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Synthesis and Mass Spectrometric Analysis of Aromatic and Indole Glucosinolates

Quan V. Vo1* and Tuan L. Nguyen2
1Department of Natural Sciences, Quang Tri Teacher Training College, Quang Tri Province, Vietnam
2Department of Chemistry, Quy Nhon University, 170 An Duong Vuong, Binh Dinh, Viet Nam

*Corresponding author (e-mail: This email address is being protected from spambots. You need JavaScript enabled to view it.; This email address is being protected from spambots. You need JavaScript enabled to view it.)

 

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ABSTRACT

The synthesis and mass spectrometric analysis of aromatic and indole glucosinolates were investigated in this study. It was found that besides the peaks at m/z 75, 80, 96, 97, 195, 259, 275, the mass spectra also contained peaks that served unambiguously to identify a particular glucosinolate based on the loss of SO3 from its unambiguousness to identify a specific ion [M-K]-, and other ions such as [R-C(=NOH)S]- and [R-C(S)OSO2]- generated from the fragmentation of the backbone skeleton of glucosinolates.

Key words: Synthesis; mass spectrometric analysis; aromatic; indole; glucosinolates; structure; purity; fragmentation pathways 
REFERENCES

Clarke, D.B. (2010) Glucosinolates, structures and analysis in food, Anal. Methods, 2(4), 310–325.

Fahey, J.W., Zalcmann, A.T. and Talalay, P. (2001) The chemical diversity and distribution of glucosinolates and isothiocyanates among plants, Phytochemistry, 56, 5–51.

Rollin, P. and Tatibouët, A. (2011) Glucosinolates: The synthetic approach, C.R. Chimie, 14, 194–210.

Bialecki, J.B., Ruzicka, J., Weisbecker, C.S., Haribal, M. and Attygallea, A.B. ( 2010) Collision-induced dissociationmass spectra of glucosinolate anions, J. Mass Spectrom., 45, 272–283.

Botting, C.H., Davidson, N.E., Griffiths, D.W., Bennett, R.N. and Botting, N.P. (2002) Analysis of intact glucosinolates by MALDI-TOF mass spec-trometry, J. Agric. Food Chem., 50(5), 983–988.

Eagles, J., Fenwick, G., Gmelin, R. and Rakow, D. (1981) The chemical ionization mass spectra of glucosinolates (mustard oil glycosides) and desulphoglucosinolates. A useful aid for structural analysis, Biol. Mass Spectrom., 8(6), 265–269.

Matthaus, B. and Luftmann, H. (2000) Glucosino-lates in members of the family brassicaceae: separation and identifi cation by LC/ESI-MS–MS., J. Agric. Food Chem., 48, 2234–2239.

Mellon, F.A., Bennett, R.N., Holst, B. and Williamson, G. (2002) Intact glucosinolate analysis in plant extracts by programmed cone voltage electrospray LC/MS: performance and comparison with LC/MS/MS methods, Anal. Biochem., 306(1), 83–91.

Song, L., Morrison, J.J., Botting, N.P. and Thornalley, P.J. (2005) Analysis of glucosinolates, isothiocyanates, and amine degradation products in vegetable extracts and blood plasma by LC–MS/MS, Anal. Biochem., 347(2), 234–243.

Rochfort, S.J., Trenerry, V.C., Imsic, M., Panozzo, J. and Jones, R. (2008) Class targeted metabolomics: ESI ion trap screening methods for glucosinolates based on MSn fragmentation, Phytochemistry, 69(8), 1671–1679.

Zrybko, C.L., Fukuda, E.K. and Rosen, R.T. (1997) Determination of glucosinolates in domestic and wild mustard by high-performance liquid chromatography with confirmation by electrospray mass spectrometry and photodiode-array detection, J. Chromatogr. A, 767(1), 43–52.

Vo, Q.V., Trenerry, C., Rochfort, S., Wadeson, J., Leyton, C. and Hughes, A.B. (2013) Synthesis and anti-inflammatory activity of aromatic glucosi-nolates, Bioorg. Med. Chem., 21(19), 5945–5954.

Vo, Q.V., Trenerry, C., Rochfort, S., White, J. and Hughes, A. (2014) Preparation and X-ray analysis of potassium (2, 3-dichlorophenyl) glucosinolate, Acta Cryst. C, 70(6), 588–594.

Benn, M.H. (1963) A new mustard oil glucoside synthesis: The synthesis of glucotropaeolin, Can. J. Chem., 41(11), 2836–2838.

Davidson, N.E., Rutherford, T.J. and Botting, N.P. (2000) Synthesis, analysis and rearrangement of novel unnatural glucosinolates, Carbohydr. Res., 330, 295–307.

Mays, J.R., Roska, R.W., Sarfaraz, S., Mukhtar, H. and Rajski, S.R. (2008) Identification, synthesis, and enzymology of non-natural glucosinolate chemopreventive candidates, ChemBioChem., 9, 729–747.

Floyd, N., Vijayakrishnan, B., Koeppe, J.R. and Davis, B.G. (2009) Thiyl glycosylation of olefinic proteins: S linked glycoconjugate synthesis, Angew. Chem. Int. Ed., 48(42), 7798–7802.

Maier, M. A., Yannopoulos, C.G., Nazim Mohamed, N., Roland, A., Fritz, H., Mohan, V., Just, G. and Manoharan, M. (2003) Synthesis of antisense oligonucleotides conjugated to a multivalent carbohydrate cluster for cellular targeting, Bioconjugate Chem., 14(1), 18–29.

Benn, M.H. (1964) The synthesis of gluconasturiin, J. Chem. Soc., 4072–4074.

Streicher, H., Latxague, L., Wiemann, T., Rollin, P. and Thiem, J. (1995) Synthesis of deoxy derivatives of the glucosinolates glucotropaeolin and glucobrassicin, Carbohydr. Res., 278, 257–270.

Viaud, M. and Rollin, P. (1990) First synthesis of an indole glucosinolate, Tetrahedron Lett., 31(10), 1417–1418.

Vo, Q.V., Trenerry, C., Rochfort, S. and Hughes, A.B. (2013) A total Synthesis of (R,S)s-Glucoraphanin, Tetrahedron, 69(41), 8731–8737.

Vo, Q.V., Trenerry, C., Rochfort, S., Wadeson, J., Leyton, C. and Hughes, A.B. (2014) Synthesis and anti-inflammatory activity of indole Glucosinolates, Bioorg. Med. Chem., 22, 856–864.

Pedras, M.S.C., Yaya, E.E. and Hossain, S. (2010) Unveiling the phytoalexin biosynthetic puzzle in salt cress: unprecedented incorporation of glucobrassicin into wasalexins A and B, Org. Biomol. Chem., 8(22), 5150–5158.

Robertson, A.A.B. and Botting, N.P. (1999) Synthesis of deuterium labelled desulfoglucosinolates as internal standards for LC-MS analysis, Tetrahedron, 55(46), 13269–13284.

Somei, M., Sato, H., Komura, N. and Kaneko, C. (1985) Heterocycles, 23, 1101–1106.

Attygalle, A.B., García-Rubio, S., Ta, J. and Meinwald, J. (2001) Collisionally-induced dissociation mass spectra of organic sulfate anions, J. Chem. Soc., Perkin Trans., 2(4), 498–506.

Bandu, M.L., Grubbs, T., Kater, M. and Desaire, H. (2006) Collision induced dissociation of alpha hydroxy acids: Evidence of an ion-neutral complex intermediate, J. Mass Spectrom., 251(1), 40–46.

Yi, L., Dratter, J., Wang, C., Tunge, J.A. and Desaire, H. (2006) Identification of sulfation sites of metabolites and prediction of the compounds’ biological effects, Anal. Bioanal. Chem., 386(3), 666–674.

Bojesen, G. and Larsen, E. (1991) Characterization of five glucosinolates by fast atom bombardment mass spectrometry and collision activation of [M− H]− 1, Biol. Mass Spectrom., 20(5), 286–288.

Kokkonen, P., Van der Greef, J., Niessen, W., Tjaden, U., Ten Hove, G. and Van de Werken, G. (1991) Identification of intact glucosinolates using direct coupling of high-performance liquid chromatography with continuous-flow frit fast atom bombardment tandem mass spectrometry, Biol. Mass Spectrom., 20(5), 259–267.

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