Applications of Direct Analysis in Real Time-Mass Spectrometry (DART-MS) in Allium Chemistry. (Z)-Butanethial S-Oxide and 1-Butenyl Thiosulfinates and Their S-(E)-1-Butenylcysteine S-Oxide Precursor from Allium siculum

被引:72
作者
Kubec, Roman [1 ]
Cody, Robert B. [3 ]
Dane, A. John [3 ]
Musah, Rabi A. [2 ]
Schraml, Jan [4 ]
Vattekkatte, Abith [2 ]
Block, Eric [2 ]
机构
[1] Univ S Bohemia, Dept Appl Chem, Ceske Budejovice 37005, Czech Republic
[2] SUNY Albany, Dept Chem, Albany, NY 12222 USA
[3] JEOL USA Inc, Peabody, MA 01960 USA
[4] AS CR, Inst Chem Proc Fundamentals, Prague 16502 6, Czech Republic
基金
美国国家科学基金会;
关键词
Allium siculum; Nectaroscordum; Allium cepa; Petiveria alliacea; DART mass spectrometry; butanethial S-oxide; S-(1-butenyl)cysteine S-oxide; structure elucidation; homoisoalliin; lachrymatory sulfines; LACHRYMATORY FACTOR SYNTHASE; PETIVERIA-ALLIACEA; GENUS ALLIUM; ONION; IDENTIFICATION; CYSTEINE; SULFOXIDES; DISCOLORATION; DERIVATIVES; PIGMENT;
D O I
10.1021/jf903733e
中图分类号
S [农业科学];
学科分类号
09 ;
摘要
Lachrymatory (Z)-butanethial S-oxide along with several 1-butenyl thiosulfinates was detected by DART mass spectrometry upon cutting Allium siculum, a popular ornamental Allium species used in some cultures as a spice. (Z)-Butanethial S-oxide isolated from the plant was shown to be identical to a synthetic sample. Its likely precursor, (R-S,R-C,E)-S-(1-butenyl)cysteine S-oxide (homoisoalliin), was isolated from homogenates of A. siculum, and a closely related species Allium tripedale, and fully characterized. Through use of LC-MS, a series of related gamma-glutamyl derivatives were tentatively identified in A. sicutum and A. tripedale homogenates, including gamma-glutamyl-(E)-S-(1-butenyl)cysteine and its S-oxide, gamma-glutamyl-S-butylcysteine and its S-oxide, and gamma-glutamyl-Smethylcysteine and its S-oxide. Because compounds containing the 1-butenyl group have not been previously identified in genus Allium species, this work extends the range of known Allium sulfur compounds, The general applicability of DART mass spectrometry in identifying naturally occurring, thermally fragile thial S-oxides and thiosulfinates is illustrated with onion, Allium cepa, as well as a plant from a different genus, Petiveria alliacea.
引用
收藏
页码:1121 / 1128
页数:8
相关论文
共 38 条
[1]   Pungent products from garlic activate the sensory ion channel TRPA1 [J].
Bautista, DM ;
Movahed, P ;
Hinman, A ;
Axelsson, HE ;
Sterner, O ;
Högestätt, ED ;
Julius, D ;
Jordt, SE ;
Zygmunt, PM .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2005, 102 (34) :12248-12252
[2]   Allium chemistry: Microwave spectroscopic identification, mechanism of formation, synthesis, and reactions of (E,Z)-Propanethial S-oxide, the lachrymatory factor of the onion (Allium cepa) [J].
Block, E ;
Gillies, JZ ;
Gillies, CW ;
Bazzi, AA ;
Putman, D ;
Revelle, LK ;
Wang, DY ;
Zhang, X .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (32) :7492-7501
[3]   LACHRYMATORY FACTOR OF THE ONION - NMR-STUDY [J].
BLOCK, E ;
REVELLE, LK ;
BAZZI, AA .
TETRAHEDRON LETTERS, 1980, 21 (14) :1277-1280
[4]   THE ORGANOSULFUR CHEMISTRY OF THE GENUS ALLIUM - IMPLICATIONS FOR THE ORGANIC-CHEMISTRY OF SULFUR [J].
BLOCK, E .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1992, 31 (09) :1135-1178
[5]  
BLOCK E, 1994, ACS SYM SER, V564, P63
[6]  
Block E, 2010, GARLIC OTHER ALLIUMS, V49, P1
[7]   THIOPROPANAL S-OXIDE - LACHRYMATORY FACTOR IN ONIONS [J].
BRODNITZ, MH ;
PASCALE, JV .
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, 1971, 19 (02) :269-+
[8]   BASE CYCLIZATION OF TRANS-S-(1-BUTENYL)-L-CYSTEINE S-OXIDE [J].
CARSON, JF ;
LUNDIN, RE ;
BOGGS, LE .
JOURNAL OF ORGANIC CHEMISTRY, 1969, 34 (06) :1996-&
[9]   Versatile new ion source for the analysis of materials in open air under ambient conditions [J].
Cody, RB ;
Laramée, JA ;
Durst, HD .
ANALYTICAL CHEMISTRY, 2005, 77 (08) :2297-2302
[10]   Observation of Molecular Ions and Analysis of Nonpolar Compounds with the Direct Analysis in Real Time Ion Source [J].
Cody, Robert B. .
ANALYTICAL CHEMISTRY, 2009, 81 (03) :1101-1107