Hydroxyl and methoxyl derivatives of benzylglucosinolate in Lepidium densiflorum with hydrolysis to isothiocyanates and non-isothiocyanate products: substitution governs product type and mass spectral fragmentation

Eleonora Pagnotta; Niels Agerbirk; Carl Erik Olsen; Luisa Ugolini; Susanna Cinti; Luca Lazzeri

doi:10.1021/acs.jafc.7b00529

Hydroxyl and methoxyl derivatives of benzylglucosinolate in Lepidium densiflorum with hydrolysis to isothiocyanates and non-isothiocyanate products: substitution governs product type and mass spectral fragmentation

Eleonora Pagnotta, Niels Agerbirk, Carl Erik Olsen, Luisa Ugolini, Susanna Cinti, Luca Lazzeri

Section for Plant Biochemistry

9 Citations (Scopus)

Abstract

A system of benzylic glucosinolates was found and characterized in common pepperweed, Lepidium densiflorum Schrad. The major glucosinolate was the novel 4-hydroxy-3,5-dimethoxybenzylglucosinolate (3,5-dimethoxysinalbin), present at high levels in seeds, leaves, and roots. Medium-level glucosinolates were 3,4-dimethoxybenzylglucosinolate and 3,4,5-trimethoxybenzylglucosinolate. Minor glucosinolates included benzylglucosinolate, 3-hydroxy- and 3-methoxybenzylglucosinolate, 4-hydroxybenzylglucosinolate (sinalbin), the novel 4-hydroxy-3-methoxybenzylglucosinolate (3-methoxysinalbin), and indole-type glucosinolates. A biosynthetic connection is suggested. NMR, UV, and ion trap MS/MS spectral data are reported, showing contrasting MS fragmentation of p-hydroxyls and p-methoxyls. Additional investigations by GC-MS focused on glucosinolate hydrolysis products. Whereas glucosinolates generally yielded isothiocyanates, the dominating 3,5-dimethoxysinalbin with a free p-hydroxyl group produced the corresponding alcohol and syringaldehyde (4-hydroxy-3,5-dimethoxybenzaldehyde). After thermal deactivation of the endogenous myrosinase enzyme, massive accumulation of the corresponding nitrile was detected. This case study points out how non-isothiocyanate glucosinolate hydrolysis products are prevalent in nature and of interest in both plant-pathogen interactions and human health.

Original language	English
Journal	Journal of Agricultural and Food Chemistry
Volume	65
Issue number	15
Pages (from-to)	3167-3178
Number of pages	12
ISSN	0021-8561
DOIs	https://doi.org/10.1021/acs.jafc.7b00529
Publication status	Published - 19 Apr 2017

Keywords

Hydrolysis
Isothiocyanates
Lepidium
Molecular Structure
Plant Extracts
Plant Leaves
Seeds
Tandem Mass Spectrometry
Thiocyanates
Thioglucosides
Journal Article

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Pagnotta, E., Agerbirk, N., Olsen, C. E., Ugolini, L., Cinti, S., & Lazzeri, L. (2017). Hydroxyl and methoxyl derivatives of benzylglucosinolate in Lepidium densiflorum with hydrolysis to isothiocyanates and non-isothiocyanate products: substitution governs product type and mass spectral fragmentation. Journal of Agricultural and Food Chemistry, 65(15), 3167-3178. https://doi.org/10.1021/acs.jafc.7b00529

Hydroxyl and methoxyl derivatives of benzylglucosinolate in Lepidium densiflorum with hydrolysis to isothiocyanates and non-isothiocyanate products: substitution governs product type and mass spectral fragmentation. / Pagnotta, Eleonora; Agerbirk, Niels; Olsen, Carl Erik et al.
In: Journal of Agricultural and Food Chemistry, Vol. 65, No. 15, 19.04.2017, p. 3167-3178.

Research output: Contribution to journal › Journal article › Research › peer-review

Pagnotta, E, Agerbirk, N, Olsen, CE, Ugolini, L, Cinti, S & Lazzeri, L 2017, 'Hydroxyl and methoxyl derivatives of benzylglucosinolate in Lepidium densiflorum with hydrolysis to isothiocyanates and non-isothiocyanate products: substitution governs product type and mass spectral fragmentation', Journal of Agricultural and Food Chemistry, vol. 65, no. 15, pp. 3167-3178. https://doi.org/10.1021/acs.jafc.7b00529

Pagnotta E, Agerbirk N, Olsen CE, Ugolini L, Cinti S, Lazzeri L. Hydroxyl and methoxyl derivatives of benzylglucosinolate in Lepidium densiflorum with hydrolysis to isothiocyanates and non-isothiocyanate products: substitution governs product type and mass spectral fragmentation. Journal of Agricultural and Food Chemistry. 2017 Apr 19;65(15):3167-3178. doi: 10.1021/acs.jafc.7b00529

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title = "Hydroxyl and methoxyl derivatives of benzylglucosinolate in Lepidium densiflorum with hydrolysis to isothiocyanates and non-isothiocyanate products: substitution governs product type and mass spectral fragmentation",

abstract = "A system of benzylic glucosinolates was found and characterized in common pepperweed, Lepidium densiflorum Schrad. The major glucosinolate was the novel 4-hydroxy-3,5-dimethoxybenzylglucosinolate (3,5-dimethoxysinalbin), present at high levels in seeds, leaves, and roots. Medium-level glucosinolates were 3,4-dimethoxybenzylglucosinolate and 3,4,5-trimethoxybenzylglucosinolate. Minor glucosinolates included benzylglucosinolate, 3-hydroxy- and 3-methoxybenzylglucosinolate, 4-hydroxybenzylglucosinolate (sinalbin), the novel 4-hydroxy-3-methoxybenzylglucosinolate (3-methoxysinalbin), and indole-type glucosinolates. A biosynthetic connection is suggested. NMR, UV, and ion trap MS/MS spectral data are reported, showing contrasting MS fragmentation of p-hydroxyls and p-methoxyls. Additional investigations by GC-MS focused on glucosinolate hydrolysis products. Whereas glucosinolates generally yielded isothiocyanates, the dominating 3,5-dimethoxysinalbin with a free p-hydroxyl group produced the corresponding alcohol and syringaldehyde (4-hydroxy-3,5-dimethoxybenzaldehyde). After thermal deactivation of the endogenous myrosinase enzyme, massive accumulation of the corresponding nitrile was detected. This case study points out how non-isothiocyanate glucosinolate hydrolysis products are prevalent in nature and of interest in both plant-pathogen interactions and human health.",

keywords = "Hydrolysis, Isothiocyanates, Lepidium, Molecular Structure, Plant Extracts, Plant Leaves, Seeds, Tandem Mass Spectrometry, Thiocyanates, Thioglucosides, Journal Article",

author = "Eleonora Pagnotta and Niels Agerbirk and Olsen, {Carl Erik} and Luisa Ugolini and Susanna Cinti and Luca Lazzeri",

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T1 - Hydroxyl and methoxyl derivatives of benzylglucosinolate in Lepidium densiflorum with hydrolysis to isothiocyanates and non-isothiocyanate products

T2 - substitution governs product type and mass spectral fragmentation

AU - Pagnotta, Eleonora

AU - Agerbirk, Niels

AU - Olsen, Carl Erik

AU - Ugolini, Luisa

AU - Cinti, Susanna

AU - Lazzeri, Luca

PY - 2017/4/19

Y1 - 2017/4/19

N2 - A system of benzylic glucosinolates was found and characterized in common pepperweed, Lepidium densiflorum Schrad. The major glucosinolate was the novel 4-hydroxy-3,5-dimethoxybenzylglucosinolate (3,5-dimethoxysinalbin), present at high levels in seeds, leaves, and roots. Medium-level glucosinolates were 3,4-dimethoxybenzylglucosinolate and 3,4,5-trimethoxybenzylglucosinolate. Minor glucosinolates included benzylglucosinolate, 3-hydroxy- and 3-methoxybenzylglucosinolate, 4-hydroxybenzylglucosinolate (sinalbin), the novel 4-hydroxy-3-methoxybenzylglucosinolate (3-methoxysinalbin), and indole-type glucosinolates. A biosynthetic connection is suggested. NMR, UV, and ion trap MS/MS spectral data are reported, showing contrasting MS fragmentation of p-hydroxyls and p-methoxyls. Additional investigations by GC-MS focused on glucosinolate hydrolysis products. Whereas glucosinolates generally yielded isothiocyanates, the dominating 3,5-dimethoxysinalbin with a free p-hydroxyl group produced the corresponding alcohol and syringaldehyde (4-hydroxy-3,5-dimethoxybenzaldehyde). After thermal deactivation of the endogenous myrosinase enzyme, massive accumulation of the corresponding nitrile was detected. This case study points out how non-isothiocyanate glucosinolate hydrolysis products are prevalent in nature and of interest in both plant-pathogen interactions and human health.

AB - A system of benzylic glucosinolates was found and characterized in common pepperweed, Lepidium densiflorum Schrad. The major glucosinolate was the novel 4-hydroxy-3,5-dimethoxybenzylglucosinolate (3,5-dimethoxysinalbin), present at high levels in seeds, leaves, and roots. Medium-level glucosinolates were 3,4-dimethoxybenzylglucosinolate and 3,4,5-trimethoxybenzylglucosinolate. Minor glucosinolates included benzylglucosinolate, 3-hydroxy- and 3-methoxybenzylglucosinolate, 4-hydroxybenzylglucosinolate (sinalbin), the novel 4-hydroxy-3-methoxybenzylglucosinolate (3-methoxysinalbin), and indole-type glucosinolates. A biosynthetic connection is suggested. NMR, UV, and ion trap MS/MS spectral data are reported, showing contrasting MS fragmentation of p-hydroxyls and p-methoxyls. Additional investigations by GC-MS focused on glucosinolate hydrolysis products. Whereas glucosinolates generally yielded isothiocyanates, the dominating 3,5-dimethoxysinalbin with a free p-hydroxyl group produced the corresponding alcohol and syringaldehyde (4-hydroxy-3,5-dimethoxybenzaldehyde). After thermal deactivation of the endogenous myrosinase enzyme, massive accumulation of the corresponding nitrile was detected. This case study points out how non-isothiocyanate glucosinolate hydrolysis products are prevalent in nature and of interest in both plant-pathogen interactions and human health.

KW - Hydrolysis

KW - Isothiocyanates

KW - Lepidium

KW - Molecular Structure

KW - Plant Extracts

KW - Plant Leaves

KW - Seeds

KW - Tandem Mass Spectrometry

KW - Thiocyanates

KW - Thioglucosides

KW - Journal Article

U2 - 10.1021/acs.jafc.7b00529

DO - 10.1021/acs.jafc.7b00529

M3 - Journal article

C2 - 28343387

SN - 0021-8561

VL - 65

SP - 3167

EP - 3178

JO - Journal of Agricultural and Food Chemistry

JF - Journal of Agricultural and Food Chemistry

IS - 15

ER -