Skip to main content
SpringerLink
Log in

Estimation of the Mean Degree of Polymerization of Condensed Tannins from the Kernel and Shell of Carya illinoinensis by HPLC/MS and Spectrophotometric Methods

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

Abstract

Rapid estimation of the degree of polymerization (DP) of pure tannins or mean degree of polymerization (mDP) of tannin samples is an analytical challenge and a necessity to better understand their bioactivity. In the present paper, four spectrophotometric analyses and normal phase HPLC/MS were performed to estimate mDP of tannin fractions from pecan nut (Carya illinoinesis) kernels and shells. Tannins were obtained by acetone extraction of phenolic compounds followed by size exclusion chromatography fractionation. Four final fractions were obtained, and their mDP was estimated by spectrophotometric and HPLC/MS analysis and results compared among the different methods. All assays showed good reproducibility. The combination of butanol–HCl depolymerization reaction with vanillin-acetic acid assay yielded mDP values equal to those estimated by HPLC/MS (alpha = 5%), proving this method both suitable and reliable for rapid mDP estimation of tannins in samples.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2

Similar content being viewed by others

References

  • Bittner K, Rzeppa S, Humpf H-U (2013) Distribution and quantification of flavan-3-ols and procyanidins with low degree of polymerization in nuts, cereals, and legumes. J Agric Food Chem 61:9148–9154

    Article  CAS  Google Scholar 

  • Bolling BW, Chen C-YO, McKay DL, Blumberg JB (2011) Tree nut phytochemicals: composition, antioxidant capacity, bioactivity, impact factors. A systematic review of almonds, brazils, cashews, hazelnuts, macadamias, pecans, pine nuts, pistachios and walnuts. Nutr Res Rev 24:244–275

    Article  CAS  Google Scholar 

  • Butler LG (1982) Relative degree of polymerization of sorghum tannin during seed development and maturation. J Agric Food Chem 30:1090–1094

    Article  CAS  Google Scholar 

  • Butler LG, Price ML, Brotherton JE (1982) Vanillin assay for proanthocyanidins (condensed tannins): modification of the solvent for estimation of the degree of polymerization. J Agric Food Chem 30:1087–1089

    Article  CAS  Google Scholar 

  • de la Rosa LA, Alvarez-Parrilla E, Shahidi F (2011) Phenolic compounds and antioxidant activity of kernels and shells of Mexican pecan (Carya illinoinensis). J Agric Food Chem 59:152–162

    Article  Google Scholar 

  • de la Rosa LA, Vazquez-Flores AA, Alvarez-Parrilla E, Rodrigo-García J, Medina-Campos ON, Ávila-Nava A, González-Reyes S, Pedraza-Chaverri J (2014) Content of major classes of polyphenolic compounds, antioxidant, antiproliferative, and cell protective activity of pecan crude extracts and their fractions. J Funct Foods 7:219–228

    Article  Google Scholar 

  • Duffau B, Rojas F, Guerrero I, Roa L, Rodríguez L, Soto M, Aguilera M, Sandoval S (2010) Guía Técnica No. 1. In: Validación de métodos y determinación de la incertidumbre de la medición: Aspectos generales sobre la validación de métodos. Instituto de Salud Pública, Santiago

    Google Scholar 

  • Feliciano RP, Shea MP, Shanmuganayagam D, Krueger CG, Howell AB, Reed JD (2012) Comparison of isolated cranberry (Vaccinium macrocarpon Ait.) proanthocyanidins to catechin and procyanidins A2 and B2 for use as standards in the 4-(Dimethylamino)cinnamaldehyde assay. J Agric Food Chem 60:4578–4585

    Article  CAS  Google Scholar 

  • González-Manzano S, Santos-Buelga C, Pérez-Alonso JJ, Rivas-Gonzalo JC, Escribano-Bailón MT (2006) Characterization of the mean degree of polymerization of proanthocyanidins in red wines using liquid chromatography−mass spectrometry (LC-MS). J Agric Food Chem 54:4326–4332

    Article  Google Scholar 

  • Gu L, Kelm MA, Hammerstone JF, Beecher G, Holden J, Haytowitz D, Prior RL (2003) Screening of foods containing proanthocyanidins and their structural characterization using LC-MS/MS and thiolytic degradation. J Agric Food Chem 51:7513–7521

    Article  CAS  Google Scholar 

  • Hellström J, Sinkkonen J, Karonen M, Mattila P (2007) Isolation and structure elucidation of procyanidin oligomers from saskatoon berries (Amelanchier alnifolia). J Agric Food Chem 55:157–164

  • 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

    Article  CAS  Google Scholar 

  • Karamać M (2009) Chelation of Cu(II), Zn(II), and Fe(II) by tannin constituents of selected edible nuts. Int J Mol Sci 10:5485–5497

    Article  Google Scholar 

  • Kennedy JA, Jones GP (2001) Analysis of proanthocyanidin cleavage products following acid-catalysis in the presence of excess phloroglucinol. J Agric Food Chem 49:1740–1746

    Article  CAS  Google Scholar 

  • Lazarus SA, Adamson GE, Hammerstone JF, Schmitz HH (1999) High-performance liquid chromatography/mass spectrometry analysis of proanthocyanidins in foods and beverages. J Agric Food Chem 47:3693–3701

    Article  CAS  Google Scholar 

  • Longstaff M, McNab JM (1991) The inhibitory effects of hull polysaccharides and tannins of field beans (Vicia faba L.) on the digestion of amino acids, starch and lipid and on digestive enzyme activities in young chicks. Br J Nut 65:199–216

    Article  CAS  Google Scholar 

  • Lorenz MM, Alkhafadji L, Stringano E, Nilsson S, Mueller-Harvey I, Udén P (2014) Relationship between condensed tannin structures and their ability to precipitate feed proteins in the rumen. J Sci Food Agr 94:963–968

    Article  CAS  Google Scholar 

  • Muchuweti M, Ndhlala AR, Kasiyamhuru A (2005) Estimation of the degree of polymerization of condensed tannins of some wild fruits of Zimbabwe (Uapaca kirkiana and Ziziphus mauritiana) using the modified vanillin-HCl method. J Sci Food Agr 85:1647–1650

    Article  CAS  Google Scholar 

  • Ogah O, Watkins CS, Ubi BE, Oraguzie NC (2014) Phenolic compounds in rosaceae fruit and nut crops. J Agric Food Chem 62:9369–9386

    Article  CAS  Google Scholar 

  • Ou K, Gu L (2014) Absorption and metabolism of proanthocyanidins. J Funct Foods 7:43–53

    Article  CAS  Google Scholar 

  • Porter JL, Hrstich LN, Chan BG (1985) The conversion of procyanidins and prodelphinidins to cyanidin and delphinidin. Phytochemistry 25:223–230

    Article  Google Scholar 

  • Price ML, Van Scoyoc S, Butler LG (1978) A critical evaluation of the vanillin reaction as an assay for tannin in sorghum grain. J Agric Food Chem 26:1214–1218

    Article  CAS  Google Scholar 

  • Robbins KS, Ma Y, Wells ML, Greenspan P, Pegg RB (2014) Separation and characterization of phenolic compounds from U.S. pecans by liquid chromatography–tandem mass spectrometry. J Agric Food Chem 62:4332–4341

    Article  CAS  Google Scholar 

  • Robbins KS, Gong Y, Wells ML, Greenspan P, Pegg RB (2015) Investigation of the antioxidant capacity and phenolic constituents of U.S. pecans. J Funct Foods 15:11–22

    Article  CAS  Google Scholar 

  • Saminathan M, Tan HY, Sieo CC, Abdullah N, Wong CM, Abdulmalek E, Ho YW (2014) Polymerization degrees, molecular weights and protein-binding affinities of condensed tannin fractions from a Leucaena leucocephala hybrid. Molecules 19:7990–8010

    Article  Google Scholar 

  • Sarnoski PJ, Johnson JV, Reed KA, Tanko JM, O’Keefe SF (2012) Separation and characterisation of proanthocyanidins in Virginia type peanut skins by LC–MSn. Food Chem 131:927–939

    Article  CAS  Google Scholar 

  • Sun B, Ricardo-da-Silva JM, Spranger I (1998) Critical factors of vanillin assay for catechins and proanthocyanidins. J Agric Food Chem 46:4267–4274

    Article  CAS  Google Scholar 

  • Tedeschi LO, Ramírez-Restrepo CA, Muir JP (2014) Developing a conceptual model of possible benefits of condensed tannins for ruminant production. Animal 8:1095–1105

    Article  CAS  Google Scholar 

  • Vazquez-Flores AA, Wong-Paz JE, Lerma-Herrera MA, Martinez-Gonzalez AI, Olivas-Aguirre FJ, Aguilar CN, Wall-Medrano A, Gonzalez-Aguilar GA, Alvarez-Parrilla E, de la Rosa LA (2017) Proanthocyanidins from the kernel and shell of pecan (Carya illinoinensis): average degree of polymerization and effects on carbohydrate, lipid and peptide hydrolysis in a simulated human digestive system. J Funct Foods 28:227–234

    Article  CAS  Google Scholar 

  • Wang Y, Singh AP, Hurst WJ, Glinski JA, Koo H, Vorsa N (2016) Influence of degree-of-polymerization and linkage on the quantification of proanthocyanidins using 4-Dimethylaminocinnamaldehyde (DMAC) assay. J Agric Food Chem 64:2190–2199

    Article  CAS  Google Scholar 

  • Yanagida A, Kanda T, Shoji T, Ohnishi-Kameyama M, Nagata T (1999) Fractionation of apple procyanidins by size-exclusion chromatography. J Chromatogr A 855:181–190

    Article  CAS  Google Scholar 

  • Yanagida A, Kanda T, Takahashi T, Kamimura A, Hamazono T, Honda S (2000) Fractionation of apple procyanidins according to their degree of polymerization by normal-phase high-performance liquid chromatography. J Chromatogr A 890:251–259

    Article  CAS  Google Scholar 

  • Yanagida A, Shoji T, Shibusawa Y (2003) Separation of proanthocyanidins by degree of polymerization by means of size-exclusion chromatography and related techniques. J Biochem Biophys Methods 56:311–322

    Article  CAS  Google Scholar 

Download references

Acknowledgements

To the National Council of Science and Technology (CONACyT, project CB-2011-01-167164) for the funding provided to this study. The first author thanks CONACyT for the scholarship granted for his Master in Science studies.

Author information

Authors and Affiliations

  1. Department of Chemical Biological Sciences, Universidad Autónoma de Ciudad Juárez, Anillo Envolvente del Pronaf y Estocolmo, s/n, Cd, 32310, Juárez, Chihuahua, Mexico

    M. A. Lerma-Herrera, J. A. Núñez-Gastélum, A. G. Díaz-Sánchez, E. Alvarez-Parrilla & L. A. de la Rosa

  2. Department of Food Science and Technology, School of Chemistry, Universidad Autónoma de Coahuila, 25280, Saltillo, Coahuila, Mexico

    J. Ascacio-Valdés & C. N. Aguilar

  3. Department of Health Sciences, Universidad Autónoma de Ciudad Juárez, Anillo envolvente del Pronaf y Estocolmo, s/n, Cd, 32310, Juarez, Chihuahua, Mexico

    J. Rodrigo-García

Authors
  1. M. A. Lerma-Herrera
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. J. A. Núñez-Gastélum
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. J. Ascacio-Valdés
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. C. N. Aguilar
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. J. Rodrigo-García
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. G. Díaz-Sánchez
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. E. Alvarez-Parrilla
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. L. A. de la Rosa
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to L. A. de la Rosa.

Ethics declarations

Funding

This study was funded by the Mexican National Council of Science and Technology (CONACyT, project CB-2011-01-167164). M. A. Lerma-Herrera received a scholarship from the Mexican National Council of Science and Technology (scholarship number 334130).

Conflict of Interest

M. A. Lerma-Herrera declares no conflict of interest, J. A. Núñez-Gastélum declares no conflict of interest, J. Ascacio-Valdés declares no conflict of interest, C. N. Aguilar declares no conflict of interest, J. Rodrigo-Garcia declares no conflict of interest, A. G. Díaz-Sánchez declares no conflict of interest, E. Alvarez-Parrilla declares no conflict of interest, L. A. de la Rosa declares no conflict of interest.

Ethical Approval

This article does not contain any studies with human or animal subjects.

Informed Consent

This article does not contain any studies for which an informed consent of participants was needed.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lerma-Herrera, M.A., Núñez-Gastélum, J.A., Ascacio-Valdés, J. et al. Estimation of the Mean Degree of Polymerization of Condensed Tannins from the Kernel and Shell of Carya illinoinensis by HPLC/MS and Spectrophotometric Methods. Food Anal. Methods 10, 3023–3031 (2017). https://doi.org/10.1007/s12161-017-0866-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-017-0866-6

Keywords

Search

Navigation