离子液体参与原子转移自由基聚合的研究进展

主要阐述了近年来离子液体作为溶剂、单体或者配位剂在原子转移自由基聚合中的应用研究情况.从对聚合反应速率的大小的影响,聚合产物分子量多分散系数的变化,聚合物分子链功能性的设计,以及反应体系中催化体系的分离与循环使用等方面总结了离子液体的参与对原子转移自由基聚合的影响,并简要总结了导致各种变化的原因.最后展望了离子液体应用于原子转移自由基聚合技术的前景,并指出离子液体自身研究的发展是二者结合的关键问题.     

Synthesis of Fischer indole derivatives using carboxyl-functionalized ionic liquid as an efficient and recyclable catalyst

Fischer indole cyclization of phenylhydrazine and various ketones using carboxyl-functionalized ionic liquid, 1-carboxymethyl-3-methylimidazolium tetrafluoroborate (abbreviated as [cmmim][BF4]) as catalyst was successfully performed. The yields of thetarget compounds were 80-92%, the purities were 96-98%. The catalyst could be rocovered and reused for at least six times without significant loss in activity.     

Two new C-glucofuranosyl isoflavones in puerarin injection

Two new C-glucofuranosyl isoflavones of impurities in puerarin injection were isolated.Their structures were determined to be 8-C-α-glucofuranosyl-7,4'-dihydroxyisoflavone and 8-C-β-glucofuranosyl-7,4'-dihydroxy-isoflavone by chemical and spectral analysis.     

聚醋酸乙烯类梳型分散剂的制备与表征

颜料在工业生产和人们的日常生活中起着重要的作用.由于颜料颗粒具有较大的比表面积和较高的比表面能,是热力学不稳定体系,当分散在介质中时容易发生团聚,影响其特性的发挥[1],因此需加入分散剂使其在分散介质中稳定分散.     

(R)-2-甲基半胱氨酸盐酸盐的合成方法改进

以L-半胱氨酸甲酯盐酸盐为起始原料,经4步反应合成了(R)-2-甲基半胱氨酸盐酸盐.在关键中间体(2R, 4R)-2-叔丁基-3-甲酰基-4-甲基-1,3-噻唑烷-4-甲酸甲酯(4)的合成中,采用Self-regeneration of stereocenters原理,用六甲基二硅胺钠取代文献方法中的二异丙基胺基锂,4的收率由文献的56%提高至90%.化合物的结构经1H NMR和MS表征.     

施用污泥对黑麦草生长及重金属含量的影响

采用单因素随机区组试验的方法,研究了金华市污水厂污泥堆肥对黑麦草生长和对重金属的吸收及富集的影响。结果表明,施用量以1kg／m^2和2kg／m^2的两个处理为宜,当年的产草量比对照分别增加了22．6％和27．8％;施用污泥黑麦草植株地上部组织重金属元素Pb、Cd和Cu的含量与对照相比无显著差异,Zn的积累量增多,重金属含量均未超过植物中的平均含量,施用污泥未对黑麦草造成重金属污染。     

气相色谱-质谱监测1-溴-2,4-二氟苯的合成条件、贡献及纯度

采用气相色谱-质谱（GC—MS）法对1,3-二氟苯溴化产物定性分析,采用了峰面积归一化法对产物进行定量分析,并通过正交设计结合多指标综合评价法优化合成条件。结果表明,通过GC—MS监测,对正交实验Z值结果分析得到最佳制备工艺：四氯化碳为溶剂,反应摩尔比（间二氟苯与液态溴）2：1,5℃下反应12h。产物纯度高于99．50％     

A theoretical study on the mechanism of the addition reaction between carbene and epoxyethane

The mechanism of addition reaction between carbene and epoxyethane has been investigated employing the MP2 and B3LYP/6-311+G* levels of theory. Geometry optimization, vibrational analysis, and energy property for the involved stationary points on the potential energy surface have been calculated. Based on the calculated results at the MP2/6-311+G* level of theory, it can be predicted that there are two reaction mechanisms (1) and (2). In the first reaction carbene attacks the atom O of epoxyethane to form an intermediate 1a (IM1a), which is a barrier-free exothermic reaction. Then, IM1a can isomerize to IM1b via a transition state 1a (TS1a), where the potential barrier is 48.6 kJ/mol. Subsequently, IM1b isomerizes to a product epoxypropane (Pro1) via TS1b with a potential barrier of 14.2 kJ/mol. In the second carbene attacks the atom C of epoxyethane firstly to form IM2 via TS2a. Then IM2 isomerizes to a product allyl alcohol (Pro2) via TS2b with a potential barrier of 101.6 kJ/mol. Correspondingly, the reaction energies for the reactions (1) and (2) are −448.4 and −501.6 kJ/mol, respectively. Additionally, the orbital interactions are also discussed for the leading intermediate. The results based on the B3LYP/6-311+G* level of theory are paralleled to those on the MP2/6-311+G* level of theory. Furthermore, the halogen and methyl substituent effects of H₂C: on the two reaction mechanisms have been investigated. The calculated results indicate that the introductions of halogen or methyl make the addition reaction difficult to proceed.     

Automorphisms of Extensions of ℚ by a Direct Sum of Finitely Many Copies of ℚ

Let G be an extension of ℚ by a direct sum of r copies of ℚ. (1) If G is abelian, then G is a direct sum of r + 1 copies of ℚ and AutG ≅ GL(r + 1, Q); (2) If G is non-abelian, then G is a direct product of an extraspecial ℚ-group E and m copies of ℚ, where E/ζE is a linear space over Q with dimension 2n and m + 2n = r. Furthermore, let AutG′G be the normal subgroup of AutG consisting of all elements of AutG which act trivially on the derived subgroup G′ of G, and AutG/ζG,ζGG be the normal subgroup of AutG consisting of all central automorphisms of G which also act trivially on the center ζG of G. Then (i) The extension 1 → AutG′G → AutG → AutG′ → 1 is split; (ii) AutG′G/AutG/ζG,ζGG ≅ Sp(2n,Q) × (GL(m, Q) ⋉ ℚ(m)); (iii) AutG/ζG,ζGG/InnG ≅ ℚ(2nm).     

One‐Step Electrochemically Deposited Nanocomposite Film of CS‐Fc/MWNTs/GOD for Glucose Biosensor Application

A simple and controllable electrodeposition approach was proposed for one‐step construction of glucose biosensors by in situ co‐deposition of ferrocene‐branched chitosan derivatives (CS‐Fc), multiwalled carbon nanotubes (MWNTs), and glucose oxidase (GOD) onto electrode surface. The formation of CS‐Fc could not only effectively prevent the leakage of Fc and retain its electrochemical activity, but also provide a biocompatible microenvironment for retaining the native activity of the immobilized biomolecules. Further entrapment of MWNTs into the CS matrix improved electronic conductivity of the biocomposite significantly. The facile procedure of immobilizing GOD and the promising feature of biocomposite will offer a versatile platform to fabricate biosensors and bioelectronic devices.