Unconventional TLC systems in lipophilicity determination: A review

ABSTRACT

This review focuses on four unusual thin-layer chromatography (TLC) approaches for the determination of lipophilicity: (1) the use of medium-polar stationary phases: CN, NH₂, and DIOL instead of RP plates, together with water-based mobile phase; (2) the use of silica gel in a typical normal-phase manner and treating extrapolated retention indices as the “reversed lipophilicity”; (3) the use of oil impregnated silica gel in the reversed-phase manner; and (4) the use of salting-out mobile phases. The chromatographic indices obtained in these systems are numerously reported as well correlated with lipophilicity and they are an interesting alternative to classical RP systems approaches.     

Lipophilicity of oils and fats estimated by TLC

A representative series of natural toxins belonging to alkaloids and mycotoxins classes was investigated by TLC on classical chemically bonded plates and also on oils‐ and fats‐impregnated plates. Their lipophilicity indices are employed in the characterization and comparison of oils and fats. The retention results allowed an accurate indirect estimation of oils and fats lipophilicity. The investigated fats and oils near classical chemically bonded phases are classified and compared by means of multivariate exploratory techniques, such as cluster analysis, principal component analysis, or fuzzy‐principal component analysis. Additionally, a concrete hierarchy of oils and fats derived from the observed lipophilic character is suggested. Human fat seems to be very similar to animal fats, but also possess RP‐18, RP‐18W, and RP‐8.     

Multivariate analysis of PRISMA optimized TLC image for predicting antioxidant activity and identification of contributing compounds from Pereskia bleo

Multivariate analysis of thin‐layer chromatography (TLC) images was modeled to predict antioxidant activity of Pereskia bleo leaves and to identify the contributing compounds of the activity. TLC was developed in optimized mobile phase using the ‘PRISMA’ optimization method and the image was then converted to wavelet signals and imported for multivariate analysis. An orthogonal partial least square (OPLS) model was developed consisting of a wavelet‐converted TLC image and 2,2‐diphynyl‐picrylhydrazyl free radical scavenging activity of 24 different preparations of P. bleo as the x‐ and y‐variables, respectively. The quality of the constructed OPLS model (1 + 1 + 0) with one predictive and one orthogonal component was evaluated by internal and external validity tests. The validated model was then used to identify the contributing spot from the TLC plate that was then analyzed by GC‐MS after trimethylsilyl derivatization. Glycerol and amine compounds were mainly found to contribute to the antioxidant activity of the sample. An alternative method to predict the antioxidant activity of a new sample of P. bleo leaves has been developed. Copyright © 2015 John Wiley & Sons, Ltd.     

薄层色谱溶剂系统优化方法进展

介绍了薄层色谱溶剂分类和溶剂强度参数的进展,综述了近年来优化溶剂系统的九种方法,并对它们进行了比较。     

Lipophilicity of some guaianolides isolated from two endemic subspecies of Amphoricarpos neumayeri (Asteraceae) from Montenegro

In this study 10 guaianolide-type sesquiterpene gamma-lactones named amphoricarpolides, isolated from the aerial parts of two endemic subspecies of Amphoricarpos neumayeri (ssp. neumayeri and ssp. murbeckii Bosnjak), were investigated by means of reversed-phase thin-layer chromatography. Methanol-water and tetrahydrofuran-water binary mixtures were used as mobile phase in order to determine lipophilicity parameters R (0) (M) and C(0). Some of the investigated compounds were screened for their cytotoxic activity against HeLa and B16 cells. Chromatographically obtained lipophilicity parameters were correlated with calculated logP values and IC(50) values. Principal component analysis identified the dominant pattern in the chromatographically obtained data.     

Determination of the lipophilicity of Salvia miltiorrhiza Radix et Rhizoma (danshen root) ingredients by microemulsion liquid chromatography: optimization using cluster analysis and a linear solvation energy relationship‐based method

We evaluated 26 microemulsion liquid chromatography (MELC) systems for their potential as high‐throughput screening platforms capable of modeling the partitioning behaviors of drug compounds in an n‐octanol–water system, and for predicting the lipophilicity of those compounds (i.e. logP values). The MELC systems were compared by cluster analysis and a linear solvation energy relationship (LSER)‐based method, and the optimal system was identified by comparing their Euclidean distances with the LSER coefficients. The most effective MELC system had a mobile phase consisting of 6.0% (w/w) Brij35 (a detergent), 6.6% (w/w) butanol, 0.8% (w/w) cyclohexane, 86.6% (w/w) buffer solution and 8 mm cetyltrimethyl ammonium bromide. The reliability of the established platform was confirmed by the agreement between the experimental data and the predicted values. The logP values of the ingredients of danshen root (Salvia miltiorrhiza Radix et Rhizoma) were then predicted. Copyright © 2015 John Wiley & Sons, Ltd.     

Modeling of Anticancer Sulfonamide Derivatives Lipophilicity by Chemometric and Quantitative Structure-Retention Relationships Approaches

Sulfonamides are a classic group of chemotherapeutic drugs with a broad spectrum of pharmacological action, including anticancer activity. In this work, reversed-phase high-performance liquid chromatography and biomimetic chromatography were applied to characterize the lipophilicity of sulfonamide derivatives with proven anticancer activities against human colon cancer. Chromatographically determined lipophilicity parameters were compared with obtained logP, employing various computational approaches. Similarities and dissimilarities between experimental and computational logP were studied using principal component analysis, cluster analysis, and the sum of ranking differences. Furthermore, quantitative structure–retention relationship modeling was applied to understand the influences of sulfonamide’s molecular properties on lipophilicity and affinity to phospholipids.     

Ligand Exchange Reactions for the Fluorescent Detection of Nanogram Amounts of Metal Ions on TLC Plates

Abstract

A number of metal ions have been separated as their diethyldithiocarbamate chelates by thin-layer chromatography and detected by means of a ligand exchange reaction between a metal/calcein complex and the diethyldithiocarbamate chelate. Visual detection limits, after development, are 0.1 to 2 ng per spot for the metal ions studied. The potential of this new method for the fluorescent analysis of metal ions is discussed. It is particularly promising as a simple field method. Spiked natural water samples are analyzed to demonstrate its usefulness.     

甾体药物薄层色谱分析数据库

利用ＴＵＲＢＯＰＲＯＬＯＧ程序设计语言,建立了一个甾体药物薄层色谱分析数据库,收集了中国药典一九九０年版、英国药典一九八八年版及美国药典第二十二版中甾体原料药及其制剂的薄层色谱数据,为甾体药物的薄层色谱分析提供了方便。     

牛蒡子中木脂素的薄层扫描测定

在高效硅胶薄层板上分离了牛蒡子中４种２,３－苄基丁内酯型木脂素──牛蒡甙元（Ｉ）、牛蒡素Ｂ（Ⅱ）、牛蒡酚Ａ（Ⅲ）、牛蒡酚Ｆ（Ⅳ）。流动相为二氯甲烷－乙醚－甲醇－己烷（４：１：０．４：１）,室温放置,自然显色。薄层扫描法定量,各木脂素的线性范围在０．４５１～４．６０８μｇ,回收率为９９．９０％～１００．９０％,并用此法测定了不同产地牛蒡子中木脂素的含量。方法简便、快速,样品用量少。     

Theoretical Study of Molecular Structure,Reactivity, Lipophilicity,and Solubility of N-Hydroxyurea,N-Hydroxythiourea,and N-Hydroxysilaurea

Ab initio molecular orbital methods at the CBS-QB3 level of theory have been used to study the structure and gas-phase stability of various tautomers and rotamers of N-hydroxyurea, N-hydroxythiourea, and N-hydroxysilaurea, their anions and protonated forms. The geometries of N-hydroxyurea, N-hydroxythiourea, and N-hydroxysilaurea, their anions and cations were optimized at the Becke3LYP/CBSB7 level of theory. For all compounds studied, the amidic form is computed to be substantially more stable than the iminolic tautomer. N-Hydroxyurea and its thio and sila derivatives are computed to behave as Nacids in the gas phase. These compounds are in gas-phase weak acids with a calculated acidity of about 1425 to 1355 kJ-mol^–1. Basicities increase in the order: N-hydroxyurea < N-hydroxythiourea < N-hydroxysilaurea. The most stable protonated structures are represented by several isomers with almost equal stability. Thus, in the N-hydroxyurea, N-hydroxythiourea, and N-hydroxysilaurea, both protonation at the double bonded (C=O, C=S and Si=O) oxygen and sulfur atoms, as well as the protonation at the N(H)OH nitrogen basic center is equally probable. The experimental pK _a value (10.6) of N-hydroxyurea and the computed value (9.7) for its monohydrated complex with the specifically hydrogen-bonded water molecule to the ionizable OH group are in a good agreement. The experimental partition coefficient of N-hydroxyurea is best reproduced by the Alog P_s method. The formation of nitroxide radical in the reaction of N-hydroxyurea and its sulfur and silicon substituted derivatives with the phenol radical is an exothermic process. Thus, the \bondN(H)OH moiety of these compounds may quench the structurally related tyrosyl radicals in the active site of ribonucleotide reductase.     

Identification of flavonoids by TLC scanning analysis

Summary A TLC-densitometric method for flavonoid analysis is described. Results are comparable to those obtained with classical methods. As the isolation step can be avoided results can be observed with 100 ng samples.     

Advances in the thin-layer chromatographic forensic analysis of inks

Advances in the use of thin layer and high-performance thin-layer chromatography for analysis of inks and ink writings in forensic investigations are reviewed. Experimental materials and techniques such as sample preparation, layers, sample application, development, detection, documentation, and interpretation of results are described and selected applications for several ink types are given. Some additional analytical techniques that complement thin-layer chromatography are also mentioned. Citations to important literature, from 2008 to 2016, are included.     

The use of a new,modified Dittmer–Lester spray reagent for phospholipid determination by the TLC image analysis technique

A new phospholipid‐specific spray reagent is described. A new phospholipid‐specific spray reagent, which is a modification of the Dittmer–Lester reagent, is described in authors' studies. The difference between these two reagents is in the addition of tin (II) chloride to the proposed spray reagent. The use of the described spray reagent together with an image analysis technique allows not only for qualitative, but also for quantitative, determination of major phospholipid classes. Separation of phosphatidylserine (PS), phosphatidylethanolamine (PE) and phosphatidylcholine (PC) was conducted on an HPTLC plate with a mixture of chloroform, methanol and 25% ammonia solution in a volume ratio of 65:25:4 as mobile phase. The calibration curves were linear in the ranges of 5.0–25.0, 1.5–15.0 and 1.0–20.0 µg/spot for PC, PS and PE, respectively. The use of the new spray reagent resulted also in lower limits of detection than the standard molybdenum method for the investigated phospholipids. The proposed method was used to determine the amount of PS in the dietary supplement ‘Session’, and of PS, PE and PC in biological samples, with good results. Copyright © 2012 John Wiley & Sons, Ltd.     

薄层扫描法测定冬眠过程中刺猬活性组织酶的周期变化

薄层扫描法测定冬眠过程中刺猬活性组织酶的周期变化冯金城（天津师范大学天津３０００７４）孙金生（天津水产研究所天津３００２２１）１前言为了跟踪观察刺猬在冬眠过程中体内乳酸脱氢酶的周期性变化，利用薄层扫描仪测定了其相关的组织同工酶的差异。实践证明，此法简...     

酰胺反应的薄层色谱法分析

用薄层色谱法监测了二氯乙酰氯与相应的胺合成二氯乙酰胺的反应过程,方法操作简便、快速、准确。     

薄层色谱分离-水合茚三酮可见分光光度法测定食品添加剂中的γ-氨基丁酸

为建立一种以水合茚三酮为显色剂准确定量检测γ-氨基丁酸(γ-aminobutyric acid,GABA)的方法,本文系统研究了显色酸度、显色剂用量、加热温度和时间等显色条件对水合茚三酮与GABA显色反应的影响,并在最优条件下对该方法进行了评价.结果表明,在pH=7.0时,GABA与1.8 g·L-1茚三酮乙醇溶液沸水...     

液相色谱法分离金属螯合物的进展

综述了用薄层液相色谱法和柱液相色谱法分离金属螯合物的进展及其在金属离子分析方面的应用。