Elaborate treatment of retention in chemoselective chromatography—The retention increment approach and non-linear effects

The retention increment approach is described which quantifies the association equilibria of a selectand and a selector in complexation and inclusion chromatography. A thermodynamic treatment of enantioselectivity based on retention phenomena in chromatography including entropy/enthalpy compensation and the isoenantioselective temperature is advanced. Kinetic parameters of enantiomerization are discussed. Non-linear effects, both existent and elusive, are described and proposed, respectively. The enantioselectivity pertaining to catalysis vs. chromatography is compared and a unified nomenclature is proposed. Through an educational effort, this account is aimed at providing a deeper insight into chemoselective aspects of chromatography thereby stimulating further research of both established and speculative phenomena of the most intriguing manifestation of chemoselectivity, that is, of enantioselectivity.     

Tuning ranges of an injection-locked excimer laser

The advantages and the practical limitations of injection locking are discussed. Experimental results for a system working in the regime between ideal injection locking and regenerative amplification are presented.     

全固态激光器抽运的PPLN光参变振荡

用全固态1064nm调Q激光输出，抽运多周期PPLN，实现了宽调谐的准相位匹配光参变振荡，振荡阈值10．3μJ（脉宽22ns)，信号光最高输出平均功率为42．5mW，斜率效率为12．5％。     

A pyrene-based dual chemosensor for colorimetric detection of Cu2+ and fluorescent detection of Fe3+

A pyrene based chemosensor was designed and synthesized. The pyrene fluorophore was connected with a pyridine unit through a Schiff base structure to give the sensor (L). L was tested with a variety of metal ions and exhibited high colorimetric selectivities for Cu²⁺ and Fe³⁺ over other ions. Upon binding with Cu²⁺ or Fe³⁺, L showed an obvious optical color change from colorless to pink for Cu²⁺ or orange for Fe³⁺ over a wide pH range from 3 to 12. Moreover, the fluorescence of L at 370 nm decreased sharply after bonding with Fe³⁺, while other metal ions including Cu²⁺ had no apparent interference. Thus, using such single chemosensor, Cu²⁺ and Fe³⁺ can be detected independently with high selectivity and sensitivity. The limits of detection toward Cu²⁺ and Fe³⁺ were 8.5 and 2.0 μM, respectively. DFT calculation results also proved the formation of stable coordination complexes and the phenomenon of fluorescence quenching by Fe³⁺. Furthermore, L was also successfully used as a bioimaging reagent for detection of Fe³⁺ in living cells.     

表面接枝法制备磁性邻苯二甲酸二丁酯印迹聚合物及其识别性能研究

采用表面接枝法对四氧化三铁纳米粒子表面进行功能化修饰,以二甲基丙烯酸乙二醇酯(EGDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂,成功制备了对邻苯二甲酸二丁酯(DBP)具有特异识别性能的磁性表面印迹聚合物(MMIPs).利用扫描电镜、透射电镜、振动样品磁强计、元素分析、红外光谱等对其进行表征.BET测试结果表明,MMIPs的比表面积(380 m2/g)大于MNIPs(324 m2/g).吸附动力学、等温线模型分析显示,MMIPs对DBP的Sips等温线模型相关系数R2=0.999,动力学Pseudo-second-order 模型相关系数(R2)为0.9797.对邻苯二甲酸二烯丙酯(DAP)、DBP和邻苯二甲酸二(2-乙基己基)酯(DEHP)的印迹因子分别为1.53、2.21和1.39,对DBP具有较高的印迹因子和较好的识别性能.磁性分子印迹聚合物经5次再生后,对DBP的吸附能力仅下降了12.3％,表明再生循环效果较好.     

Retention behaviors of novel ionic liquid stationary phases and their selectivity for capillary gas chromatography

<正>One chloride-terminated ionic liquid(CTIL) and two hydroxyl-terminated ionic liquids(HTILs) were synthesized and used as stationary phases for capillary gas chromatography(CGC).Molecular interactions of these stationary phases were evaluated by Abraham solvation parameter model,indicating that the CTIL exhibits remarkably strong H-bond basicity and the HTILs possess both H-bond basicity and acidity.The molecular interactions were further confirmed by separation of a complex mixture consisting of ketones,aldehydes,esters,alcohols and aromatic compounds.It was found that the obtained solvation parameters correlate well with the chromatographic performances of the analytes in terms of elution order and resolution.The well correlated relationship between the solvation parameters and the selectivity of the CTIL and HTILs stationary phases is quite helpful in predicting and understanding the retention behaviors of different types of analytes on these stationary phases.     

Analytical and preparative separation of PEGylated lysozyme for the characterization of chromatography media

The effect of PEGylation on cation exchange chromatography was studied with poly(ethylene glycol) of different chain lengths (5 kDa, 10 kDa and 30 kDa) using lysozyme as a model system. A stable binding via reduction of a Schiff base was formed during random PEGylation on lysine residues with methoxy-PEG-aldehyde. A purification method for PEGylated proteins using cation exchange chromatography was developed, and different isoforms of mono-PEGylated lysozyme were isolated. TSKgel SP-5PW and Toyopearl GigaCap S-650M showed the best performance of all tested cation exchange resins, and the separation of PEGylated lysozyme could be also scaled up to semi-preparative level. Size-exclusion chromatography, SDS-PAGE and MALDI-TOF mass spectrometry were used for analysis. Separated mono-PEGylated lysozyme of different sizes was used to determine dynamic binding capacities (DBC) and selectivity of cation exchange chromatography resins. An optimization of binding conditions resulted in a more than 20-fold increase of DBC for Toyopearl GigaCap S-650M with 30 kDa mono-PEGylated lysozyme.     

铜催化的乙酰苯胺间位碳氢芳基化反应机理的理论研究

通过系统的理论计算研究了Gaunt报道的一个新颖的间位选择性C-H键芳基化反应的机理. Oxycupration机理含有一个关键的Cu(III)基团和酰胺氧原子对苯环C2=C3键的反式加成步. 但是计算结果表明这个反应路径的活化能太高(>175.56 kJ/mol),所以是动力学禁阻的. 提出了一个含有关键的酰胺导向的Cu(III)-Aryl对底物C2=C3键的顺式加成步的机理,这一步是反应的决速步,也是决定产物区域选择性的一步. 这个机理的活化能与实验条件是符合的,而且这个机理预测的产物区域选择性与实验