离线全二维逆流色谱-液相色谱分离莪术油成分

中药挥发油成分复杂,一维色谱分离由于有限的峰容量难以完全分离中药挥发油成分,全二维气相色谱为分离挥发油成分提供了有力的方法,然而气相色谱一般无法用于天然活性成分的筛选。为建立挥发油成分全二维色谱分析新方法,研究建立以液相色谱为基础的全二维色谱分离分析方法。本文主要研究全二维逆流色谱-液相色谱分离莪术油成分的方法,并探讨两种色谱技术之间的正交性,为活性成分筛选提供新的技术支持。通过优化离线全二维逆流色谱-液相色谱分离方法,对全二维色谱峰容量、正交性和空间覆盖率进行度量。优化液相色谱分析条件并筛选逆流色谱分离两相溶剂体系,通过比色法筛选了逆流色谱两相溶剂体系并采用下相为流动相进行梯度洗脱。在290～375 min采用推挤洗脱,莪术油在第一维逆流色谱分离中达到了良好的分离。第二维反相高效液相色谱的流动相组成为乙腈(A)和水(B)。梯度洗脱程序为0～10 min, 50%A～65%A; 10～14 min, 65%A; 14～21 min, 65%A～85%A; 21～25 min, 85%A～95%A; 25～30 min, 95%A～55%A; 30～40 min, 55%A。在上述条件下...     

胰岛素反相制备色谱的方法开发

以胰岛素反相制备色谱方法的开发和优化为目标,通过考察色谱保留参数、峰展宽及样品流出曲线的浓度分布等色谱参数,对流动相梯度、色谱填料、载样量等色谱条件进行了优化,并建立了胰岛素制备色谱峰参数的描述方法。结果表明,所建立的方法可快速筛选出最适于胰岛素分离的色谱条件(包括流动相梯度及分离填料),即流动相中的强洗脱溶剂(有机相)需采取缓梯度窄区间的变化条件,筛选出的分离填料需具备峰向两侧展宽且展宽程度较小、样品最高浓度居中分布的特点。将方法用于实际胰岛素粗品的纯化制备,获得了杂质去除效果好、胰岛素纯度高的产品。该法为胰岛素反相色谱纯化制备方法的快速建立提供了指导,具有较强的实用价值,同时为发展大分子化合物的制备色谱方法提供了参考。     

环糊精衍生物固定相毛细管气相色谱法分离甲酚位置异构体

采用了环糊精衍生物固定相毛细管气相色谱法对甲酚位置异构体进行分离。着重考察了气相色谱中柱头压、柱温、检测器温度、进样器温度对保留时间和峰面积的精密度的影响,并通过正交实验优化色谱条件使峰面积的相对标准偏差小于1%,异构体达到基线分离。     

智能搜索用于实际样品的液相色谱分离条件的优化

〕本文提出了可用于色谱操作条件自动优化的串形优化指标和智能搜索法。串形优化指标可正确地评价一张色谱图的质量,而智能搜索法把宽度优先和深度优先的原理及单纯形中多种逻辑算法相结合而进行色谱操作条件的最优化。实验表明：该法用于水溶性维生素及芳烃化合物的优化可获得满意的结果。     

小波神经网络-遗传算法用于2-(9-咔唑)乙基氯甲酸酯衍生化氨基酸的胶束电动力学色谱分离优化

将小波神经网络和遗传算法应用到2-(9-咔唑)-乙基氯甲酸酯衍生化氨基酸的胶束电动力学色谱分离优化。小波神经网络结合正交试验设计用于分离过程的多因素模型建立。以训练好的小波神经网络模型为目标函数,采用实数编码的遗传算法搜寻确定最佳分离条件,在此条件下分离得到的归一化分离度积与正交试验设计中最佳条件相比,提高了12．5％。     

正交设计法用于取代茂铁硼烷化合物的TLC溶剂系统的选择

采用薄层色谱技术分离一组取代茂铁硼烷化合物。以含有烷基卤化铵离子对试剂的丙酮－环己烷流动相,用正交设计法选择色谱分离条件。把离子对试剂种类、浓度和丙酮、环己烷含量作为影响分离效果的因素。实验条件按〔Ｌ９（３４）〕正交设计表安排。应用统计力学方差分析法对反映分离效果的薄层色谱指标——色谱总分离度（ＤＳ）进行分析,确定了影响化合物分离的主要因素和最佳展开剂体系。在最佳条件下的结果令人满意。     

全二维气相色谱技术及其进展

 许多分析问题的解决需要得到比一维色谱技术能提供的更高的分辨率。分离能力可通过使用多种分离技术或机理的组合来增强。此时 ,样品被分散在不同的时间维 ,最终的分辨率强烈地依赖于这些维间分离特性的差异。当它们之间没有关联 ,也即相互间正交时 ,系统可获得最高的分辨率。全二维气相色谱 (GC×GC)提供了一个真正的正交分离系统。它把分离机理不同而又互相独立的两支色谱柱以串联方式结合组成二维气相色谱。在这两支色谱柱之间装有的一个调制器起捕集再传送的作用。全二维色谱的峰容量为组成它的两支色谱柱各自峰容量的乘积。     

模拟退火神经网络用于药物液相色谱梯度分离条件的优化

模拟退火神经网络用于药物液相色谱梯度分离条件的优化。使用均匀设计法以乙腈在线性梯度展开时的初始浓度和线性梯度的斜率为优化参数,对六种药物混合体系进行优化。采用退火神经网络方法建立了有效的分离条件预测模型。对神经网络模型所预测的最佳分离条件进行试验,分离结果满意。模拟退火神经网络可有效地用于药物液相色谱分离条件的优化。     

气相色谱柱温智能优化用于实际样品分离的方法发展

本文叙述了气相色谱柱温智能最佳化程序在分离三个空气中毒物样品的应用。针对“难分离物质对”设计升温阶梯不仅容易找到最佳条件，而且计算量少。预测的保留时间精密度在±１．５％以内，难分离对的总分离效能指标的精密度在±５％以内。     

回归正交极谱法测定相互干扰组分锌,钴和镍

分析中干扰组分的分离和掩蔽是麻烦而困难的问题。应用适当的多元正交回归设计可以同时测定相互干扰的几种组分，而不必分离和掩蔽。在乙二胺体系（ｐＨ１２．２）的不同条件下，对相互干扰的组分Ｚｎ，Ｃｏ和Ｎｉ进行回归正交实验研究，得到了极谱电流与组分浓度间的归方程组。通过解此方程组，同时测定了土壤和植物（辣椒）中的Ｚｎ，Ｃｏ和Ｎｉ的含量。结果表明，分析相对标准偏差不大于５．３％，而样品回收率在９５％－１０８％     

An assisted approach of the global optimization for the experimental conditions in capillary electrophoresis

Experimental conditions have effect on the separation of capillary electrophoresis (CE) directly. In this work, a set of index to describe the separation in CE was established properly. Based on a combination of genetic algorithm and least square support vector machine, an assisted approach of global optimization for experimental conditions was proposed for the first time, and it was applied to the separation of four synthetic compounds by CE in nonaqueous system. Under the optimum conditions obtained by this approach, the result of the experiment was satisfactory and proved that this novel approach was effective. Furthermore, we investigated the most important conditions that mainly affect the separation effectiveness of CE by partial least squares regression analysis. Because of the generalization of this new approach proposed, it can be applied to the optimization of other experimental processes.     

Systematic optimization of micellar electrokinetic chromatographic separation of flavonoids

Summary A simple and rapid systematic optimization scheme was described for the micellar electrokinetic chromatographic separation of a group of flavonoids. The scheme employed an interpretative optimization approach to predict the optimum conditions for the separation of a group of flavonoids by micellar electrokinetic chromatography. By performing a set of nine pre-planned experiments conducted over the maximum working range for the system, global optimum separation conditions could be determined. To validate the optimization procedure, additional experiments were performed using the optimum experimental conditions derived from the optimization scheme. The results showed that satisfactory separation of all the peaks could be obtained. In addition, the application of the method in micropreparative micellar electrokinetic chromatography of the flavonoids was demonstrated.     

Computer-aided target optimization for traditional Chinese medicine by ultra-performance liquid chromatography

A new strategy of target optimization was developed for resolving the separation problems of complex samples. Computer-aided target optimization for separation of complex samples by ultra-performance liquid chromatography (UPLC) was studied. Taking traditional Chinese medicine (TCM) (Rhizoma Coptidis) as an example, separation conditions of target compounds - overlapping peaks and all components - were optimized based on moved overlapping separation ranging map (OSRM) and artificially intervention. After calculating retention parameters and peak shape parameters of the target peaks, the optimization was operated in an emulational picture through the computer without further experiments. The emulational chromatogram was proved to be authentic by the estimated values, which were almost identical to experimental results. The method was very helpful for obtaining the satisfied separation conditions of target compounds rapidly and efficiently.     

Computer-assisted multifactor optimization of selectivity in gas chromatography

Summary A computer-assisted method is presented for the simultaneous multifactor optimization (stationary phase loading, column temperature and carrier gas flow rate) of the analytical conditions for the optimum separation of multicomponent samples in gas chromatography. The optimization of the separation over the experimental region is based on a special polynomial from twelve preliminary experiments using the resolution as the selection criterion. Computer scanning technique was used for optimum selection in three dimensions. Excellent agreement was obtained between the predicted data and the experimental results.     

计算机辅助柱色谱最优化分离氨基酸

计算机辅助柱色谱最优化分离氨基酸王琴孙，颜炳文，王寿亭，陶雪（南开大学元素有机化学研究所，天津，３０００７１）（南开大学高分子化学研究所）关键词计算机，色谱最优化，柱色谱微型计算机的发展推动了整个色谱优化领域的发展，也陆续出现了一些优化分离方法［１～...     

利用氧化和希夫碱反应制备具有手性分离功能的滤纸

纸色谱具有微量、快速、高效和灵活程度高等特点。以滤纸为原料用高碘酸钠氧化法合成了二醛基滤纸,通过希夫碱反应接枝手性氨基酸,合成了一种具有手性分离功能的新型纸色谱材料。通过单因素试验和正交试验确定滤纸氧化的最佳合成条件为：高碘酸钠的质量分数为4%, pH值为2,反应温度45℃和反应时间4 h,该条件下氧化滤纸醛基含量为57.93%（物质的量分数）。氧化滤纸与L-谷氨酸通过微波合成得到具有手性分离功能的色谱用纸。利用该种手性滤纸分离外消旋酒石酸,展开剂配方为100 mL 50%正丁醇,50 mL乙酸和0.1000 g溴酚绿。结果显示,L-酒石酸比移值（R_f）为0.52, D-酒石酸R_f为0.40。该方法不需要使用大型设备,适合一般的教学、研究及工业应用。     

薄层色谱溶剂系统的优化设计

采用复合形法,根据色谱优化函数对肾上腺皮质激素类、磺胺类药物及银杏粉针剂的薄层溶剂系统进行了最优化设计。肾上腺皮质激素类药物的最佳溶剂系统为１,２－二氯乙烷－苯－甲醇（４．８１４．４２０．７８）;磺胺类药物的最佳溶剂系统为甲苯－无水乙醇－二氯乙烷－氯仿（２．３０１．４６３．３２２．９２）;银杏粉针剂的最佳溶剂系统为氯仿－甲醇－乙酸乙酯（３．３０３．２９３．４１）,实验结果与计算结果一致。     

Simultaneous determination of multiclass preservatives including isothiazolinones and benzophenone‐type UV filters in household and personal care products by micellar electrokinetic chromatography

In this work, a simple and reliable micellar electrokinetic chromatography method for the separation and quantification of 14 preservatives, including isothiazolinones, and two benzophenone‐type UV filters in household, cosmetic and personal care products was developed. The selected priority compounds are widely used as ingredients in many personal care products, and are included in the European Regulation concerning cosmetic products. The electrophoretic separation parameters were optimized by means of a modified chromatographic response function in combination with an experimental design, namely a central composite design. After optimization of experimental conditions, the BGE selected for the separation of the targets consisted of 60 mM SDS, 18 mM sodium tetraborate, pH 9.4 and 10% v/v methanol. The MEKC method was checked in terms of linearity, LODs and quantification, repeatability, intermediate precision, and accuracy, providing appropriate values (i.e. R² ≥ 0.992, repeatability RSD values ?9%, and accuracy 90–115%). Applicability of the validated method was successfully assessed by quantifying preservatives and UV filters in commercial consumer products.