Selective Catalytic Isomerization of β-Pinene Oxide to Perillyl Alcohol Enhanced by Protic Tetraimidazolium Nitrate

A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of β-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO₃]₄ under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss.     

On the redox reactions between allyl radicals and NOx

NO_x mitigation is a central focus of combustion technologies with increasingly stringent emission regulations. NO_x can also enhance the autoignition of hydrocarbon fuels and can promote soot oxidation. The reaction between allyl radical (C₃H₅) and NO_x plays an important role in the oxidation kinetics of propene. In this work, we measured the absolute rate coefficients for the redox reaction between C₃H₅ and NO_x over the temperature range of 1000–1252 K and pressure range of 1.5–5.0 bar using a shock tube and UV laser absorption technique. We produced C₃H₅ by shock heating of C₃H₅I behind reflected shock waves. Using a Ti:Sapphire laser system with frequency quadrupling, we monitored the kinetics of C₃H₅ at 220 nm. Unlike low-temperature chemistry, the two target reactions, C₃H₅ + NO → products (R1) and C₃H₅ + NO₂ → products (R2), exhibited a strong positive temperature dependence for this radical-radical type reaction. However, these reactions did not show any pressure dependence over the pressure range of 1.5–5.0 bar, indicating that the measured rate coefficients are close to the high-pressure limit. The measured values of the rate coefficients resulted in the following Arrhenius expressions (in unit of cm³/molecule/s):$k_1\left({\mathrm{C}}_3{\mathrm{H}}_5+\text{NO}\right)=1.49\times {10}^{?10}\exp \left(?6083.6\frac{\mathrm{K}}{T}\right)\left(1017?1252K\right)$$k_2\left({\mathrm{C}}_3{\mathrm{H}}_5+\mathrm{N}{\mathrm{O}}_2\right)=1.71\times {10}^{?10}\exp \left(?3675.7\frac{\mathrm{K}}{T}\right)\left(1062?1250K\right)$To our knowledge, these are the first high-temperature measurements of allyl + NO_x reactions. The reported data will be highly useful in understanding the interaction of NO_x with resonantly stabilized radicals as well as the mutual sensitization effect of NO_x on hydrocarbon fuels.     

12β-Acetyloxyperforatin,a New Limonoid from Harrisonia Perforata

A new A, D-seco limonoid, named 12-acetyloxyperforatin (1), along with three known ones, were isolated from the leaves of Harrisonia perforata. Their structures were elucidated on the basis of spectroscopic analysis, including extensive NMR techniques and computational modelling. These compounds showed no inhibitory activity against the 11β-HSD1 enzyme.     

Photodegradation mechanisms of acyclovir in water and the toxicity of photoproducts

Journal of Radioanalytical and Nuclear Chemistry - In the present work the final products of coumarin radiation chemical transformation are investigated by chromatography. During radiolysis of...     

TiO2/CuInS2-sensitized structure for sensitive photoelectrochemical immunoassay of cortisol in saliva

Journal of Solid State Electrochemistry - Cortisol, a steroid hormone, has been confirmed as a kind of biomarker that reflects the stress response of psychobiology and related adverse health...     

Pure tetrahedral quadruple systems with index two

An oriented tetrahedron defined on four vertices is a set of four cyclic triples with the property that any ordered pair of vertices is contained in exactly one of the cyclic triples. A tetrahedral quadruple system of order $n$ with index $\lambda$, denoted by ${\text{TQS}}_{\lambda }\left(n\right)$, is a pair $\left(X,\mathrm{?}\right)$, where $X$ is an $n$‐set and $\mathrm{?}$ is a set of oriented tetrahedra (blocks) such that every cyclic triple on $X$ is contained in exactly $\lambda$ members of $\mathrm{?}$. A ${\text{TQS}}_{\lambda }\left(n\right)$ is pure if there do not exist two blocks with the same vertex set. When $\lambda =1$, the spectrum of a pure TQS $\left(n\right)$ has been completely determined by Ji. In this paper, we show that there exists a pure ${\text{TQS}}_2\left(n\right)$ if and only if $n\equiv 1,2\left(\mathrm{mod}3\right)$ and $n\ge 7$. A corollary is that a simple ${\text{QS}}_4\left(n\right)$ also exists if and only if $n\equiv 1,2\left(\mathrm{mod}3\right)$ and $n\ge 7$.     

高压下β-InSe弹性常数、电子结构的第一性原理研究

基于密度泛函理论的第一性原理计算方法,本文研究了高压对β-InSe弹性常数、机械性能和电子结构的影响.在0～20 GPa范围内,随着压力的增大,β-InSe的晶格常数、晶胞体积逐渐减小,结构参数a/a_0、c/c_0、V/V_0单调减小.在0～12 GPa范围内,弹性模量G、E、B和泊松比v随着压力增大而增大,在16 GPa时大幅减小,G、E、B分别减小了34.9%、53.3%、82.9%.随着压力增大,Se-In和In-In原子之间的电荷密度增大,Se-In原子之间的共价键增强,层间距减小.而且,β-InSe在20 GPa时带隙消失,发生了半导体向半金属的相变.     

基质刚性影响声孔效应介导的单细胞基因转染

实验研究了基质刚性对单细胞质粒DNA转染效果的影响。实验采用高声压短脉冲(0.45MPa,10μs)条件的超声对培养在不同硬度凝胶基质(软的凝胶基质：0.2kPa,硬的凝胶基质：40kPa)上的力学敏感细胞NIH 3T3进行质粒DNA转染实验。实验结果表明,培养在硬的凝胶基质上的细胞,质粒DNA转染效率明显高于培养在软的凝胶基质上的细胞。进一步对质粒DNA进行荧光示踪可知培养在不同刚性基质上的细胞导入质粒DNA的方式不同。当细胞被培养在硬的凝胶基质上时,通过声致穿孔产生的小孔进入细胞内的质粒DNA更多,而培养在软的凝胶基质上的细胞,更多的质粒DNA可以通过非声致穿孔作用,例如内吞方式导入细胞。 细胞骨架蛋白分布规律表明,硬的凝胶基质上培养的细胞内有更多的F肌动蛋白微丝,可以更好地支撑起细胞的铺展形态,相对不容易发生内吞作用。而软的凝胶基质上培养的细胞内F肌动蛋白则更多以球形状态存在,细胞形貌骗向圆形,此时更容易发生胞吞作用。