二丙胺的结构微调对磷酸铝分子筛晶化过程影响的凝胶组成依赖性

以二丙胺异构体（二正丙胺DPA和二异丙胺D-iPA）为结构导向剂,在200℃加热2组反应原料物质的量之比不同的初始凝胶,合成出了高结晶度的磷酸铝分子筛AlPO₄-11。利用X射线粉末衍射分析、元素分析等表征手段,研究了凝胶的晶化过程和液相的pH值以及Al和P的浓度演化。初始凝胶各组分物质的量之比为n_Al2O3：n_P2O5：n_DPA/D-iPA：n_H2O2=1.0：1.0：1.2：75时,以DPA为结构导向剂,晶化过程中无中间相生成,而以D-iPA为结构导向剂时,晶化过程中生成了具有12元环孔道结构的磷酸铝分子筛AlPO₄-5中间相;初始凝胶各组分物质的量之比为n_Al2O3：n_P2O5：n_DPA/D-iPA：n_H2O2=1.0：1.0：1.0：75时,以DPA为结构导向剂,晶化过程中生成了具有18元环孔道结构的磷酸铝分子筛VPI-5中间相,而以D-iPA为结构导向剂时,晶化过程中同时出现了VPI-5及AlPO₄-5两种中间相。表明对于同一种有机胺,凝胶物质的量之比的改变影响了其结构导向效应。理论计算结果显示质子化的DPA及D-iPA中N原子上的电荷有差异,表明有机胺的结构微调影响其结构导向效应,但该影响依赖于凝胶组成。     

Enantiomeric separations of four basic drugs containing N-alkyl groups by a RP-HPLC system using SBE-β-CD as chiral mobile phase additive

The chiral separations of four pharmaceutical racemates which contain N-alkyl groups were satisfactorily resolved using SBE-β-CD as a chiral mobile phase additive(CMPA)in a RP-HPLC system(the resolution is 2.701 for ondansetron hydrochloride,1.996 for sulpiride,1.293 for clenbuterol hydrochloride and 0.816 for omeprazole).In addition,the effects of different parameters such as CD type and CD concentration were investigated.The separation mechanism arises through the combination of several potential interactions,including electrostatic interactions as well as hydrogen bonding interactions and hydrophobic inclusion interactions,which allow for the SBE-β-CD–drug complexation with strong stereoselectivity and stability.The resolution also relates to the number and location of N atoms in the enantiomers.This method will be applicable to the isolation of various types of biologically important enantiomers containing N-alkyl groups.     

硫酸铜掺杂TiO2涂层对碳纤维抗氧化性能的影响

采用溶胶-浸渍法,以CuSO₄为烧结助剂在碳纤维表面制得TiO₂涂层。利用XRD、SEM和TEM分析了涂层相组成及形貌,通过静态等温氧化实验考察了涂层碳纤维抗氧化性能。结果表明：掺杂CuSO₄制备TiO₂涂层均匀完整致密,涂层相组成均为锐钛矿型TiO₂,且涂层厚度从45 nm提高至185 nm;与普通TiO₂涂层碳纤维相比,完全氧化温度从667 ℃上升到800 ℃,氧化活化能从118.390 kJ·mol^-1提高到152.562 kJ·mol^-1,CuSO₄的掺杂大大提高了TiO₂涂层碳纤维的抗氧化性能。     

枝晶簇四方相钛酸钡的制备及其电场响应性能的研究

为了提高BaTiO3粒子在含水复合弹性体中的电场响应能力,本文采用简单的水热合成法,在不引入任何表面活性剂的情况下,仅通过对反应温度和溶液pH值的调控获得了新颖形貌的钛酸钡粒子。通过借助X射线衍射(XRD)、拉曼光谱(Raman)、扫描电子显微镜(SEM)及接触角(Contact Angle)测量等手段对粒子的微观结构和表面特性进行表征发现:该粒子为高纯四方相枝晶簇结构,具有良好的亲水性,而且在含水复合弹性体中对电场具有优良的响应能力。     

卟啉单晶微纳米棒的合成及光电性能研究

通过相界面反应制备了一维卟啉微纳米棒,并通过紫外、红外和X衍射仪等多种表征方法对其进行了表征.结果表明,在无机酸的作用下,卟啉分子通过-,氢键和静电作用等多种相互作用聚集成有序的J-聚集体.将此一维卟啉微纳米棒构筑为微纳米器件,并测试其光电性能.该纳米器件在可见光照射下的光电流很大,关闭光源,电流在40 s内降到最低,再次打开光源,电流又在120 s内升到了最大.经过多次＂开＂、＂关＂光源,电导的光响应依旧没有降低.这种具有光电响应的卟啉微纳米棒有望成为微纳电子器件的光电元件.     

气相滴定在臭氧计量标准溯源中的应用

利用臭氧和一氧化氮发生快速反应生成二氧化氮的原理,设计气相滴定反应系统,通过对参加反应的一氧化氮标准气体浓度变化的准确测定,计算出组分臭氧混合气体的浓度。利用设计的气相滴定系统（GPT）,对基于紫外分光原理的臭氧测量标准装置SRP41产生的空气中臭氧标准气体进行了比对及相互验证。比对结果表明：二者偏差不大于2．6％,均在分析不确定度范围内等效。这为臭氧测量计量溯源问题提供了解决方案。     

选择性富集分离虎杖中白藜芦醇苷的分子印迹聚合物的制备及分子识别性能研究

以白藜芦醇苷(POL)为模板分子,分别以丙烯酰胺(AM)、4-乙烯基吡啶(4-VP)、甲基丙烯酸羟乙酯(HEMA)、甲基丙烯酸(MAA)为功能单体,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,采用本体聚合法制备白藜芦醇苷分子印迹聚合物。采用静态平衡结合实验研究了印迹聚合物对模板分子及不同底物的识别性能。结果表明,以丙烯酰胺为功能单体的印迹聚合物(MIP1)对模板分子的识别性能最好,其次是以4-VP为功能单体的聚合物(MIP2),以HEMA为功能单体的聚合物(MIP3)以及以MAA为功能单体的聚合物(MIP4)的分子识别性能较差。表明功能单体与模板分子之间相互作用的强弱对MIP的识别能力有较大的影响。静态平衡结合法以及Scatchard分析法表明,MIP1对模板分子呈现较好的结合能力和选择性,该印迹聚合物中形成了2类不同的结合位点,离解常数分别为7.43×10-5、3.70×10-3mol/L。将MIP1用于虎杖提取物中POL的固相萃取分离,效果良好。     

Analysis of polar peptides using a silica hydride column and high aqueous content mobile phases

The retention behavior of a set of polar peptides separated on a silica hydride stationary phase was examined with a capillary HPLC system coupled to ESI‐MS detection. The mobile phases consisted of formic acid or acetic acid/acetonitrile/water mixtures with the acetonitrile content ranging from 5 to 80% v/v. The effects on peptide retention of these two acidic buffer additives and their concentrations in the mobile phase were systematically investigated. Strong retention of the peptides on the silica hydride phase was observed with relatively high‐organic low‐aqueous mobile phases (i.e. under aqueous normal‐phase conditions). However, when low concentrations of acetic acid were employed as the buffer additive, strong retention of the peptides was also observed even when high aqueous content mobile phases were employed. This unique feature of the stationary phase therefore provides an opportunity for chromatographic analysis of polar peptides with water‐rich eluents, a feature usually not feasible with traditional RP sorbents, and thus under conditions more compatible with analytical green chemistry criteria. In addition, both isocratic and gradient elution procedures can be employed to optimize peptide separations with excellent reproducibility and resolution under these high aqueous mobile phase conditions with this silica hydride stationary phase.     

Estimation of the Interfacial Tension Between the Lamellar and the Sponge Phases of a Lyotropic System

In lyotropic systems, the sponge and the lamellar phases possess the same local structure: a membrane made of a bilayer of surfactants. In the quasiternary lyotropic system CPCl/brine/hexanol, the bilayer is continuous through the interface between the lamellar and the sponge phases. A model based on this phenomenon has predicted a very low value of the interfacial free energy. The study of hydrodynamic relaxation time of distorted spherical lamellar droplets gives an estimation of the interfacial tension value. Results confirm the validity of the model and the dependence on membrane volume fraction is explained by a simple scaling law.     

Electropolymerization of single‐walled carbon nanotubes composited with polypyrrole as a solid‐phase microextraction fiber for the detection of acrylamide in food samples using GC with electron‐capture detection

We developed a solid‐phase microextraction coupled to GC with electron‐capture detection method for the detection of acrylamide in food samples. Single‐walled carbon nanotubes and polypyrrole were electropolymerized onto a stainless‐steel wire as a coating, which possessed a homogeneous, porous, and wrinkled surface, chemical and mechanical stability, long lifespan (over 300 extractions), and good extraction efficiency for acrylamide. The linearity range between the signal intensity and the acrylamide concentration was found to be in the range 0.001–1 μg/mL, and the coefficient of determination was 0.9985. The LOD, defined as three times the baseline noise, was 0.26 ng/mL. The reproducibility for each single fiber (n = 6) and the fiber‐to‐fiber (n = 5) repeatability prepared in the same batch were less than 4.1 and 11.2%, respectively.