-aminomethyl-pyridine derivative ligands are N-(pyridin-3-ylmethyl)acetamide (1) ≈ N-(pyridin-3-ylmethyl)propionamide (2) > N-(pyridin-3-ylmethyl)pivalamide (3) > t-butyl(pyridin-3-ylmethyl)carbamate (4). The competitive coordination results in the formation of a series of new six-coordinate peroxovanadium species [OV(O₂)₂L]^? (L = 1–4). The results of density functional calculations indicated that the solvation effects play an important role in these reactions, providing a reasonable explanation on the relative reactivity of the 3-aminomethyl-pyridine derivatives.     

A Practical High-Energy Cathode for Sodium-Ion Batteries Based on Uniform P2-Na0.7CoO2 Microspheres

Layered metal oxides have attracted increasing attention as cathode materials for sodium-ion batteries (SIBs). However, the application of such cathode materials is still hindered by their poor rate capability and cycling stability. Here, a facile self-templated strategy is developed to synthesize uniform P2-Na_0.7CoO₂ microspheres. Due to the unique microsphere structure, the contact area of the active material with electrolyte is minimized. As expected, the P2-Na_0.7CoO₂ microspheres exhibit enhanced electrochemical performance for sodium storage in terms of high reversible capacity (125 mAh g⁻¹ at 5 mA g⁻¹), superior rate capability and long cycle life (86 % capacity retention over 300 cycles). Importantly, the synthesis method can be easily extended to synthesize other layered metal oxide (P2-Na_0.7MnO₂ and O3-NaFeO₂) microspheres.     

Quantum reaction dynamics of C(1D) + HD → CH(CD) + D(H) on the ground state potential energy surface

We present accurate quantum dynamic calculations of the reaction C(¹D) + HD on the latest version of the potential energy surface [Zhang et al., J. Chem. Phys. 140, 234301 (2014)]. Using a Chebyshev real wave packet method with full Coriolis coupling, we obtain the initial state‐specified ( ) reaction probabilities, integral cross sections, and rate constants. The resulting probabilities display oscillatory structures due to numerous long‐lived resonances supported by the deep potential well. The calculated rate constants and CD/CH product branching ratio at room temperature are in reasonably good agreement with the experimental measurements.     

高效固体酸SBA-15-Zr(OTf)3催化胺或醇开环环氧化合物

通过简单的一锅两步法制备了三氟金属(铝,钛,锆)接枝介孔SBA-15 (AlTf/S,TiTf/S,ZrTf/S)固体酸材料,并通过XRD,N2吸附,TGA,FTIR,原位吡啶FTIR和元素分析对这些材料进行了详细的表征.其中,ZrTf/S能够高效催化环氧化物温和条件下被胺或醇开环生成对应β-氨基醇或β-烷氧基醇,并且催化剂能循环利用.ZrTf/S相较于AlTf/S和TiTf/S酸性最强,因而催化活性也最高.     

液晶润滑添加剂的减摩作用机理研究

液晶润滑添加剂具有优良的减摩性能，但在已有的文献报道中涉及其减摩机理的研究内容却还很少。因此，利用向列型液晶材料已氧基苯甲酸和正辛基苯甲酸作为ＨＵ－２０汽轮机油的添加剂，在给定的压力、速度和温度条件下于Ｆａｌｅｘ试验机上进行了液晶的减摩性能试验研究，并且用Ｘ射线衍射、俄歇电子能谱和扫描电子显微镜等技术，对溶解于矿物油中的液晶结构、磨损表层的元素组成及其表面形貌作了观察、分析与研究，在此基础上又对液     

点、线接触真实粗糙表面的弹流润滑研究

本文给出了点、线接触的真实粗糙表面的微弹流数值解。在给定随机粗糙表面样本后,求解大小不同的载荷和粗糙的弹流问题。从计算结果可以看出,由于Reynolds方程中速度项的作用,在表面对应粗糙的位置处引起了压力变化,从而因其产生的弹性变形使粗糙变得平滑。对此光滑表面解可以看出,因粗糙引起的压力和膜厚的变化在光滑解附近波动。载荷较大时,压力分节接近固体接触情况。     

结合部切向接触刚度分形模型研究

根据球体与平面接触的切向接触刚度和粗糙表面的接触分形理论，从理论上首次建立了结合部切向接触刚度分形模型，该模型具有尺度独立性。通过对所建模型的数字仿真，直观地给出了结合部切向接触刚度与其影响因素之间的非线性关系，并与实验研究结果具有较好的一致性，从而说明了该模型是合理的。     

铸铁材料在边界润滑条件下形成薄片状磨屑的塑性流动机制

本文在铸铁材料油润滑线接触滑动磨损状态研究的基础上,对边界润滑区典型的薄片状磨屑之形成过程进行了考察。通过对磨损表面的几何形貌、磨屑的形态和内部显微组织变化的分析,提出了薄片状磨屑的塑性流动形成机制。作者认为,薄片状磨屑的形成是磨损表面材料在局部应力和摩擦热的作用下以3种方式发生塑性流动的结果:当摩擦方向垂直于磨削加工条纹时为单侧塑性流动;当摩擦方向平行于磨削加工条纹时为双侧塑性流动;而在峰顶平台(磨削加工粗糙条纹磨合后形成的微平台)较大且载荷较高时,则为平台上的材料沿着摩擦方向向前挤压流动。     

Two new eudesmane derivatives from Verbesina virginica

<正>Two new eudesmane derivatives were isolated from the leaves and flowers of Verbesina virginica,along with the known 6-O-β-E -p-coumaroyl-4α-hydroxyeudesmane(1).Their structures were determined as 6-O-β-Z-p-coumaroyl-4α-hydroxyeudesmane(2) and 6-O-α-E-p-coumaroyl-1β-4α-dihydroxyeudesmane(3) by spectroscopic methods.     

Kinetic comparison between ferric ion and decamethyferrocene at the liquid/liquid interface as studied by scanning electrochemical microscopy

<正>Comparison in electron transfer(ET) processes from decamethyferrocene(DMFe) in nitrobenzene(NB) to ferric ion in aqueous phase was investigated for the first time by the scanning electrochemical microscopy(SECM).As compared with the system of Fe(CN)_6~(3-)-DMFe,the ET rate obtained from Fe~(3+)-DMFe was lower in spite of larger driving force,which may arise from the effect of reorganization energy.Otherwise,the effect of common ion on rate constants was also probed and results suggested additional complexity of the ET mechanism between Fe(CN)_6~(3-) and DMFe.