Biological chromatographic fingerprinting is a relatively new concept in the quality control of herbal samples. Originally it has been developed with the application of HPLC, and recently herbal samples' biological profiles have been obtained by means of thin-layer chromatography (TLC). This paper summarizes the application of liquid chromatographic techniques for the purpose of biological fingerprint analysis (BFA) of complex herbal samples. In case of biological TLC fingerprint, which is a relatively novel solution, perspectives of its further development are outlined in more detail. Apart from already published data, some novel results are also shown and briefly discussed. The paper aims at drawing scientists' attention to the unique solutions offered by biological fingerprint construction. 1. Introduction Fingerprint construction has become an important quality control tool of herbal samples in the light of constantly growing interest in natural origin medicines. Fingerprint analysis has been accepted by WHO as a methodology for the quality control of herbal samples [1, 2]. It is applied to identify closely related plant species, to detect adulterations, to control the extraction process or to study the quality of a finished product. Herbal sample fingerprint can be defined as a set of characteristic chromatographic or spectroscopic signals, whose comparison leads to an unambiguous sample recognition. Several chromatographic methods have been applied for fingerprint construction, namely, high-performance liquid chromatography (HPLC), thin-layer chromatography (TLC), gas chromatography (GC), or high-speed counter current chromatography (HSCCC). However, it is difficult to indicate with 100% certainty which signals (peaks, bands, etc.) should be present in the obtained fingerprint to confirm sample identity. For that purpose the analyzed sample can be compared with a defined Botanical Reference Material (BRM) or a set of standard compounds. Defining and obtaining BRM for every plant species is a difficult task, therefore, new solutions are sought for fingerprint comparison. More recently a concept of multiple fingerprints construction and multidimensional fingerprinting have gained much attention, as large amount of chromatographic and/or spectroscopic signals enable more comprehensive data analysis [3]. Multiple chromatographic fingerprint consists of more than one chromatographic profile [3], while in multidimensional fingerprinting hyphenated detectors are used (e.g., DAD and MS) that both record eluting compounds [1]. Usually the set of obtained
References
[1]
C. Tistaert, B. Dejaegher, and Y. V. Heyden, “Chromatographic separation techniques and data handling methods for herbal fingerprints: a review,” Analytica Chimica Acta, vol. 690, no. 2, pp. 148–161, 2011.
[2]
WHO, General Guidelines for Methodologies on Research and Evaluation of Traditional Medicine, World Health Organization, Geneva, Switzerland, 2000.
[3]
X. H. Fan, Y. Y. Cheng, Z. L. Ye, R. C. Lin, and Z. Z. Qian, “Multiple chromatographic fingerprinting and its application to the quality control of herbal medicines,” Analytica Chimica Acta, vol. 555, no. 2, pp. 217–224, 2006.
[4]
X. Su, L. Kong, X. Lei, L. Hu, M. Ye, and H. Zou, “Biological fingerprinting analysis of traditional Chinese medicines with targeting ADME/Tox property for screening of bioactive compounds by chromatographic and MS methods,” Mini-Reviews in Medicinal Chemistry, vol. 7, no. 1, pp. 87–98, 2007.
[5]
F. Yu, L. Kong, H. Zou, and X. Lei, “Progress on the screening and analysis of bioactive compounds in traditional Chinese medicines by biological fingerprinting analysis,” Combinatorial Chemistry and High Throughput Screening, vol. 13, no. 10, pp. 855–868, 2010.
[6]
X. Lei, L. Kong, H. Zou, H. Ma, and L. Yang, “Evaluation of the interaction of bioactive compounds in Cortex Pseudolarix and Radix Stephaniae by the microdialysis probe coupled with high performance liquid chromatography-mass spectrometry,” Journal of Chromatography A, vol. 1216, no. 11, pp. 2179–2184, 2009.
[7]
X. Su, L. Hu, L. Kong, X. Lei, and H. Zou, “Affinity chromatography with immobilized DNA stationary phase for biological fingerprinting analysis of traditional Chinese medicines,” Journal of Chromatography A, vol. 1154, no. 1-2, pp. 132–137, 2007.
[8]
X. Su, L. Kong, X. Li, X. Chen, M. Guo, and H. Zou, “Screening and analysis of bioactive compounds with biofingerprinting chromatogram analysis of traditional Chinese medicines targeting DNA by microdialysis/HPLC,” Journal of Chromatography A, vol. 1076, no. 1-2, pp. 118–126, 2005.
[9]
Y. Wang, L. Kong, L. Hu et al., “Biological fingerprinting analysis of the traditional Chinese prescription Longdan Xiegan Decoction by on/off-line comprehensive two-dimensional biochromatography,” Journal of Chromatography B, vol. 860, no. 2, pp. 185–194, 2007.
[10]
M. Guo, X. Su, L. Kong, X. Li, and H. Zou, “Characterization of interaction property of multicomponents in Chinese Herb with protein by microdialysis combined with HPLC,” Analytica Chimica Acta, vol. 556, no. 1, pp. 183–188, 2006.
[11]
X. Mao, L. Kong, Q. Luo, X. Li, and H. Zou, “Screening and analysis of permeable compounds in Radix Angelica Sinensis with immobilized liposome chromatography,” Journal of Chromatography B, vol. 779, no. 2, pp. 331–339, 2002.
[12]
Y. Wang, L. Kong, X. Lei et al., “Comprehensive two-dimensional high-performance liquid chromatography system with immobilized liposome chromatography column and reversed-phase column for separation of complex traditional Chinese medicine Longdan Xiegan Decoction,” Journal of Chromatography A, vol. 1216, no. 11, pp. 2185–2191, 2009.
[13]
J. L. Zhang, M. Cui, Y. He, H. L. Yu, and D. A. Guo, “Chemical fingerprint and metabolic fingerprint analysis of Danshen injection by HPLC-UV and HPLC-MS methods,” Journal of Pharmaceutical and Biomedical Analysis, vol. 36, no. 5, pp. 1029–1035, 2005.
[14]
H. A. G. Niederl？nder, T. A. van Beek, A. Bartasiute, and I. I. Koleva, “Antioxidant activity assays on-line with liquid chromatography,” Journal of Chromatography A, vol. 1210, no. 2, pp. 121–134, 2008.
[15]
M. Musialik, R. Kuzmicz, T. S. Pawlowski, and G. Litwinienko, “Acidity of hydroxyl groups: an overlooked influence on antiradical properties of flavonoids,” Journal of Organic Chemistry, vol. 74, no. 7, pp. 2699–2709, 2009.
[16]
Y. X. Chang, X. P. Ding, J. Qi et al., “The antioxidant-activity-integrated fingerprint: an advantageous tool for the evaluation of quality of herbal medicines,” Journal of Chromatography A, vol. 1208, no. 1-2, pp. 76–82, 2008.
[17]
T. A. van Beek, K. K. R. Tetala, I. I. Koleva et al., “Recent developments in the rapid analysis of plants and tracking their bioactive constituents,” Phytochemistry Reviews, vol. 8, no. 2, pp. 387–399, 2009.
[18]
A. M. van Nederkassel, M. Daszykowski, D. L. Massart, and Y. Vander Heyden, “Prediction of total green tea antioxidant capacity from chromatograms by multivariate modeling,” Journal of Chromatography A, vol. 1096, no. 1-2, pp. 177–186, 2005.
[19]
M. Daszykowski, Y. Vander Heyden, and B. Walczak, “Robust partial least squares model for prediction of green tea antioxidant capacity from chromatograms,” Journal of Chromatography A, vol. 1176, no. 1-2, pp. 12–18, 2007.
[20]
M. Dumarey, A. M. van Nederkassel, E. Deconinck, and Y. Vander Heyden, “Exploration of linear multivariate calibration techniques to predict the total antioxidant capacity of green tea from chromatographic fingerprints,” Journal of Chromatography A, vol. 1192, no. 1, pp. 81–88, 2008.
[21]
N. Nguyen Hoai, B. Dejaegher, C. Tistaert et al., “Development of HPLC fingerprints for Mallotus species extracts and evaluation of the peaks responsible for their antioxidant activity,” Journal of Pharmaceutical and Biomedical Analysis, vol. 50, no. 5, pp. 753–763, 2009.
[22]
C. Tistaert, B. Dejaegher, N. Nguyen Hoai et al., “Potential antioxidant compounds in Mallotus species fingerprints. Part I: indication, using linear multivariate calibration techniques,” Analytica Chimica Acta, vol. 649, no. 1, pp. 24–32, 2009.
[23]
M. Dumarey, I. Smets, and Y. Vander Heyden, “Prediction and interpretation of the antioxidant capacity of green tea from dissimilar chromatographic fingerprints,” Journal of Chromatography B, vol. 878, no. 28, pp. 2733–2740, 2010.
[24]
E. Reich and A. Schibli, High-Performance Thin-Layer Chromatography for the Analysis of Medicinal Plants, Thieme, New York, NY, USA, 2006.
[25]
？. Cie？la, D. Staszek, M. Hajnos, T. Kowalska, and M. Waksmundzka-Hajnos, “Development of chromatographic and free radical scavenging activity fingerprints by thin-layer chromatography for selected Salvia species,” Phytochemical Analysis, vol. 22, no. 1, pp. 59–65, 2011.
[26]
T. Yrj？nen, L. Peiwu, J. Summanen, A. Hopia, and H. Vuorela, “Free radical-scavenging activity of phenolics by reversed-phase TLC,” Journal of the American Oil Chemists' Society, vol. 80, no. 1, pp. 9–14, 2003.
[27]
？. Cie？la and M. Waksmundzka-Hajnos, “Application of thin-layer chromatography for the quality control and screening the free radical scavenging activity of selected pharmacuetical preparations containing Salvia officinalis L. extract,” Acta Poloniae Pharmaceutica—Drug Research, vol. 67, no. 5, pp. 481–485, 2010.
[28]
S. B. Chen, H. P. Liu, R. T. Tian et al., “High-performance thin-layer chromatographic fingerprints of isoflavonoids for distinguishing between Radix Puerariae Lobate and Radix Puerariae Thomsonii,” Journal of Chromatography A, vol. 1121, no. 1, pp. 114–119, 2006.
[29]
？. Cie？la, “Thin-layer chromatography with biodetection for the search of new potential drugs to treat neurodegenerative diseases—state of the art and future perspectives,” Medicinal Chemistry. In press.
[30]
A. Marston, “Thin-layer chromatography with biological detection in phytochemistry,” Journal of Chromatography A, vol. 1218, no. 19, pp. 2676–2683, 2011.
[31]
I. M. Choma and E. M. Grzelak, “Bioautography detection in thin-layer chromatography,” Journal of Chromatography A, vol. 1218, no. 19, pp. 2684–2691, 2011.
[32]
Z.-D. Yang, Z.-W. Song, J. Ren, M.-J. Yang, and S. Li, “Improved thin-layer chromatography bioautographic assay for the detection of acetylcholinesterase inhibitors in plants,” Phytochemical Analysis, vol. 22, no. 6, pp. 509–515, 2011.
[33]
？. Cie？la, J. Kryszeń, A. Stochmal, and M. Waksmundzka-Hajnos, “TLC-DPPH test revisited,” in Proceedings of the 34th Symposium: Chromatographic Methods of Investigating the Organic Compounds, Katowice-Szczyrk, Poland, June 2011.
[34]
？. Cie？la, J. Kryszeń, and M. Waksmundzka-Hajnos, “unpublished results”.
[35]
P. J. Houghton, M. J. Howes, C. C. Lee, and G. Steventon, “Uses and abuses of in vitro tests in ethnopharmacology: visualizing an elephant,” Journal of Ethnopharmacology, vol. 110, no. 3, pp. 391–400, 2007.
[36]
I. K. Rhee, M. van de Meent, K. Ingkaninan, and R. Verpoorte, “Screening for acetylcholinesterase inhibitors from Amaryllidaceae using silica gel thin-layer chromatography in combination with bioactivity staining,” Journal of Chromatography A, vol. 915, no. 1-2, pp. 217–223, 2001.
[37]
S. Di Giovanni, A. Borloz, A. Urbain et al., “In vitro screening assays to identify natural or synthetic acetylcholinesterase inhibitors: thin layer chromatography versus microplate methods,” European Journal of Pharmaceutical Sciences, vol. 33, no. 2, pp. 109–119, 2008.
[38]
？. Cie？la and M. Waksmundzka-Hajnos, “Two-dimensional thin-layer chromatography in the analysis of secondary plant metabolites,” Journal of Chromatography A, vol. 1216, no. 7, pp. 1035–1052, 2009.
[39]
？. Cie？la and M. Waksmundzka-Hajnos, “Multidimensional and multimodal separations by HPTLC in phytochemistry,” in High-Performance Thin-Layer Chromatography (HPTLC), M. M. Srivastava, Ed., Springer, Berlin, Germany, 2011.
[40]
？. Cie？la, A. Bogucka-Kocka, M. Hajnos, A. Petruczynik, and M. Waksmundzka-Hajnos, “Two-dimensional thin-layer chromatography with adsorbent gradient as a method of chromatographic fingerprinting of furanocoumarins for distinguishing selected varieties and forms of Heracleum spp,” Journal of Chromatography A, vol. 1207, no. 1-2, pp. 160–168, 2008.
[41]
L. Cie？la, K. Skalicka-Wo？niak, M. Hajnos, M. Hawry？, and M. Waksmundzka-Hajnos, “Multidimensional TLC procedure for separation of complex natural mixtures spanning a wide polarity range; Application for fingerprint construction and for investigation of systematic relationships within the Peucedanum genus,” Acta Chromatographica, vol. 21, no. 4, pp. 641–657, 2009.
[42]
？. Komsta, T. Cie？la, A. Bogucka-Kocka, A. Józefczyk, J. Kryszeń, and M. Waksmundzka-Hajnos, “The start-to-end chemometric image processing of 2D thin-layer videoscans,” Journal of Chromatography A, vol. 1218, no. 19, pp. 2820–2825, 2011.
[43]
L. Cie？la, M. Hajnos, and M. Waksmundzka-Hajnos, “Application of hydrophilic interaction TLC systems for separation of highly polar glycosidic compounds from the flowers of selected Verbascum species,” Journal of Planar Chromatography—Modern TLC, vol. 24, no. 4, pp. 295–300, 2011.
[44]
G. Morlock and W. Schwack, “Hyphenations in planar chromatography,” Journal of Chromatography A, vol. 1217, no. 43, pp. 6600–6609, 2010.
[45]
M. Sajewicz, ？. Wojtal, M. Hajnos, M. Waksmundzka-Hajnos, and T. Kowalska, “Low-temperature TLC-MS of essential oils from five different sage (Salvia) species,” Journal of Planar Chromatography—Modern TLC, vol. 23, no. 4, pp. 270–276, 2010.
[46]
M. Sajewicz, L. Wojtal, D. Staszek, M. Hajnos, M. Waksmundzka-Hajnos, and T. Kowalska, “Low temperature planar chromatography-densitometry and gas chromatography of essential oils from different sage (Salvia) species,” Journal of Liquid Chromatography and Related Technologies, vol. 33, no. 7-8, pp. 936–947, 2010.
[47]
M. A. Hawry？ and M. Waksmundzka-Hajnos, “Two-dimensional thin-layer chromatography of selected Polygonum sp. extracts on polar-bonded stationary phases,” Journal of Chromatography A, vol. 1218, no. 19, pp. 2812–2819, 2011.
