Relationships between Structures of Condensed Tannins from Texas Legumes and Methane Production During In Vitro Rumen Digestion
Previous studies showed that a series of purified condensed tannins (CTs) from warm-season perennial legumes exhibited high variability in their modulation of methane production during in vitro rumen digestion. The molecular weight differences between these CTs did not provide correlation with eithe...
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MDPI AG
2018-08-01
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| Series: | Molecules |
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| Online Access: | http://www.mdpi.com/1420-3049/23/9/2123 |
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| author | Harley Naumann Rebecka Sepela Aira Rezaire Sonia E. Masih Wayne E. Zeller Laurie A. Reinhardt Jamison T. Robe Michael L. Sullivan Ann E. Hagerman |
| author_facet | Harley Naumann Rebecka Sepela Aira Rezaire Sonia E. Masih Wayne E. Zeller Laurie A. Reinhardt Jamison T. Robe Michael L. Sullivan Ann E. Hagerman |
| author_sort | Harley Naumann |
| collection | DOAJ |
| description | Previous studies showed that a series of purified condensed tannins (CTs) from warm-season perennial legumes exhibited high variability in their modulation of methane production during in vitro rumen digestion. The molecular weight differences between these CTs did not provide correlation with either the in vitro CH4 production or the ability to precipitate bovine serum albumin. In an effort to delineate other structure-activity relationships from these methane abatement experiments, the structures of purified CTs from these legumes were assessed with a combination of methanolysis, quantitative thiolysis, 1H-13C HSQC NMR spectroscopy and ultrahigh-resolution MALDI-TOF MS. The composition of these CTs is very diverse: procyanidin/prodelphinidin (PC/PD) ratios ranged from 98/2 to 2/98; cis/trans ratios ranged from 98/2 to 34/66; mean degrees of polymerization ranged from 6 to 39; and % galloylation ranged from 0 to 75%. No strong correlation was observed between methane production and the protein precipitation capabilities of the CT towards three different proteins (BSA, lysozyme, and alfalfa leaf protein) at ruminal pH. However, a strong non-linear correlation was observed for the inhibition of methane production versus the antioxidant activity in plant sample containing typical PC- and PD-type CTs. The modulation of methane production could not be correlated to the CT structure (PC/PD or cis/trans ratios and extent of galloylation). The most active plant in methane abatement was Acacia angustissima, which contained CT, presenting an unusual challenge as it was resistant to standard thiolytic degradation conditions and exhibited an atypical set of cross-peak signals in the 2D NMR. The MALDI analysis supported a 5-deoxy flavan-3-ol-based structure for the CT from this plant. |
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| spelling | doaj.art-2d393ad10fb74c4ea940a22afbadb2082022-12-22T02:20:38ZengMDPI AGMolecules1420-30492018-08-01239212310.3390/molecules23092123molecules23092123Relationships between Structures of Condensed Tannins from Texas Legumes and Methane Production During In Vitro Rumen DigestionHarley Naumann0Rebecka Sepela1Aira Rezaire2Sonia E. Masih3Wayne E. Zeller4Laurie A. Reinhardt5Jamison T. Robe6Michael L. Sullivan7Ann E. Hagerman8Division of Plant Sciences, University of Missouri, 110 Waters, Columbia, MO 65211, USADepartment of Chemistry & Biochemistry, Miami University, Oxford, OH 45056, USADepartment of Chemistry & Biochemistry, Miami University, Oxford, OH 45056, USADepartment of Chemistry & Biochemistry, Miami University, Oxford, OH 45056, USAUSDA-ARS, U.S. Dairy Forage Research Center, Madison, WI 53706, USAUSDA-ARS, U.S. Dairy Forage Research Center, Madison, WI 53706, USAUSDA-ARS, U.S. Dairy Forage Research Center, Madison, WI 53706, USAUSDA-ARS, U.S. Dairy Forage Research Center, Madison, WI 53706, USADepartment of Chemistry & Biochemistry, Miami University, Oxford, OH 45056, USAPrevious studies showed that a series of purified condensed tannins (CTs) from warm-season perennial legumes exhibited high variability in their modulation of methane production during in vitro rumen digestion. The molecular weight differences between these CTs did not provide correlation with either the in vitro CH4 production or the ability to precipitate bovine serum albumin. In an effort to delineate other structure-activity relationships from these methane abatement experiments, the structures of purified CTs from these legumes were assessed with a combination of methanolysis, quantitative thiolysis, 1H-13C HSQC NMR spectroscopy and ultrahigh-resolution MALDI-TOF MS. The composition of these CTs is very diverse: procyanidin/prodelphinidin (PC/PD) ratios ranged from 98/2 to 2/98; cis/trans ratios ranged from 98/2 to 34/66; mean degrees of polymerization ranged from 6 to 39; and % galloylation ranged from 0 to 75%. No strong correlation was observed between methane production and the protein precipitation capabilities of the CT towards three different proteins (BSA, lysozyme, and alfalfa leaf protein) at ruminal pH. However, a strong non-linear correlation was observed for the inhibition of methane production versus the antioxidant activity in plant sample containing typical PC- and PD-type CTs. The modulation of methane production could not be correlated to the CT structure (PC/PD or cis/trans ratios and extent of galloylation). The most active plant in methane abatement was Acacia angustissima, which contained CT, presenting an unusual challenge as it was resistant to standard thiolytic degradation conditions and exhibited an atypical set of cross-peak signals in the 2D NMR. The MALDI analysis supported a 5-deoxy flavan-3-ol-based structure for the CT from this plant.http://www.mdpi.com/1420-3049/23/9/2123proanthocyanidinscondensed tanninsthiolysisNMR spectroscopyultrahigh-resolution negative mode MALDI-TOF mass spectrometryantioxidantORAC assayAcaciaforage legume |
| spellingShingle | Harley Naumann Rebecka Sepela Aira Rezaire Sonia E. Masih Wayne E. Zeller Laurie A. Reinhardt Jamison T. Robe Michael L. Sullivan Ann E. Hagerman Relationships between Structures of Condensed Tannins from Texas Legumes and Methane Production During In Vitro Rumen Digestion Molecules proanthocyanidins condensed tannins thiolysis NMR spectroscopy ultrahigh-resolution negative mode MALDI-TOF mass spectrometry antioxidant ORAC assay Acacia forage legume |
| title | Relationships between Structures of Condensed Tannins from Texas Legumes and Methane Production During In Vitro Rumen Digestion |
| title_full | Relationships between Structures of Condensed Tannins from Texas Legumes and Methane Production During In Vitro Rumen Digestion |
| title_fullStr | Relationships between Structures of Condensed Tannins from Texas Legumes and Methane Production During In Vitro Rumen Digestion |
| title_full_unstemmed | Relationships between Structures of Condensed Tannins from Texas Legumes and Methane Production During In Vitro Rumen Digestion |
| title_short | Relationships between Structures of Condensed Tannins from Texas Legumes and Methane Production During In Vitro Rumen Digestion |
| title_sort | relationships between structures of condensed tannins from texas legumes and methane production during in vitro rumen digestion |
| topic | proanthocyanidins condensed tannins thiolysis NMR spectroscopy ultrahigh-resolution negative mode MALDI-TOF mass spectrometry antioxidant ORAC assay Acacia forage legume |
| url | http://www.mdpi.com/1420-3049/23/9/2123 |
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