Aerobic oxidation of β-isophorone catalyzed by N-hydroxyphthalimide: the key features and mechanism elucidated

Due to the insufficient understanding of the selective oxidation mechanism of α/β-isophorones (α/β-IP) to ketoisophorone (KIP), the key features in the β-IP oxidation catalyzed by N-hydroxyphthalimide (NHPI) have been explored via theoretical calculations. β-IP is more favourable to being activated by phthalimide-N-oxyl radical (PINO˙) and peroxyl radical (ROO˙) than α-IP owing to the different C-H strengths at their reactive sites, thereby exhibiting selective product distributions. It was found that NHPI accelerates β-IP activation due to the higher reactivity of PINO˙ than ROO˙ and the equilibrium reaction between them, yielding considerable hydroperoxide (ROOH) and ROO˙. In addition, the ROOH decomposition is more favourable viaα-H abstraction by radicals than its self-dehydration and thermal dissociation. The strong exothermicity of this α-H abstraction, along with that from H-abstraction by co-yielded hot HO˙, is in favor of the straightforward formation of KIP, simultaneously leading to the isomerization of a few β-IP to α-IP and production of 4-hydroxyisophorone (HIP) and water. The proposed mechanisms, consistent with the experimental observations, allow for the deeper understanding and effective design of oxidation systems involving similar substrates or NHPI analogues that are of industrial importance.     

Propagation of Gaussian array beams in uniaxial crystals orthogonal to the optical axis

The propagation of phase-locked and non-phase-locked Gaussian array beams in uniaxial crystals orthogonal to the optical axis is investigated. Analytical formulas are derived and the propagation properties of phase-locked and non-phase-locked Gaussian array beams are illustrated by numerical examples. Our results show that for non-phase-locked combination, the Gaussian array beams involve into an elliptical Gaussian-like distribution when the propagation distance is far enough, while for phase-locked combination, the Gaussian array beams involve into a central peak distribution and some small peaks are around the center peak when the propagation distance is far enough.     

Order-Disorder Phase Transition and Dielectric Mechanism in Relaxor Ferroelectrics

IntroductionSince Pb(Mg1/ 3Nb2 / 3) O3(PMN) was first syn-thesized by Smolenski and Agranovuskaya in thelate1 950 s[1] ,a series of relaxor ferroelectrics withcomplex perovskite structure whose dielectric andferroelectric properties are rather different fromthose of normal ferroelectrics have been studied.For the lead- based relaxor ferroelectrics,thedielectric permittivity is unusually high,thesintering temperature is rather low,and thetemperature coefficient of capacitance is quitesmall,w…     

反相高效液相色谱法测定化妆品中的酮麝香

 酮麝香是化妆品中的限用物质,对人体有致癌作用,因此,有必要对其含量进行分析。采用超声辅助提取法对不同基质类型的化妆品样品进行预处理。利用反相高效液相色谱法测定化妆品中的酮麝香。色谱条件为Kromasil C₁₈(250mm×4.6mm i.d.,5μm)色谱柱,流动相V(乙腈):V(水)= 80:20,流速1.0mL/min,检测波长235nm。结果表明,在此条件下,酮麝香在0.5-150 μg/mL范围内与相应的峰面积具有良好的线性关系(相关系数r为0.9998),线性回归方程为A=13500ρ-4829,回收率为90.5%-102.5%,RSD为0.45%-0.98%。因此,研究建立的利用反相高效液相色谱法测定化妆品中的酮麝香的方法准确、可靠、适用性广,可为酮麝香的分析及国家相关法规的制定提供一定的参考。     

连通容器甲烷-空气混合物抑爆影响因素

为了研究连通器甲烷-空气混合物抑爆的影响因素,利用小球容器、管道、大球容器建立了5种结构的连通容器气体爆炸测试系统,在40目丝网结构条件下,研究了管道长度、丝网层数、传爆容器、抑爆位置等对连通容器甲烷-空气混合物爆炸强度的影响。结果表明:小球容器与管道连通时,随着丝网层数和接管长度的增加,管道末端的压力逐渐降低;当增加传爆容器时,球形容器与管道内气体爆炸强度增加;小球容器与1段管道以及大球容器连通时,丝网层数越多,抑爆效果越明显;小球容器与2段管道以及大球容器连通时,丝网结构能够产生一定的抑爆效果,但抑爆效果不明显;小球容器与3段管道连通时,抑爆位置对连通容器抑爆效果产生较大影响。抑爆位置对连通容器抑爆效果与丝网结构的层数有关。因此,在实际生产应用中,应综合考虑多种因素的影响,以达到最佳的抑爆效果。     

壳聚糖基磁性树脂对Au~(3 )和Ag~ 的吸附特性I吸附平衡和动力学研究

利用反相乳液分散-化学交联法制备磁性壳聚糖微球(TMCS),并经硫脲改性,用于吸附水溶液中Au3 和Ag 。用光学显微图、红外图谱(FTIR)、X射线衍射(XRD)等对吸附剂进行了表征。考察了TMCS对Au3 和Ag 的吸附特性。结果表明,等温吸附线可用Langmuir模型拟合,饱和吸附容量分别为:Au3 3.53mmol/g;Ag 1.98mmol/g。二者的吸附容量均随pH升高而增加。吸附动力学可用拟二级模型拟合。双组分吸附实验表明,TMCS对Au3 和Ag 有良好的吸附选择性。     

柱隙锥齿型黑体模拟器

持黑体光壁腔观点用几何光学方法模拟黑体，得一柱隙锥齿型黑体模拟器，写出黑体数学模拟式，给出适用模拟器的身体参数。     

Preparation of Fe-loaded activated carbon and its adsorption property of U(VI) in aqueous solution

Three kinds of method were employed to prepare Fe loaded activated carbon (Fe-AC), liquid reduction method, carbonthermal method, incipient wetness method, respectively. Before and after adsorption, the adsorption property of Fe-AC had been analysed. Results indicated that the removal mechanisms were mainly redox reaction, adsorption and precipitation. In addition, the adsorption models fitted with the kinetic model and adsorption isotherm model. Based on the analysis of six influencing factors, we obtain some actual information to deal with the humic acid and the “back to acid”.     

栗黄枯叶蛾核型多角体病毒病毒粒子的拉曼光谱研究

通过对栗黄枯叶蛾核型多角体病毒TvNPV(Trabala vishnou Nuclear Po-lyhedrosis Virus)的病毒粒子的拉曼光谱研究,讨论了它的蛋白质分子空间构象.其蛋白质主要为β折叠结构、α螺旋结构以及少量无规卷曲(其中包括β回折)结构.蛋白质中酪氨酸残基多数暴露于分子表面,少数埋藏在分子内部;色氨酸残基大多埋藏在疏水环境中.蛋白质分子侧链C—C—S—S—C—C构型为反式—扭曲—反式.     

Free Phosphoric Acid of Diatomite-Phosphate Solid Acid and its Catalytic Performance for Propylene Oligomerization

Free phosphoric acid in the diatomite-phosphate solid acid catalysts was characterized by means of ion chromatography (IC), Hammett pH indicators and chemical titration. The results show that the free phosphoric acid is composed of 535 wt.% H₃PO₄, 17 wt.% H₄P₂O₇ and < 1 wt.% polyphosphoric acid, and its composition determines the acid strength distribution of the catalyst. When the total amount of free phosphoric acid containing >3 wt.% H₄P₂O₇ is within 9 26 wt.% (in P₂O₅), the catalyst shows higher catalytic activity for propylene oligomerization with propylene conversion >75wt.%. Besides, free phosphoric acid has an important effect on the catalytic selectivity. The relationship between them is discussed.