Abstract
An NMR protocol based on multiple-quantum spectroscopy is presented for an analytical screening of polyphenols in olive oils. Three Italian olive oils with different total polyphenols content were used as study case. A total of 24 compounds were identified as follows: 1 polyphenol in the 5Q–1Q, 15 more in the 4Q–1Q, and 8 components in the 3Q–1Q spectra, consisting of organic phenols, secoiridoids, lignans, and flavonols. In the three Italian olive oils investigated here, the polyphenols profile turned out to be significantly different, with specific characteristics going beyond simple considerations based on the total polyphenol content. The approach presented here can be easily extended for rapid qualitative and semi-quantitative screening of the polyphenol composition in many food products.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Alonso-Salces RM, Moreno-Rojas JM, Holland MV, Reniero F, Guillou C, Kr H (2010) Virgin olive oil authentication by multivariate analyses of 1H NMR fingerprints and δ13C and δ2H data. J Agric Food Chem 58:5586–5596. https://doi.org/10.1021/jf903989b
Aparicio R, Luna G (2002) Characterisation of monovarietal virgin olive oils. Eur J Lipid Sci Technol 104:614–627. https://doi.org/10.1002/1438-9312(200210)104:9/10%3C614::AID-EJLT614%3E3.0.CO;2-L
Baishya B, Reddy GNM, Prabhu UR, Row TNG, Suryaprakash N (2008) Simplifying the complex 1H NMR spectra of fluorine-substituted benzamides by spin system filtering and spin-state selection: multiple-quantum−single-quantum correlation. J Phys Chem A 112:10526–10532. https://doi.org/10.1021/jp8055174
Barjat H, Morris GA, Swanson AG (1998) A three-dimensional DOSY–HMQC experiment for the high-resolution analysis of complex mixtures. J Magn Reson 131:131–138. https://doi.org/10.1006/jmre.1997.1332
Bastoni L, Bianco A, Piccioni F, Uccella N (2001) Biophenolic profile in olives by nuclear magnetic resonance. Food Chem 73:145–151. https://doi.org/10.1016/S0308-8146(00)00250-8
Bendini A, Cerretani L, Carrasco-Pancorvo A, Gomez-Caravaca A-M, Segura-Carretero A, Fernandez-Gutierrez A et al (2007) Phenolic molecules in virgin olive oils: a survey of their sensory properties, health effects, antioxidant activity and analytical methods. An overview of the last decade. Molecules 12:1679–1719
Camin F, Pavone A, Bontempo L, Wehrens R, Paolini M, Faberi A et al (2016) The use of IRMS, 1H NMR and chemical analysis to characterise Italian and imported Tunisian olive oils. Food Chem 196:98–105. https://doi.org/10.1016/j.foodchem.2015.08.132
Charisiadis P, Kontogianni VG, Tsiafoulis CG, Tzakos AG, Gerothanassis IP (2017) Determination of polyphenolic phytochemicals using highly deshielded –OH 1H-NMR signals. Phytochem Anal 28:159–170. https://doi.org/10.1002/pca.2656
Christophoridou S, Dais P (2009) Detection and quantification of phenolic compounds in olive oil by high resolution 1H nuclear magnetic resonance spectroscopy. Anal Chim Acta 633:283–292. https://doi.org/10.1016/j.aca.2008.11.048
Christophoridou S, Dais P, Tseng L-H, Spraul M (2005) Separation and identification of phenolic compounds in olive oil by coupling high-performance liquid chromatography with postcolumn solid-phase extraction to nuclear magnetic resonance spectroscopy (LC-SPE-NMR). J Agric Food Chem 53:4667–4679. https://doi.org/10.1021/jf040466r
Dalvit C, Bohlen JM (1997) Analysis of biofluids and chemical mixtures in non-deuterated solvents with H-1 diffusion-weighted PFG phase-sensitive double-quantum NMR spectroscopy. NMR Biomed 10:285–291. https://doi.org/10.1002/(sici)1099-1492(199709)10:6<285::aid-nbm485>3.0.co;2-1
Duthie GG, Duthie SJ, Kyle JAM (2000) Plant polyphenols in cancer and heart disease: implications as nutritional antioxidants. Nutr Res Rev 13:79–106
Ernst RR, Bodenhausen G, Wokaun A (1990) Principles of Nuclear Magnetic Resonance in One and Two Dimensions. Clarendon Press
Ferguson LR (2001) Role of plant polyphenols in genomic stability. Mutat Res, Fundam Mol Mech Mutagen 475:89–111. https://doi.org/10.1016/S0027-5107(01)00073-2
Franco MN, Galeano-Díaz T, López Ó, Fernández-Bolaños JG, Sánchez J, De Miguel C et al (2014) Phenolic compounds and antioxidant capacity of virgin olive oil. Food Chem 163:289–298. https://doi.org/10.1016/j.foodchem.2014.04.091
Fuentes de Mendoza M, De Miguel GC, Marín Expóxito J, Sánchez Casas J, Martínez Cano M, Martín Vertedor D et al (2013) Chemical composition of virgin olive oils according to the ripening in olives. Food Chem 141:2575–2581. https://doi.org/10.1016/j.foodchem.2013.05.074
Guennec AL, Giraudeau P, Caldarelli S, Dumez J-N (2015) Ultrafast double-quantum NMR spectroscopy. Chem Commun (Camb) 51:354–357. https://doi.org/10.1039/c4cc07232d
Gutfinger T (1981) Polyphenols in olive oils. J Am Oil Chem Soc 58:966–968. https://doi.org/10.1007/BF02659771
Haddada FM, Manai H, Daoud D, Fernandez X, Lizzani-Cuvelier L, Zarrouk M (2007) Profiles of volatile compounds from some monovarietal Tunisian virgin olive oils. Comparison with French PDO. Food Chem 103:467–476. https://doi.org/10.1016/j.foodchem.2006.08.023
Ignat I, Volf I, Popa VI (2011) A critical review of methods for characterisation of polyphenolic compounds in fruits and vegetables. Food Chem 126:1821–1835. https://doi.org/10.1016/j.foodchem.2010.12.026
Johnson CS Jr (1999) Diffusion ordered nuclear magnetic resonance spectroscopy: principles and applications. Prog Nucl Magn Reson Spectrosc 34:203–256. https://doi.org/10.1016/S0079-6565(99)00003-5
Köcher SS, Heydenreich T, Zhang Y, Reddy GNM, Caldarelli S, Yuan H et al (2016) Time-optimal excitation of maximum quantum coherence: physical limits and pulse sequences. J Chem Phys 144:164103. https://doi.org/10.1063/1.4945781
Lesage-Meessen L, Navarro D, Maunier S, Sigoillot JC, Lorquin J, Delattre M et al (2001) Simple phenolic content in olive oil residues as a function of extraction systems. Food Chem 75:501–507. https://doi.org/10.1016/S0308-8146(01)00227-8
Lin M, Shapiro MJ (1997) Mixture analysis by NMR spectroscopy. Anal Chem 69:4731–4733. https://doi.org/10.1021/ac970594x
Longobardi F, Ventrella A, Napoli C, Humpfer E, Schütz B, Schäfer H et al (2012) Classification of olive oils according to geographical origin by using 1H NMR fingerprinting combined with multivariate analysis. Food Chem 130:177–183. https://doi.org/10.1016/j.foodchem.2011.06.045
Manjunatha Reddy GN, Caldarelli S (2013) Improved excitation uniformity in multiple-quantum NMR experiments of mixtures. Magn Reson Chem 51:240–244. https://doi.org/10.1002/mrc.3938
Manjunatha Reddy GN, Guru Row TN, Suryaprakash N (2009a) Discerning the degenerate transitions of scalar coupled 1H NMR spectra: correlation and resolved techniques at higher quantum. J Magn Reson 196:119–126. https://doi.org/10.1016/j.jmr.2008.10.018
Manjunatha Reddy GN, Nayak SK, Guru Row TN, Suryaprakash N (2009b) Proton NMR studies of dihalogenated phenyl benzamides: two-dimensional higher quantum methodologies. Magn Reson Chem 47:684–692. https://doi.org/10.1002/mrc.2449
Manjunatha Reddy GN, Yemloul M, Caldarelli S (2016) Combined maximum-quantum and DOSY 3D experiments provide enhanced resolution for small molecules in mixtures. Magn Reson Chem n/a-n/a. https://doi.org/10.1002/mrc.4465
Mannina L, Sobolev AP (2011) High resolution NMR characterization of olive oils in terms of quality, authenticity and geographical origin. Magn Reson Chem 49:S3–S11. https://doi.org/10.1002/mrc.2856
Mannina L, Patumi M, Proietti N, Bassi D, Segre AL (2001) Geographical characterization of Italian extra virgin olive oils using high-field 1H NMR spectroscopy. J Agric Food Chem 49:2687–2696. https://doi.org/10.1021/jf001408i
Mannina L, Dugo G, Salvo F, Cicero L, Ansanelli G, Calcagni C et al (2002) Study of the cultivar−composition relationship in Sicilian olive oils by GC, NMR, and statistical methods. J Agric Food Chem 51:120–127. https://doi.org/10.1021/jf025656l
Mannina L, Marini F, Gobbino M, Sobolev AP, Capitani D (2010) NMR and chemometrics in tracing European olive oils: the case study of Ligurian samples. Talanta 80:2141–2148. https://doi.org/10.1016/j.talanta.2009.11.021
Martineau E, Giraudeau P, Tea I, Akoka S (2011) Fast and precise quantitative analysis of metabolic mixtures by 2D H-1 INADEQUATE NMR. J Pharm Biomed Anal 54:252–257. https://doi.org/10.1016/j.jpba.2010.07.046
Martineau E, Tea I, Akoka S, Giraudeau P (2012) Absolute quantification of metabolites in breast cancer cell extracts by quantitative 2D 1H INADEQUATE NMR. NMR Biomed 25:985–992. https://doi.org/10.1002/nbm.1816
Montedoro G, Servili M, Baldioli M, Selvaggini R, Miniati E (1992) Simple and hydrolysable phenolic compounds in virgin olive oil. J Agric Food Chem 40:1571
Montedoro G, Servili M, Baldioli M, Selvaggini R, Miniati E, Macchioni A (1993) Simple and hydrolyzable compounds in virgin olive oil. 3. Spectroscopic characterizations of the secoiridoid derivatives. J Agric Food Chem 41:2228
Munowitz M, Pines A (1986) Multiple-quantum nuclear magnetic resonance spectroscopy. Science 233:525–531. https://doi.org/10.1126/science.233.4763.525
Newman DJ, Cragg GM (2007) Natural products as sources of new drugs over the last 25 years. J Nat Prod 70:461–477. https://doi.org/10.1021/np068054v
Nilsson M, Duarte IF, Almeida C, Delgadillo I, Goodfellow BJ, Gil AM et al (2004) High-resolution NMR and diffusion-ordered spectroscopy of port wine. J Agric Food Chem 52:3736–3743. https://doi.org/10.1021/jf049797u
Ocakoglu D, Tokatli F, Ozen B, Korel F (2009) Distribution of simple phenols, phenolic acids and flavonoids in Turkish monovarietal extra virgin olive oils for two harvest years. Food Chem 113:401–410. https://doi.org/10.1016/j.foodchem.2008.07.057
Piotto M, Manjunatha Reddy GN, Caldarelli S (2011) Non-uniformly sampled maximum quantum spectroscopy. J Magn Reson 213:107–111. https://doi.org/10.1016/j.jmr.2011.09.016
Quideau S, Deffieux D, Douat-Casassus C, Pouységu L (2011) Plant polyphenols: chemical properties, biological activities, and synthesis. Angew Chem Int Ed 50:586–621. https://doi.org/10.1002/anie.201000044
Reddy GNM, Caldarelli S (2010) Demixing of severely overlapping NMR spectra through multiple-quantum NMR. Anal Chem 82:3266–3269. https://doi.org/10.1021/ac100009y
Reddy GNM, Caldarelli S (2011) Maximum-quantum (MaxQ) NMR for the speciation of mixtures of phenolic molecules. Chem Commun 47:4297–4299. https://doi.org/10.1039/C1CC10226E
Reddy GNM, Caldarelli S (2012) Identification and quantification of EPA 16 priority polycyclic aromatic hydrocarbon pollutants by maximum-quantum NMR. Analyst 137:741–746. https://doi.org/10.1039/C1AN16047H
Reddy GNM, Ballesteros-Garrido R, Lacour J, Caldarelli S (2013) Determination of labile chiral supramolecular ion pairs by chromatographic NMR spectroscopy. Angew Chem Int Ed 52:3255–3258. https://doi.org/10.1002/anie.201209616
Sacchi R, Mannina L, Fiordiponti P, Barone P, Paolillo L, Patumi M et al (1998) Characterization of Italian extra virgin olive oils using 1H-NMR spectroscopy. J Agric Food Chem 46:3947–3951. https://doi.org/10.1021/jf970666l
Tsimidou M, Papadopoulos G, Boskou D (1992) Phenolic compounds and stability of virgin olive oil—part I. Food Chem 45:141–144. https://doi.org/10.1016/0308-8146(92)90025-W
Viel S, Caldarelli S (2008) Improved 3D DOSY-TOCSY experiment for mixture analysis. Chemical Communications 2013-2015. https://doi.org/10.1039/B802789G
Vinha AF, Ferreres F, Silva BM, Valentão P, Gonçalves A, Pereira JA et al (2005) Phenolic profiles of Portuguese olive fruits (Olea europaea L.): influences of cultivar and geographical origin. Food Chem 89:561–568. https://doi.org/10.1016/j.foodchem.2004.03.012
Visioli F, Bellomo G, Galli C (1998) Free radical-scavenging properties of olive oil polyphenols. Biochem Biophys Res Commun 247:60–64. https://doi.org/10.1006/bbrc.1998.8735
Yang D-P, Kong D-X, Zhang H-Y (2007) Multiple pharmacological effects of olive oil phenols. Food Chem 104:1269–1271. https://doi.org/10.1016/j.foodchem.2006.12.058
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
This study was funded by “eALIERB-OPENLAB” Project (Regione Lazio LR13/2008—Dipartimento di Chimica e Tecnologie del Farmaco), LR13/2008; Agence nationale de la RechercheANR-08-BLAN-273-01; Region PACA APO-G-2009.
Conflict of Interest
G. N. Manjunatha Reddy declares that he has no conflict of interest. Luisa Mannina declares that she has no conflict of interest. Anatoly P. Sobolev declares that he has no conflict of interest. Stefano Caldarelli declares that he has no conflict of interest.
Ethical Approval
This article does not contain any studies with human participants or animals performed by any of the authors.
Informed Consent
Not applicable.
Rights and permissions
About this article
Cite this article
Manjunatha Reddy, G.N., Mannina, L., Sobolev, A.P. et al. Polyphenols Fingerprinting in Olive Oils Through Maximum-Quantum NMR Spectroscopy. Food Anal. Methods 11, 1012–1020 (2018). https://doi.org/10.1007/s12161-017-1069-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12161-017-1069-x