v10n4doi10.5935/sc.2019.001en
https://dx.doi.org/10.5935/sc.2019.001
Analytical methods for determination of isoflavones in complex matrices
Silva L. F., Sinisterra M. J., Lanças F. M.
Keywords: isoflavones, complex matrices, analytical methods, sample preparation, separation techniques.
Abstract: Isoflavones are an important subclass of phytoestrogens. They are throughout the plant kingdom, often present in our diet and are associated with several benefits to human health, such as prevention of cardiovascular diseases and breast cancer. These factors have aroused the interest of the scientific community, causing a significant increase in the number of publications related to these compounds in the last two decades. In this work we present an overview on sample preparation techniques, chromatographic separation techniques, and chromatography coupled to different detection techniques applied to the analysis of isoflavones in several matrices, from 2010 to the present days. Studies have reported on the analysis of isoflavones in soybean, soy derivatives, bovine milk, urine, plasma, water and others. Among the sample preparation techniques, there are reports involving LLE, SLE, SPE, QuEChERS, MSPD SPME and MEPS. Classical sample preparation techniques are often used. There are well-developed micro-techniques such as SPME and MEPS, however their use in sample preparation aiming to determine isoflavones is very limited, practically restricted to analytical development studies. Among the chromatographic techniques HPLC, UHPLC and GC are the most popular ones, being followed by the electrophoretic techniques. The most common detectors in this analytical niche are mass spectrometers and UV-Vis spectrophotometers, respectively.
Referências Bibliográficas
[1] Wu Q, Wang M, Simon JE. Analytical methods to determine phytoestrogenic compounds. J Chromatogr B Anal Technol Biomed Life Sci. 2004 Dec;812(1–2 SPEC. ISS.):325–55. Available from: https://doi.org/10.1016/j.jchromb.2004.08.008
[2] Bhathena SJ, Velasquez MT. Beneficial role of dietary phytoestrogens in obesity and diabetes. Am J Clin Nutr. 2002 Dec;76(6):1191–201. Available from: https://doi.org/10.1093/ajcn/76.6.1191
[3] López-Biedma A, Sánchez-Quesada C, Delgado-Rodríguez M, Gaforio JJ. The biological activities of natural lignans from olives and virgin olive oils: A review. J Funct Foods. 2016 Oct;26:36–47. Available from: https://doi.org/10.1016/j.jff.2016.07.005
[4] Yu J, Wu Q, Qiao S, Yu Z, Jin N, Yu B. Simultaneous determination of phytoestrogens and key metabolites in breast cancer patients’ urine by liquid chromatography-tandem mass spectrometry. J Pharm Biomed Anal. 2009 Dec;50(5):939–46. Available from: https://doi.org/10.1016/j.jpba.2009.06.032
[5] Matsumura A, Ghosh A, Pope GS, Darbre PD. Comparative study of oestrogenic properties of eight phytoestrogens in MCF7 human breast cancer cells. J Steroid Biochem Mol Biol. 2005 Apr;94(5):431–43. Available from: https://doi.org/10.1016/j.jsbmb.2004.12.041
[6] Vejdovszky K, Schmidt V, Warth B, Marko D. Combinatory estrogenic effects between the isoflavone genistein and the mycotoxins zearalenone and alternariol in vitro. Mol Nutr Food Res. 2017 Oct;61(3):1–12. Available from: https://doi.org/10.1002/mnfr.201600526
[7] Nijveldt RJ, Nood Ev, van Hoorn DEC, Boelens PG, van Norren K, van Leeuwen PA. Flavonoids: a review of probable mechanisms of action. Am J Clin Nutr. 2001 Oct;74:418–25. Available from: https://doi.org/10.1093/ajcn/74.4.418
[8] Rice-Evans CA, Miller NJ, Paganga G. Structure-antioxidant activity relationships of flavonoids and phenolic acids. Free Radic Biol Med. 1996 Nov;20(7):933–56. Available from: https://doi.org/10.1016/0891-5849(95)02227-9
[9] Pietta PG. Flavonoids as antioxidants. J Nat Prod. 2000 May;63(7):1035–42. Available from: https://pubs.acs.org/doi/abs/10.1021/np9904509
[10] Ren MQ, Kuhn G, Wegner J, Chen J. Isoflavones, substances with multi-biological and clinical properties. Eur J Nutr. 2001 Aug;40(4):135–46. Available from: https://doi.org/10.1007/PL00007388
[11] Wu AH, Ziegler RG, Horn-Ross PL, Nomura AM, West DW, Kolonel LN, Rosenthal JF, Hoover RN, Pike MC. Tofu and risk of breast cancer in Asian-Americans. Cancer Epidemiol Biomarkers Prev [Internet]. 1996 Nov;5(11):901–6. Available from: https://cebp.aacrjournals.org/content/5/11/901.short
[12] Adlercreutz H. Phytoestrogens and breast cancer. J Steroid Biochem Mol Biol. 2002 Dec;83(1–5):113–8. Available from: https://doi.org/10.1016/S0960-0760(02)00273-X
[13] Anthony MS, Clarkson TB, Williams JK. Effects of soy isoflavones on atherosclerosis: Potential mechanisms. Am J Clin Nutr. 1998 Dec;68(6 SUPPL.):1390–3. Available from: https://doi.org/10.1093/ajcn/68.6.1390S
[14] Zhi CD, Lowik C. Dose-dependent effects of phytoestrogens on bone. Trends Endocrinol Metab. 2005 Jul;16(5):207–13. Available from: https://doi.org/10.1016/j.tem.2005.05.001
[15] Knight DC, Eden JA. A review of the clinical effects of phytoestrogens. Obstet Gynecol. 1996 May;87(5):897–904. Available from: https://www.sciencedirect.com/science/article/pii/S0029784496804613
[16] Tsunoda N, Pomeroy S, Nestel P. Absorption in Humans of Isoflavones from Soy and Red Clover Is Similar. J Nutr. 2018 Aug;132(8):2199–201. Available from: https://doi.org/10.1093/jn/132.8.2199
[17] Manchón N, D’Arrigo M, García-Lafuente A, Guillamón E, Villares A, Ramos A, Martínez, JA, Rostagno, MA. Fast analysis of isoflavones by high-performance liquid chromatography using a column packed with fused-core particles. Talanta. 2010 Oct;82(5):1986–94. Available from: https://doi.org/10.1016/j.talanta.2010.08.050
[18] Lee JH, Choung MG. Determination of curcuminoid colouring principles in commercial foods by HPLC. Food Chem. 2011 Feb;124(3):1217–22. Available from: https://doi.org/10.1016/j.foodchem.2010.07.049
[19] Yanaka K, Takebayashi J, Matsumoto T, Ishimi Y. Determination of 15 isoflavone isomers in soy foods and supplements by high-performance liquid chromatography. J Agric Food Chem. 2012 Mar;60(16):4012–6. Available from: https://pubs.acs.org/doi/abs/10.1021/jf205154x
[20] Jankowiak L, Kantzas N, Boom R, Van Der Goot AJ. Isoflavone extraction from okara using water as extractant. Food Chem. 2014 Oct;160:371–8. Available from: https://doi.org/10.1016/j.foodchem.2014.03.082
[21] Desfontaine V, Guillarme D, Francotte E, Nováková L. Supercritical fluid chromatography in pharmaceutical analysis. J Pharm Biomed Anal [Internet]. 2015 Sep;113:56–71. Available from: https://doi.org/10.1016/j.jpba.2015.03.007
[22] Yuk HJ, Song YH, Curtis-Long MJ, Kim DW, Woo SG, Lee YB, Uddin Z, Kim CY, Park KH. Ethylene Induced a High Accumulation of Dietary Isoflavones and Expression of Isoflavonoid Biosynthetic Genes in Soybean (Glycine max) Leaves. J Agric Food Chem. 2016 Sep;64(39):7315–24. Available from: https://pubs.acs.org/doi/abs/10.1021/acs.jafc.6b02543
[23] Yilmaz A, Rudolph HL, Hurst JJ, Wood TD. High-Throughput Metabolic Profiling of Soybean Leaves by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Anal Chem. 2016 Dec;88(2):1188–94. Available from: https://pubs.acs.org/doi/abs/10.1021/acs.analchem.5b03340
[24] Zhang M, Sun J, Chen P. Development of a Comprehensive Flavonoid Analysis Computational Tool for Ultrahigh-Performance Liquid Chromatography-Diode Array Detection-High-Resolution Accurate Mass-Mass Spectrometry Data. Anal Chem. 2017 Jun;89(14):7388–97. Available from: https://pubs.acs.org/doi/abs/10.1021/acs.analchem.7b00771
[25] Góes-Favoni SP, Carrão-Panizzi MC, Beleia A. Changes of isoflavone in soybean cotyledons soaked in different volumes of water. Food Chem. 2010 Apr;119(4):1605–12. Available from: https://doi.org/10.1016/j.foodchem.2009.09.051
[26] Lee JH, Choung MG. Determination of optimal acid hydrolysis time of soybean isoflavones using drying oven and microwave assisted methods. Food Chem. 2011 Nov;129(2):577–82. Available from: https://doi.org/10.1016/j.foodchem.2011.04.069
[27] Terigar BG, Balasubramanian S, Boldor D, Xu Z, Lima M, Sabliov CM. Continuous microwave-assisted isoflavone extraction system: Design and performance evaluation. Bioresour Technol. 2010 Apr;101(7):2466–71. Available from: https://doi.org/10.1016/j.biortech.2009.11.039
[28] Zafra-Gómez A, Garballo A, García-Ayuso LE, Morales JC. Improved sample treatment and chromatographic method for the determination of isoflavones in supplemented foods. Food Chem. 2010 Dec;123(3):872–7. Available from: https://doi.org/10.1016/j.foodchem.2010.05.009
[29] Moreira BJ, Yokoya JMC, Gaitani CM De. Microextração líquido-líquido dispersiva (DLLME): fundamentos , inovações e aplicações biológicas. Sci Chromatogr. 2014 Dec;6(3):186–204. Available from: https://dx.doi.org/10.4322/sc.2015.005
[30] Nara K, Nihei KI, Ogasawara Y, Koga H, Kato Y. Novel isoflavone diglycoside in groundnut (Apios americana Medik). Food Chem. 2011 Feb;124(3):703–10. Available from: https://doi.org/10.1016/j.foodchem.2010.05.107
[31] Zhang Wd, Yang Wj, Wang Xj, Gu Y, Wang R. Simultaneous determination of tectorigenin, irigenin and irisflorentin in rat plasma and urine by UHPLC-MS/MS: Application to pharmacokinetics. J Chromatogr B Anal Technol Biomed Life Sci. 2011 Dec;879(31):3735–41. Available from: https://doi.org/10.1016/j.jchromb.2011.10.022
[32] Matsumoto D, Kotani A, Hakamata H, Takahashi K, Kusu F. Column switching high-performance liquid chromatography with two channels electrochemical detection for high-sensitive determination of isoflavones. J Chromatogr A. 2010 Apr;1217(17):2986–9. Available from: https://doi.org/10.1016/j.chroma.2010.02.050
[33] Park HJ, Jung MY. One step salting-out assisted liquid-liquid extraction followed by UHPLC-ESI-MS/MS for the analysis of isoflavones in soy milk. Food Chem. 2017 Aug;229:797–804. Available from: https://doi.org/10.1016/j.foodchem.2017.02.145
[34] Kašparovská J, Dadáková K, Lochman J, Hadrová S, Křížová L, Kašparovský T. Changes in equol and major soybean isoflavone contents during processing and storage of yogurts made from control or isoflavone-enriched bovine milk determined using LC–MS (TOF) analysis. Food Chem. 2017 May;222:67–73. Available from: https://doi.org/10.1016/j.foodchem.2016.12.010
[35] Kunisue T, Tanabe S, Isobe T, Aldous KM, Kannan K. Profiles of phytoestrogens in human urine from several Asian countries. J Agric Food Chem. 2010 Aug;58(17):9838–46. Available from: https://pubs.acs.org/doi/abs/10.1021/jf102253j
[36] Ma Y, Zhang L, Zhao X, Shen Q. Analysis of daidzein in nanoparticles after oral co-administration with sodium caprate to rats by ultra-performance liquid chromatography-quadrupole-time-of-flight mass spectrometry. J Chromatogr B. 2012 Oct;907:21–6. Available from: https://doi.org/10.1016/j.jchromb.2012.08.026
[37] Fiechter G, Raba B, Jungmayr A, Mayer HK. Characterization of isoflavone composition in soy-based nutritional supplements via ultra performance liquid chromatography. Anal Chim Acta. 2010 Jul;672(1–2):72–8. Available from: https://doi.org/10.1016/j.aca.2010.04.004
[38] Jardim ICSF. Extração em Fase Sólida : Fundamentos Teóricos e Novas Estratégias para Preparação de Fases Sólidas. Sci Chromatogr. 2010;2(1):13–25. Available from: https://www.iicweb.org/scientiachromatographica.com/files/v2n1a2.pdf
[39] Nováková L, Vlčková H. A review of current trends and advances in modern bio-analytical methods : Chromatography and sample preparation. Anal Chim Acta. 2009 Dec;656:8–35. Available from: https://doi.org/10.1016/j.aca.2009.10.004
[40] Hosoda K, Furuta T, Ishii K. Simultaneous determination of glucuronic acid and sulfuric acid conjugated metabolites of daidzein and genistein in human plasma by high-performance liquid chromatography. J Chromatogr B Anal Technol Biomed Life Sci. 2010 Mar;878(7–8):628–36. Available from: https://doi.org/10.1016/j.jchromb.2010.01.028
[41] Saracino MA, Raggi MA. Analysis of soy isoflavone plasma levels using HPLC with coulometric detection in postmenopausal women. J Pharm Biomed Anal. 2010 Nov;53(3):682–7. Available from: https://doi.org/10.1016/j.jpba.2010.06.001
[42] Rodríguez-Morató J, Farré M, Pérez-Maná C, Papaseit E, Martínez-Riera R, de la Torre R, Pizarro, N. Pharmacokinetic Comparison of Soy Isoflavone Extracts in Human Plasma. J Agric Food Chem. 2015 Jul;63(31):6946–53. Available from: https://pubs.acs.org/doi/abs/10.1021/acs.jafc.5b02891
[43] Baranowska I, Magiera S, Baranowski J. UHPLC method for the simultaneous determination of β-blockers, isoflavones, and flavonoids in human urine. J Chromatogr Sci. 2011 Mar;49(10):764–73. Available from: https://doi.org/10.1016/j.jchromb.2011.01.026
[44] Redruello B, Guadamuro L, Cuesta I, Álvarez-Buylla JR, Mayo B, Delgado S. A novel UHPLC method for the rapid and simultaneous determination of daidzein, genistein and equol in human urine. J Chromatogr B Anal Technol Biomed Life Sci. 2015 Nov;1005:1–8. Available from: https://doi.org/10.1016/j.jchromb.2015.09.029
[45] Li T, Wang Y, Wang Y, Liang R, Zhang D, Zhang H, Chen L, Yang W. Development of an SPE-HPLC-MS method for simultaneous determination and pharmacokinetic study of bioactive constituents of Yu Ping Feng San in rat plasma after oral administration. J Ethnopharmacol. 2013 Feb;145(3):784–92. Available from: https://doi.org/10.1016/j.jep.2012.12.010
[46] Procházková T, Sychrová E, Javůrková B, Večerková J, Kohoutek J, Lepšová-Skácelová O, Bláha L, Hilscherová K. Phytoestrogens and sterols in waters with cyanobacterial blooms - Analytical methods and estrogenic potencies. Chemosphere. 2017 Mar;170:104–12. Available from: https://doi.org/10.1016/j.chemosphere.2016.12.006
[47] Benedetti B, Di Carro MD, Magi E. Phytoestrogens in soy-based meat substitutes: Comparison of different extraction methods for the subsequent analysis by liquid chromatography-tandem mass spectrometry. J Mass Spectrom. 2018 Jul;53(9):862–70. Available from: https://doi.org/10.1002/jms.4268
[48] González-Curbelo MÁ, Socas-Rodríguez B, Herrera-Herrera AV, González-Sálamo J, Hernández-Borges J, Rodríguez-Delgado MÁ. Trends in Analytical Chemistry Evolution and applications of the QuEChERS method. Trends Anal Chem [Internet]. 2015 Sep;71:169–85. Available from: https://doi.org/10.1016/j.trac.2015.04.012
[49] Delgado-Zamarreño MM, Pérez-Martín L, Bustamante-Rangel M, Carabias-Martínez R. A modified QuEChERS method as sample treatment before the determination of isoflavones in foods by ultra-performance liquid chromatography-triple quadrupole mass spectrometry. Talanta. 2012 Oct;100:320–8. Available from: https://doi.org/10.1016/j.talanta.2012.07.070
[50] Merlanti R, Lucatello L, Inacio JL, Pastore RM, Laverda S, Capolongo F. Isoflavones quantification in rainbow trout muscle by QuEChERS tecnique and liquid chromatography coupled with mass spectrometry. J Food Compos Anal [Internet]. 2018 Jul;70:114–24. Available from: https://doi.org/10.1016/j.jfca.2018.04.009
[51] Capriotti AL, Cavaliere C, Giansanti P, Gubbiotti R, Samperi R, Laganà A. Recent developments in matrix solid-phase dispersion extraction. J Chromatogr A. 2010 Apr;1217:2521–32. Available from: https://doi.org/10.1016/j.chroma.2010.01.030
[52] Barker SA. Matrix solid phase dispersion (MSPD). J Biochem Biophys Methods. 2007 Mar;70:151–62. Available from: https://doi.org/10.1016/j.jbbm.2006.06.005
[53] Peng L, Li Q, Chang Y, An M, Yang R, Tan Z, Hao J, Cao J, Xu JJ, Hu SS. Determination of natural phenols in olive fruits by chitosan assisted matrix solid-phase dispersion microextraction and ultrahigh performance liquid chromatography with quadrupole time-of-flight tandem mass spectrometry. J Chromatogr A [Internet]. 2016 Jul;1456:68–76. Available from: https://dx.doi.org/10.1016/j.chroma.2016.06.011
[54] Visnevschi-Necrasov T, Barreira JCM, Cunha SC, Pereira G, Oliveira MBPP. Advances in Isoflavone Profile Characterisation using Matrix Solid-phase Dispersion Coupled to HPLC / DAD in Medicago Species. Phytochem Anal. 2015 Aug;26:40–6. Available from: https://doi.org/10.1002/pca.2534
[55] Xu, L.; Shi, H.; Liang, T.; Feng, J.; Jin, Y.; Ke, Y.; Liang X. Selective separation of flavonoid glycosides in Dalbergia odorifera by matrix solid-phase dispersion using titania. J Sep Sci. 2011 Apr;34(11):1347–54. Available from: https://doi.org/10.1002/jssc.201100024
[56] Balasubramanian S, Panigrahi S. Solid-Phase Microextraction (SPME) Techniques for Quality Characterization of Food Products: A Review. Food Bioprocess Technol. 2011 Jan;4(1):1–26. Available from: https://doi.org/10.1007/s11947-009-0299-3
[57] Aulakh JS, Malik AK, Kaur V, Schmitt-Kopplin P. A review on solid phase micro extraction - High performance liquid chromatography (SPME-HPLC) analysis of pesticides. Crit Rev Anal Chem. 2005 Oct;35(1):71–85. Available from: https://doi.org/10.1080/10408340590947952
[58] Aresta A, Di Grumo F, Zambonin C. Determination of Major Isoflavones in Soy Drinks by Solid-Phase Micro Extraction Coupled to Liquid Chromatography. Food Anal Methods. 2016 Jul;9(4):925–33. Available from: https://doi.org/10.1007/s12161-015-0260-1
[59] Calvello R, Aresta A, Trapani A, Zambonin C, Cianciulli A, Salvatore R, Clodoveo ML, Corbo F, Franchini C, Panaro MA. Bovine and soybean milk bioactive compounds : Effects on inflammatory response of human intestinal Caco-2 cells. Food Chem. 2016 Nov;210:276–85. Available from: https://doi.org/10.1016/j.foodchem.2016.04.067
[60] Abdel-Rehim M. New trend in sample preparation: on-line microextraction in packed syringe for liquid and gas chromatography applications I . Determination of local anaesthetics in human plasma samples using gas chromatography – mass spectrometry. J Chromatogr B. 2004 Mar;801(2):317–21. Available from: https://doi.org/10.1016/j.jchromb.2003.11.042
[61] Gonçalves J, Mendes B, Silva CL, Câmara JS. Development of a novel microextraction by packed sorbent-based approach followed by ultrahigh pressure liquid chromatography as a powerful technique for quantification phenolic constituents of biological interest in wines. J Chromatogr A. 2012 Mar;1229:13–23. Available from: https://doi.org/10.1016/j.chroma.2012.01.023
[62] Chang Y, Zhao C, Wu Z, Zhou J, Zhao S, Lu X, Xu, G. Chip-based nanoflow high performance liquid chromatography coupled to mass spectrometry for profiling of soybean flavonoids. Electrophoresis [Internet]. 2012 Jun;33(15):2399–406. Available from: https://doi.wiley.com/10.1002/elps.201100581
[63] Bustamante-Rangel M, Delgado-Zamarreño MM, Carabias-Martínez R, Domínguez-Álvarez J. Analysis of isoflavones in soy drink by capillary zone electrophoresis coupled with electrospray ionization mass spectrometry. Anal Chim Acta [Internet]. 2012 Jan;709:113–9. Available from: https://doi.org/10.1016/j.aca.2011.10.015
[64] Vacek J, Klejdus B, Lojková L, Kubán V. Current trends in isolation, separation, determination and identification of isoflavones: A review. J Sep Sci [Internet]. 2008 Jul;31(11):2054–67. Available from: https://doi.wiley.com/10.1002/jssc.200700569
[65] Engida AM, Kasim NS, Tsigie YA, Ismadji S, Huynh LH, Ju Y-H. Extraction, identification and quantitative HPLC analysis of flavonoids from sarang semut (Myrmecodia pendan). Ind Crops Prod [Internet]. 2013 Jan;41:392–6. Available from: https://doi.org/10.1016/j.indcrop.2012.04.043
[66] Merken HM, Beecher GR. Measurement of Food Flavonoids by High-Performance Liquid Chromatography: A Review. 2000 Feb; Available from: https://pubs.acs.org/doi/abs/10.1021/jf990872o
[67] Zaheer K, Akhtar MH. Critical Reviews in Food Science and Nutrition An updated review of dietary isoflavones: Nutrition, processing, bioavailability and impacts on human health An updated review of dietary isoflavones: Nutrition, processing, bioavailability and impacts on human health. 2015 Nov; Available from: https://doi.org/10.1080/10408398.2014.989958
[68] Uifălean A, Farcaş A, Ilieş M, Hegheş SC, Ionescu C, Iuga CA. Assessment of isoflavone aglycones variability in soy food supplements using a validated hplc-uv method. Orig Res Clujul Med [Internet]. 2015 Jul;88(3):373–80. Available from: https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4632898/pdf/cm-88-373.pdf
[69] Fiechter G, Opacak I, Raba B, Mayer HK. A new ultra-high pressure liquid chromatography method for the determination of total isoflavone aglycones after enzymatic hydrolysis: Application to analyze isoflavone levels in soybean cultivars. 2013 Mar; Available from: https://doi.org/10.1016/j.foodres.2011.03.038
[70] Klejdus B, Vacek J, Benešová L, Kopecký J, Lapčík O, Kubáň V. Rapid-resolution HPLC with spectrometric detection for the determination and identification of isoflavones in soy preparations and plant extracts. Anal Bioanal Chem [Internet]. 2007 Dec;389(7–8):2277–85. Available from: https://doi.org/10.1007/s00216-007-1606-3
[71] Repollés C, Herrero-Martínez JM, Ràfols C. Analysis of prominent flavonoid aglycones by high-performance liquid chromatography using a monolithic type column. J Chromatogr A [Internet]. 2006 Oct;1131(1–2):51–7. Available from: https://doi.org/10.1016/j.chroma.2006.07.012
[72] Jandera P. Advances in the development of organic polymer monolithic columns and their applications in food analysis—A review. J Chromatogr A [Internet]. 2013 Oct;1313:37–53. Available from: https://doi.org/10.1016/j.chroma.2013.08.010
[73] Herrero M, Ibáñez E, Cifuentes A. Analysis of natural antioxidants by capillary electromigration methods. J Sep Sci [Internet]. 2005 Jun;28(9–10):883–97. Available from: https://doi.wiley.com/10.1002/jssc.200400104
[74] Wieczorek P, Ligor M, Buszewski B. Applications of Electromigration Techniques: Applications of Electromigration Techniques in Food Analysis. In Springer, Berlin, Heidelberg; 2013 Apr; 105:299–333. Available from: https://doi.org/10.1007/978-3-642-35043-6_17
[75] Shihabi ZK, Kute T, Garcia LL, Hinsdale M. Analysis of isoflavones by capillary electrophoresis. J Chromatogr A [Internet]. 1994 Sep;680(1):181–5. Available from: https://doi.org/10.1016/0021-9673(94)80066-9
[76] Bustamante-Rangel M, Delgado-Zamarreño MM, Pérez-Martín L, Carabias-Martínez R. QuEChERS method for the extraction of isoflavones from soy-based foods before determination by capillary electrophoresis-electrospray ionization-mass spectrometry. Microchem J [Internet]. 2013 May;108:203–9. Available from: https://doi.org/10.1016/j.microc.2012.10.023
[77] Xiao W, Chen C, Zhang Q, Zhang Q-H, Hu Y-J, Xia Z-N, Yang, F-Q. Separation Study of Eight Isoflavones by MEKC with Different Surfactants. Chromatographia [Internet]. 2015 Nov;78(21–22):1385–93. Available from: https://doi.org/10.1007/s10337-015-2969-9
[78] Martí R, Valcárcel M, Herrero-Martínez JM, Cebolla-Cornejo J, Roselló S. Simultaneous determination of main phenolic acids and flavonoids in tomato by micellar electrokinetic capillary electrophoresis. Food Chem [Internet]. 2017 Apr;221:439–46. Available from: https://doi.org/10.1016/j.foodchem.2016.10.105
[79] Fiechter G, Opacak I, Raba B, Mayer HK. A new ultra-high pressure liquid chromatography method for the determination of total isoflavone aglycones after enzymatic hydrolysis: Application to analyze isoflavone levels in soybean cultivars. Food Research International. 2013 Mar; 50(2):586-592. Available from: https://doi.org/10.1016/j.foodres.2011.03.038
[80] Bustamante-Rangel M, Delgado-Zamarreño MM, Pérez-Martín L, Carabias-Martínez R. QuEChERS method for the extraction of isoflavones from soy-based foods before determination by capillary electrophoresis-electrospray ionization-mass spectrometry. Microchem J. 2013 May;108:203–9. Available from: https://doi.org/10.1016/j.microc.2012.10.023
[81] Martí R, Valcárcel M, Herrero-Martínez JM, Cebolla-Cornejo J, Roselló S. Simultaneous determination of main phenolic acids and flavonoids in tomato by micellar electrokinetic capillary electrophoresis. Food Chem. 2017 Apr;221:439–46. Available from: https://doi.org/10.1016/j.foodchem.2016.10.105
[82] Song Z, Hashi Y, Sun H, Liang Y, Lan Y, Wang H, Chen S. Simultaneous determination of 19 flavonoids in commercial trollflowers by using high-performance liquid chromatography and classification of samples by hierarchical clustering analysis. Fitoterapia. 2013 Dec;91:272–9. Available from: https://doi.org/10.1016/j.fitote.2013.09.006
[83] Ganzera M. Supercritical fluid chromatography for the separation of isoflavones. J Pharm Biomed Anal. 2015 Mar;107:364–9. Available from: https://doi.org/10.1016/j.jpba.2015.01.013
[84] VanderMolen KM, Cech NB, Paine MF, Oberlies NH. Rapid Quantitation of Furanocoumarins and Flavonoids in Grapefruit Juice using Ultra-Performance Liquid Chromatography. Phytochem Anal. 2013 Jun;24(6):654–60. Available from: https://doi.org/10.1002/pca.2449
[85] Barfi B, Asghari A, Rajabi M, Barfi A, Saeidi I. Simplified miniaturized ultrasound-assisted matrix solid phase dispersion extraction and high performance liquid chromatographic determination of seven flavonoids in citrus fruit juice and human fluid samples: Hesperetin and naringenin as biomarkers. J Chromatogr A. 2013 Oct;1311:30–40. Available from: https://doi.org/10.1016/j.chroma.2013.08.078
[86] Ahmed AYBH, Obbed MS, Wabaidur SM, AlOthman ZA, Al-Shaalan NH. High-Performance Liquid Chromatography Analysis of Phenolic Acid, Flavonoid, and Phenol Contents in Various Natural Yemeni Honeys Using Multi-walled Carbon Nanotubes as a Solid-Phase Extraction Adsorbent. J Agric Food Chem. 2014 Jun;62(24):5443–50. Available from: https://pubs.acs.org/doi/abs/10.1021/jf5011758
[87] Shim Y-S, Yoon W-J, Hwang J-B, Park H-J, Seo D, Ha J. Rapid method for the determination of 14 isoflavones in food using UHPLC coupled to photo diode array detection. Food Chem. 2015 Nov;187:391–7. Available from: https://doi.org/10.1016/j.foodchem.2015.04.077
[88] Schmidt L, Müller J, Göen T. Simultaneous monitoring of seven phenolic metabolites of endocrine disrupting compounds (EDC) in human urine using gas chromatography with tandem mass spectrometry. Anal Bioanal Chem [Internet]. 2013 Feb;405(6):2019–29. Available from: https://link.springer.com/10.1007/s00216-012-6618-y
[89] Roh C. Biotransformation of Isoflavone Using Enzymatic Reactions. Molecules [Internet]. 2013 Mar;18(3):3028–40. Available from: https://doi.org/10.3390/molecules18033028
[90] Nakata R, Yoshinaga N, Teraishi M, Okumoto Y, Huffaker A, Schmelz EA, Mori, N. A fragmentation study of isoflavones by IT-TOF-MS using biosynthesized isotopes. Biosci Biotechnol Biochem [Internet]. 2018 Aug;82(8):1309–15. Available from: https://www.tandfonline.com/doi/full/10.1080/09168451.2018.1465810
[91] Yan Y, Chai C-Z, Wang D-W, Wu J, Xiao H-H, Huo L-X, Zhu D-N, Yu B.Y. Simultaneous determination of puerarin, daidzin, daidzein, paeoniflorin, albiflorin, liquiritin and liquiritigenin in rat plasma and its application to a pharmacokinetic study of Ge-Gen Decoction by a liquid chromatography–electrospray ionization-tandem mass spectrometry. J Pharm Biomed Anal [Internet]. 2014 Jul;95:76–84. Available from: https://doi.org/10.1016/j.jpba.2014.02.013
[92] Lei Z, Jing L, Qiu F, Zhang H, Huhman D, Zhou Z, Sumner LW. Construction of an Ultrahigh Pressure Liquid Chromatography-Tandem Mass Spectral Library of Plant Natural Products and Comparative Spectral Analyses. Anal Chem [Internet]. 2015 Jun;87(14):7373–81. Available from: https://pubs.acs.org/doi/10.1021/acs.analchem.5b01559
[93] Parets L, Alechaga É, Núñez O, Saurina J, Hernández-Cassou S, Puignou L. Ultrahigh pressure liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry for the determination of polyphenolic profiles in the characterization and classification of cranberry-based pharmaceutical preparations and natural extracts. Anal Methods [Internet]. 2016 Jun;8(22):4363–78. Available from: https://xlink.rsc.org/?DOI=C6AY00929H
[94] Schmidt J. Negative ion electrospray high-resolution tandem mass spectrometry of polyphenols. J Mass Spectrom [Internet]. 2016 Jan;51(1):33–43. Available from: https://doi.wiley.com/10.1002/jms.3712
[95] Jorgenson JW, Lukacs KA. Zone electrophoresis in open-tubular glass capillaries: Preliminary data on performance. J High Resolut Chromatogr [Internet]. 1981 May;4(5):230–1. Available from: https://doi.wiley.com/10.1002/jhrc.1240040507
[96] Perez-Martin L, Bustamante-Rangel M, Delgado-Zamarreno MM. Determination of Isoflavones in Legumes by QuEChERS-Capillary Electrophoresis-Electrospray Ionization-Mass Spectrometry. Bentham Science Publishers. 2015 Apr;11(2):117-123 Available from: https://www.ingentaconnect.com/content/ben/cac/2015/00000011/00000002/art00008#
[97] Olivares JA, Nguyen NT, Yonker CR, Smith RD. On-line mass spectrometric detection for capillary zone electrophoresis. Anal Chem [Internet]. 1987 Apr;59(8):1230–2. Available from: https://pubs.acs.org/doi/abs/10.1021/ac00135a034
[98] Zhong X, Chen Z, Snovida S, Liu Y, Rogers JC, Li L. Capillary Electrophoresis-Electrospray Ionization-Mass Spectrometry for Quantitative Analysis of Glycans Labeled with Multiplex Carbonyl-Reactive Tandem Mass Tags. Anal Chem [Internet]. 2015 Jul;87(13):6527–34. Available from: https://pubs.acs.org/doi/10.1021/acs.analchem.5b01835
[99] Zhao J, Hu D-j, Lao K, Yang Z-m, Li S. Advance of CE and CEC in phytochemical analysis (2012-2013). Electrophoresis [Internet]. 2014 Jan;35(1):205–24. Available from: https://doi.wiley.com/10.1002/elps.201300321
[100] Karas M, Bachmann D, Bahr U, Hillenkamp F. Matrix-assisted ultraviolet laser desorption of non-volatile compounds. Int J Mass Spectrom Ion Process [Internet]. 1987 Sep;78:53–68. Available from: https://doi.org/10.1016/0168-1176(87)87041-6
[101] Theparee T, Das S, Thomson RB. Total Laboratory Automation and Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry Improve Turnaround Times in the Clinical Microbiology Laboratory: a Retrospective Analysis. J Clin Microbiol [Internet]. 2018 Jan;56(1):e01242-17. Available from: https://www.ncbi.nlm.nih.gov/pubmed/29118171
[102] Sakamoto S, Yusakul G, Pongkitwitoon B, Paudel MK, Tanaka H, Morimoto S. Simultaneous determination of soy isoflavone glycosides, daidzin and genistin by monoclonal antibody-based highly sensitive indirect competitive enzyme-linked immunosorbent assay. Food Chem [Internet]. 2015 Feb;169:127–33. Available from: https://doi.org/10.1016/j.foodchem.2014.08.004
[103] Cui Q, Peng X, Yao X-H, Wei Z-F, Luo M, Wang W, Zhao, C-J, Fu Y-J, Zu Y-G. Deep eutectic solvent-based microwave-assisted extraction of genistin, genistein and apigenin from pigeon pea roots. Sep Purif Technol [Internet]. 2015 Aug;150:63–72. Available from: https://doi.org/10.1016/j.seppur.2015.06.026
[104] Wang L, Wang ZQ, Hu DD, Cui J. Proteomic analysis of Trichinella spiralis muscle larval excretory-secretory proteins recognized by early infection sera. Biomed Res Int [Internet]. 2013 Jun;2013:139745. Available from: https://dx.doi.org/10.1155/2013/139745
[105] Giménez-Cassina B, Schmidt EM, Eberlin MN, Sawaya ACHF. Phytochemical markers of different types of red propolis. Food Chem [Internet]. 2014 Mar;146:174–80. Available from: https://doi.org/10.1016/j.foodchem.2013.09.063