Gel Chromatography of Metal Acetylacetonates in Organic Solvents

Abstract

Tris (acetylacetonato)cobalt(III) and tris(acetylacetonato)-chromium(III) have been eluted by gel chromatography through styrene-divinylbenzene copolymer gel using an organic solvent as an eluent. Elution counts of these chelates in these solvents reflect some mutual interactions between metal chelate, gel and solvent. When benzene or chloroform was used as an eluent, sieving effect seems to be dominant for the separation of these chelates. Discussions were done in relation to solubility parameters of the solvent, the complex and the gel.     

Application of Crown Ether in Chemical Analysis Extraction of Copper(II)-Zincon Chelate Anion with Crown Ether Complex

Abstract

Crown ether-potassium ion complex extracts selectively copper-zincon anion complex as ion-pairs into chloroform phase in the presence of copper-zincon and zinc-zincon chelate anion, whereas quarternary ammonium ion extracts both anions. By measuring the absorbance of the chloroform phase at 615 nm, copper in the presence of zinc has been determined spectrophotometrically. The composition of extracted species was estimated to be Cu²⁺-zincon^4?-(KL⁺)₂.     

PCM study of the solvent and substituent effects on bond dissociation energies of the O?NO Bond—A DFT study

A PCM continuum model, at the B3LYP, B3P86, and B3PW91 three‐parameter hybrid DFT methods with 6‐311G** basis set, is used to study the bond dissociation energies (BDEs) of benzyl nitrites. Compared the computed results with the experimental values, it is noted that B3PW91 functional is the best method to compute the BDEs of benzyl nitrites. The solvent and substituent effects on the BDEs of the O? NO bond are analyzed, and it is shown that the BDE of the O? NO bond decreases with the increment of the Hammett constants of substituent groups on benzene for benzyl nitrites except C₆H₅CH₂O? NO. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Theoretical study of static (Hyper)polarizabilities of twisted intramolecular charge transfer chromophores

Density functional theory calculations are performed to study the (hyper)polarizabilities of a series of planar and twisted intramolecular charge transfer molecules (tictoids) with different electron‐donating and electron‐withdrawing groups. Both similarity and difference between the planar and twisted molecules are noted in their (hyper)polarizability variation with respect to substituent and solvent dielectric constant. When compared with dramatic enhancements resulting from geometry twist and solvent effect, substitution to D/A pairs leads to relatively moderate variation in (hyper) polarizability. In addition, tictoids with different substituents may exhibit different solvent effects in their hyperpolarizability magnitudes. Our calculations suggest that the nonlinear optical response of the tictoids could be tuned by appropriately selecting the donor/acceptor pairs and solvents. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Comparison of Liquid–Liquid Extraction,Simultaneous Distillation Extraction,Ultrasound-Assisted Solvent Extraction,and Headspace Solid-Phase Microextraction for the Determination of Volatile Compounds in Jujube Extract by Gas Chromatography/Mass Spectrometry

Jujube extract has a unique flavor that has been used as a common fragrance due to the volatile compounds. In this study, the volatiles of jujube extract were isolated by liquid–liquid extraction, simultaneous distillation extraction, ultrasound-assisted solvent extraction, and headspace solid-phase microextraction, and analyzed by gas chromatography–mass spectrometry. Altogether 92 compounds were identified by the four methods, of which 53 components were identified for the first time; however, only 21 compounds were identified by all these methods. The performance characteristics of the four pretreatment techniques were compared by principal component analysis which showed that the volatile compounds obtained by liquid–liquid extraction and ultrasound-assisted solvent extraction were similar both in categories and in content; whereas, the volatiles extracted by simultaneous distillation extraction, ultrasound-assisted solvent extraction, and headspace solid-phase microextraction greatly varied. The results indicated that a multi-pretreatment technique should be adopted in order to obtain the most complete information about the volatile compounds in jujube extract. The ultrasound-assisted solvent extraction method exhibited excellent repeatability and recoveries, and was very suitable for quantitative analysis. Although the recoveries and reproducibility of headspace solid-phase microextraction were inferior to the other methods, it was more sensitive than other methods.     

共晶基陶瓷复合材料的强度模型

根据细观结构内界面的强约束特性,通过纤维-基体内界面切应力确定了共晶陶瓷棒体的细观应力场.然后分析了两相界面处位错塞积产生的应力集中,获得基体内的最大应力,当最大拉应力等于基体理论断裂强度时,得到共晶棒体的断裂强度的解析表达式.考虑共晶陶瓷棒体长度和方位的随机性,根据概率理论得到共晶陶瓷基复合材料的宏观强度的理论模型.结果表明复合材料的宏观强度与亚微米纤维的直径和长度、以及亚微米纤维、基体、共晶陶瓷棒体的弹性常数有关.理论与实验结果十分接近,说明文中理论模型是合理的,同时证明了共晶界面对陶瓷复合材料的重要影响.     

耐有机溶剂微生物及酶类在生物催化中的应用*

将生物催化剂运用到有机相催化具有多种优势,然而酶是一类不稳定的催化剂很容易在有机溶剂存在的条件下失去活性。耐有机溶剂微生物是一类新颖的极端微生物,它们可以在高浓度的有机溶剂存在的条件下生存,而这类微生物所产的一些酶类往往具有耐有机溶剂的性能。随着这一领域开发和发展,从这类极端微生物中寻找高效生物催化剂逐渐成为新的研究热点,并被越来越多的运用到有机相生物催化领域。本文综述了新型耐有机溶剂催化剂的开发、应用与发展,并讨论了该领域的研究所带来的机遇与挑战。     

深部灰岩三轴蠕变特性实验研究

采用MTS815岩石材料力学试验机,在温度28℃条件下,对重庆市万盛区某煤矿深部掘进巷道灰岩进行了三轴蠕变试验,对不同偏应力水平下该巷道灰岩的蠕变特性进行了分析。结果表明,蠕变试验的曲线显示该灰岩蠕变具有非线性特征,其蠕变特性随着围压的增加而更加明显。对深部灰岩的蠕变模型进行初步探讨,回归得出深部灰岩在不同应力水平下蠕变应变随时间变化的Burgers蠕变方程。分析表明,Burgers模型能较好地反映该深部灰岩的蠕变规律。该模型所确定的本构关系可以作为该深部灰岩蠕变本构模型来预测其蠕变发展。     

碳化物抗氧化稳定性及其与基体的协同作用对Cr—Ni合金铸铁高温耐磨性的影响

通过改变Cr-Ni合金铸铁中共晶碳化物的抗氧化稳定性,在可控气氛高温磨料磨损试验机上研究了碳化物及其与基体的氧化协同性对合金耐高温磨料磨损能力的影响。结果表明：碳化物的抗氧化稳定性以及碳化物与基体的氧化大无畏同性对合金在大气气氛中的高温耐磨性起着重要的作用。在Cr-Ni合金铸铁中,碳化物在高温氧化气氛中将优先于合金基体发生氧化腐蚀,使合金的耐磨性得到极大损害,因此,使碳化物与合金基体在高温下保持协同的高温稳定性对合金的高温耐磨性非常有利。     

酪氨酸与色氨酸间电子转移——氧化还原活性及电子跃迁能的从头算研究

在HF/6-31G和GASSCF/6-31G水平上对色氨酸和酪氨酸间的电子转移进行了理论 研究。用类导体屏蔽模型考察体系的溶剂效应。通过对给、受体几何构型的优化, 计算了孤立的给、受体之间电子转移反应的内重组能和反应能差。分别用 Koopmans定理和CASSCF/6-31G方法计算了色氨酸和酪氨酸的电离能。计算了此两种 氨基酸从基态到最低激发态的跃迁能。理论计算结果很好地解释了N_3~·高选择性 地氧化色氨酸残基,并诱发电子从酪氨酸残基向色氨酸残基转移的实验现象。