Endocyclic double bond isomers and by-products from rebaudioside A and stevioside formed under acid conditions

Perera, Wilmer H.; Docampo, Maite L.; Wiggers, Frank T.; Hufford, Charles D.; Fronczek, Frank R.; Avula, Bharathi; Khan, Ikhlas A.; McChesney, James D.

doi:10.1016/j.phytol.2018.04.007

Cited by 6 publications

(6 citation statements)

References 21 publications

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“…The acid hydrolysis of DGs has been studied since several soft drinks and juices prepared with DGs from S. rebaudiana as sweeteners can produce undesirable products under inappropriate temperature storage that may affect the taste of these acidic beverages. Even under different mild acid conditions a double bond isomerization process occurs yielding some by-products that have been isolated and characterized [ 33 , 34 , 35 , 36 , 37 , 38 , 39 ]. However, proper high-resolution analytical methods need to be developed to differentiate natural DGs from their endocyclic isomer compounds since they elute very closely in HPLC [ 40 ].…”

Section: Resultsmentioning

confidence: 99%

“…Hence, acid hydrolysis is not a good method to produce steviol in quantities. Recently, these three structurally close aglycones have been purified in their intact form by a two-step gradient high-performance silica gel chromatography [ 38 ]. In Table 1 are shown all the DGs formed under basic or acidic conditions while all the aglycones produced from steviol glycosides under acidic conditions and others reported from S. rebaudiana are compiled in Figure 1 .…”

Section: Resultsmentioning

confidence: 99%

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Approaches toward the Separation, Modification, Identification and Scale up Purification of Tetracyclic Diterpene Glycosides from Stevia rebaudiana (Bertoni) Bertoni

Perera¹,

McChesney

2021

Molecules

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Stevia rebaudiana (Bertoni) Bertoni is a plant species native to Brazil and Paraguay well-known by the sweet taste of their leaves. Since the recognition of rebaudioside A and other steviol glycosides as generally recognized as safe by the United States Food and Drug Administration in 2008 and grant of marketing approval by the European Union in 2011, the species has been widely cultivated and studied in several countries. Several efforts have been dedicated to the isolation and structure elucidation of minor components searching for novel non-caloric sugar substitutes with improved organoleptic properties. The present review provides an overview of the main chemical approaches found in the literature for identification and structural differentiation of diterpene glycosides from Stevia rebaudiana: High-performance Thin-Layer Chromatography, High-Performance Liquid Chromatography, Electrospray Ionization Mass Spectrometry and Nuclear Magnetic Resonance Spectroscopy. Modification of diterpene glycosides by chemical and enzymatic reactions together with some strategies to scale up of the purification process saving costs are also discussed. A list of natural diterpene glycosides, some examples of chemically modified and of enzymatically modified diterpene glycosides reported from 1931 to February 2021 were compiled using the scientific databases Google Scholar, ScienceDirect and PubMed.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Approaches toward the Separation, Modification, Identification and Scale up Purification of Tetracyclic Diterpene Glycosides from Stevia rebaudiana (Bertoni) Bertoni

Perera¹,

McChesney

2021

Molecules

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“…Additionally, three known compounds were purified in gram quantities and identified as rebaudiosides A ( 5 ), H (6 ) and J ( 7 ). The purification of the degradation products formed under acidic condition from rebaudioside A and stevioside was recently reported [8]. Preparation of a high-quality crystal of iso-stevioside, one of the by-products, allowed the confirmation of its structure by X-ray diffraction (Figure 4) .…”

Section: Resultsmentioning

confidence: 84%

“…Further sequential loss of three hexoses ([M − H] − H 2 O – 3 × 162 Da) − m / z = 641.3185, m / z = 479.2635 and m / z = 317.2146 from the C-13 moiety was observed at 70 eV. Acid hydrolysis of 1 furnished a mixture of aglycones and only D-glucose which was identified by comparison of the HPLC retention times of thiocarbamoyl thiazolidine derivatives prepared from sugar standards as previously described [8,9]. Hence compound 1 is a rebaudioside A isomer.…”

Section: Resultsmentioning

confidence: 99%

“…The rapid elution of compound 3 , <7 min, suggested that it is a highly substituted glycoside with a single sugar unit linked at C-19. Acid hydrolysis of 3 furnished a mixture of aglycones and only D-glucose which was identified by comparison of the HPLC retention times of thiocarbamoyl thiazolidine derivatives prepared from sugar standards, as previously described [8,9].…”

Section: Resultsmentioning

confidence: 99%

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Tetra-glucopyranosyl Diterpene ent-Kaur-16-en-19-oic Acid and ent-13(S)-Hydroxyatisenoic Acid Derivatives from a Commercial Extract of Stevia rebaudiana (Bertoni) Bertoni

et al. 2018

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Stevia rebaudiana and its diterpene glycosides are one of the main focuses of food companies interested in developing novel zero calorie sugar substitutes since the recognition of steviol glycosides as Generally Recognized as Safe (GRAS) by the United States Food and Drug Administration. Rebaudioside A, one of the major steviol glycosides of the leaves is more than 200 times sweeter than sucrose. However, its lingering aftertaste makes it less attractive as a table-top sweetener, despite its human health benefits. Herein, we report the purification of two novel tetra-glucopyranosyl diterpene glycosides 1 and 3 (rebaudioside A isomers) from a commercial Stevia rebaudiana leaf extract compounds, their saponification products compounds 2 and 4, together with three known compounds isolated in gram quantities. Compound 1 was determined to be 13-[(2-O-β-d-glucopyranosyl-6-O-β-d-glucopyranosyl-β-d-glucopyranosyl) oxy]ent-kaur-16-en-19-oic acid-β-d-glucopyranosy ester (rebaudioside Z), whereas compound 3 was found to be 13-[(2-O-β-d-glucopyranosyl-3-O-β-d-glucopyranosyl-β-d-glucopyranosyl) oxy]ent-hydroxyatis-16-en-19-oic acid -β-d-glucopyranosy ester. Two new tetracyclic derivatives with no sugar at position C-19 were prepared from rebaudiosides 1 and 3 under mild alkaline hydrolysis to afford compounds 2 13-[(2-O-β-d-glucopyranosyl-6-O-β-d-glucopyranosyl-β-d-glucopyranosyl) oxy]ent-kaur-16-en-19-oic acid (rebaudioside Z1) and 4 13-[(2-O-β-d-glucopyranosyl-3-O-β-d-glucopyranosyl-β-d-glucopyranosyl) oxy]ent-hydroxyatis-16-en-19-oic acid. Three known compounds were purified in gram quantities and identified as rebaudiosides A (5), H (6) and J (7). Chemical structures were unambiguously elucidated using different approaches, namely HRESIMS, HRESI-MS/MS, and 1D-and 2D-NMR spectroscopic data. Additionally, a high-quality crystal of iso-stevioside was grown in methanol and its structure confirmed by X-ray diffraction.

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Reaction coupling separation for isosteviol production from stevioside catalyzed by acidic ion-exchange resin

Zhou

Zhang

et al. 2020

Bioprocess Biosyst Eng

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Isosteviol, a prodrug used to be obtained via Wagner-Meerwein rearrangement from steviol with low yield and long reaction time. Herein, an in-situ separation-coupling-reaction is presented to prepare isosteviol from the natural sweetener stevioside. Simply with in-situ water-washing, the product containing 92.98% purity of isosteviol was obtained with a stevioside conversion of 97.23% from a packet bed reactor without further separation. Within the assayed inorganic acid, organic acids and acidic ionic liquids, the acidic ion-exchange resins provided higher product specificity towards isosteviol. Furthermore, comparing to 5-Fluorouracil, the product presented similar and even stronger inhibition on proliferation of the assayed human cancer cells in a time and dose-dependence by causing cell phase arrest. Isosteviol treatment caused G1 arrest on SGC-7901, HCT-8 and HCT-116 cells, S arrest on HepG2, Huh-7 and HepG3B cells, and G2 arrest on MGC-803 cells, respectively. Graphic abstractReaction coupling separation for isosteviol production catalyzed by acidic ion-exchange resin.

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Endocyclic double bond isomers and by-products from rebaudioside A and stevioside formed under acid conditions

Cited by 6 publications

References 21 publications

Approaches toward the Separation, Modification, Identification and Scale up Purification of Tetracyclic Diterpene Glycosides from Stevia rebaudiana (Bertoni) Bertoni

Approaches toward the Separation, Modification, Identification and Scale up Purification of Tetracyclic Diterpene Glycosides from Stevia rebaudiana (Bertoni) Bertoni

Tetra-glucopyranosyl Diterpene ent-Kaur-16-en-19-oic Acid and ent-13(S)-Hydroxyatisenoic Acid Derivatives from a Commercial Extract of Stevia rebaudiana (Bertoni) Bertoni

Reaction coupling separation for isosteviol production from stevioside catalyzed by acidic ion-exchange resin

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