基于六氟异丙醇/芳樟醇超分子液液微萃取环境水样和饮料中罗丹明B和柯衣定

建立了一种基于超分子溶剂的涡旋辅助液液微萃取和高效液相色谱联用法检测罗丹明B和柯衣定。使用六氟异丙醇和芳樟醇制备超分子溶剂,并研究了其相行为和相率。将六氟异丙醇加入到芳樟醇水溶液中,形成超分子溶剂且密度大于水。在最优萃取条件下,六氟异丙醇/芳樟醇超分子溶剂对罗丹明B和柯衣定的线性范围为5～1000μg/L,检出限在1.3～1.5μg/L之间,定量限在4.5～5.0μg/L之间,日内、日间相对标准偏差（RSD）小于5.2%。方法用于检测环境水样和饮料中的罗丹明B和柯衣定,回收率为84.4%～109.1%, RSD在0.5%～7.6%之间。     

烟叶中油分的萃取方法研究

比较了烟叶中油分的萃取方法,分别采用超声、索氏、ASE加速溶剂和CO2超临界萃取方法萃取烟叶中的油分,萃取物再经硅胶氧化铝柱分离成3种不同极性的馏分,馏分使用气相色谱分离,质谱鉴定结构.在同时考虑萃取率和萃取物组成成分的基础上最终选择索氏萃取.通过对萃取溶剂和萃取时间进行单因素试验,确定了最佳萃取条件为:萃取溶剂三氯甲烷,萃取时间16 h.方法所得组分全面,有利于后期卷烟配方的调整与设计.     

金属检测中新型前处理技术研究进展及应用

精准检测环境和食品中金属含量对环境保护和人体健康至关重要.样品的准备环节是造成样品损失和二次污染的关键步骤, 因此合适的前处理方法可以提高金属分析的选择性和灵敏度.从液相萃取和非液相萃取新技术两方面综述了浊点萃取、离子液体、超分子溶剂-分散液液微萃取、顶空固相微萃取技术、超临界流体萃取特点及在复杂样品前处理中的应用和研究进展, 并对其未来发展方向进行了展望.     

离子液体在萃取分离中的应用研究进展

室温离子液体作为一种新型绿色溶剂,具有液程宽、几乎不挥发、溶解能力强及结构可调等独特的物理化学性质,近年来逐渐被人们认识了解,它在各个领域的应用也得到了初步的发展.本文重点概述了离子液体在萃取分离金属离子方面的研究进展,并对离子液体萃取分离有机物和生物分子的研究作了简要介绍.引用文献54篇.     

超分子溶剂萃取/超高效液相色谱-串联质谱法测定血浆中他克莫司含量

该文建立了血浆中免疫抑制剂他克莫司（TAC）的超分子溶剂（SUPRAS）萃取/超高效液相色谱-串联质谱分析方法。通过单因素实验结合响应面设计对超分子溶剂组成、用量及涡旋萃取时间等关键因素进行优化后,血浆样本以正戊醇、四氢呋喃和水形成的超分子溶剂进行高效萃取。萃取液经Waters ACQUITY UPLC BEH C18(50 mm×2.1 mm,1.7μm)色谱柱分离后,在电喷雾质谱正离子模式下,以多反应监测（MRM）模式对他克莫司进行测定,内标法定量。结果表明,他克莫司在0.5～30 ng/mL质量浓度范围内的线性关系良好,相关系数（r）为0.998 6;方法检出限和定量下限分别为0.1、0.5 ng/mL;在低、中、高3个加标水平下,平均回收率（n=3）为91.9%～99.9%,相对标准偏差（RSD）为1.7%～5.7%。所建立的方法快速、灵敏、稳定,适用于血浆中他克莫司的准确测定。     

酸性有机磷类萃取剂单分子膜的气-液界面行为:亚相pH和铺展溶剂的影响

液-液两相萃取过程中,有机磷类萃取剂分子的界面行为决定了其以何种形式参与到界面萃取反应中.为了阐明萃取剂分子界面行为的变化特点,采用Langmuir单分子膜技术研究了单分子膜中P507分子在气-液界面的吸附和聚集行为随亚相pH、有机溶剂极性的变化.通过测定表面压-分子面积等温线,并采用界面红外反射吸收光谱（IRRAS）分析表征气-液界面P507分子间相互作用,结果发现,以正己烷作铺展溶剂时,随亚相pH的降低,P507单分子膜质子化程度提高,P507分子极性端水化能力削弱,分子间相互作用增强,单分子膜中形成含有分子间氢键的聚集体.但采用极性有机溶剂（二氯甲烷和氯仿）铺展P507单分子膜,膜内P507分子界面聚集状态发生变化.铺展溶剂极性增强,单分子膜内会含有更多极性端水化能力强的P507分子单体,并且亚相pH降低,单分子膜不会出现类似正己烷条件下的π-A曲线收缩和P-O-H基团峰位红移现象.这证实了有机铺展溶剂极性可以改变P507单分子膜中分子界面存在形式和聚集状态.本工作为深入理解溶剂萃取过程中水油两相界面处酸性有机磷类萃取剂分子的聚集行为变化及其对界面反应活性的影响机制奠定了基础.     

超分子溶剂直提测定水中的多环芳烃

超分子溶剂是两亲化合物通过分子间有序的自组装过程形成的具有纳米结构的胶束聚集体,是一种高效提取溶剂。该文以高效液相色谱-荧光检测法为测试手段,系统地对超分子溶剂组成及用量进行了优化,发展了一种直接提取、快速测定水中多环芳烃的方法,并进行了方法学验证及实际样品检测。结果表明,采用四氢呋喃和1-辛醇制备的超分子溶剂对4种多环芳烃的回收率为89.08%~102.47%,相对标准偏差(RSD,n=5)为1.38%~3.92%。4种多环芳烃在一定范围内线性关系良好(相关系数R~20.999),检出限为1.26~9.23 ng/L。该方法前处理过程简单,有利于实现快速分析;溶剂使用量少,符合绿色化学的发展趋势,具有一定的推广价值。     

疏水性低共熔溶剂及其在含水体系萃取分离中的应用

低共熔溶剂是一类新型的绿色溶剂,但目前文献报道的低共熔溶剂大多是亲水性的.它们在水中不稳定,很难在含水体系中得到应用.为了解决这一问题,近年来疏水性低共熔溶剂受到特别的关注.本文在介绍低共熔溶剂基本概念的基础上,以含水体系中短链脂肪胺、低碳醇、双酚A、杀虫剂、重金属和稀有金属的萃取/分离为例,综述了近年来疏水性低共熔溶剂在液-液萃取、液相微萃取等分离方面的研究进展,分析了进一步的发展趋势,提出了目前尚待解决的主要问题.     

4-硝基-1,3-丁二烯基胺分子的氢键效应

在从头计算的水平上, 利用杂化密度泛函理论研究了溶剂对4-硝基-1,3-丁二烯基胺分子的几何结构、分子内的电荷分布和电荷转移态的能量漂移的影响. 在四种极性溶剂中, 我们构造了包括氢键作用的超分子结构. 分别研究了由极化连续模型模拟的溶剂和溶质分子的长程相互作用, 溶剂和溶质分子的氢键作用, 以及溶剂和溶质分子的整体作用对分子结构和性质的影响. 研究结果表明氢键作用引起了溶质分子结构和性质的较大变化, 从而将明显地影响该类分子的非线性光学性质. 因此, 在模拟溶剂效应时需要考虑氢键作用.     

超分子凝胶性质与溶剂参数关系的研究进展

为了能有效地开发功能性凝胶,人们对超分子凝胶机理做了大量研究.但目前的研究还局限于凝胶因子结构和外界环境等影响因素,而有关溶剂对超分子凝胶体系的影响规律还不十分清楚.本文将结合最新研究进展详细地讨论凝胶性质(如凝胶-溶胶转变温度(Tgel)、临界凝胶浓度(CGC)、凝胶流变学性质等)与溶剂参数(如ε、ET(30)、χ、δ、δd、δp、δh等)的关系,揭示溶剂影响凝胶性质的规律;在此基础上,进一步介绍了超分子凝胶行为预测模型:一维模型、Teas图模型和Hansen空间模型,并讨论了各模型的优缺点,以期为新型超分子凝胶体系的设计提供参考.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.