TY - JOUR
T1 - Gas-phase fragmentation reactions of protonated benzofuran- and dihydrobenzofuran-type neolignans investigated by accurate-mass electrospray ionization tandem mass spectrometry
AU - Dias, Herbert J.
AU - Baguenard, Manon
AU - Crevelin, Eduardo J.
AU - Palaretti, Vinicius
AU - Gates, Paul J.
AU - Vessecchi, Ricardo
AU - Crotti, Antônio E.M.
PY - 2019/1
Y1 - 2019/1
N2 - We have investigated gas‐phase fragmentation reactions of protonated
benzofuran neolignans (BNs) and dihydrobenzofuran neolignans (DBNs) by
accurate‐mass electrospray ionization tandem and multiple‐stage (MSn)
mass spectrometry combined with thermochemical data estimated by
Computational Chemistry. Most of the protonated compounds fragment into
product ions B ([M + H–MeOH]+), C ([B–MeOH]+), D ([C–CO]+), and E ([D–CO]+)
upon collision‐induced dissociation (CID). However, we identified a
series of diagnostic ions and associated them with specific structural
features. In the case of compounds displaying an acetoxy group at C‐4,
product ion C produces diagnostic ions K ([C–C2H2O]+), L ([K–CO]+), and P ([L–CO]+). Formation of product ions H ([D–H2O]+) and M ([H–CO]+) is associated with the hydroxyl group at C‐3 and C‐3′, whereas product ions N ([D–MeOH]+) and O ([N–MeOH]+) indicate a methoxyl group at the same positions. Finally, product ions F ([A–C2H2O]+), Q ([A–C3H6O2]+), I ([A–C6H6O]+), and J ([I–MeOH]+) for DBNs and product ion G ([B–C2H2O]+)
for BNs diagnose a saturated bond between C‐7′ and C‐8′. We used these
structure‐fragmentation relationships in combination with deuterium
exchange experiments, MSn data, and Computational Chemistry
to elucidate the gas‐phase fragmentation pathways of these compounds.
These results could help to elucidate DBN and BN metabolites in in vivo and in vitro studies on the basis of electrospray ionization ESI‐CID‐MS/MS data only.
AB - We have investigated gas‐phase fragmentation reactions of protonated
benzofuran neolignans (BNs) and dihydrobenzofuran neolignans (DBNs) by
accurate‐mass electrospray ionization tandem and multiple‐stage (MSn)
mass spectrometry combined with thermochemical data estimated by
Computational Chemistry. Most of the protonated compounds fragment into
product ions B ([M + H–MeOH]+), C ([B–MeOH]+), D ([C–CO]+), and E ([D–CO]+)
upon collision‐induced dissociation (CID). However, we identified a
series of diagnostic ions and associated them with specific structural
features. In the case of compounds displaying an acetoxy group at C‐4,
product ion C produces diagnostic ions K ([C–C2H2O]+), L ([K–CO]+), and P ([L–CO]+). Formation of product ions H ([D–H2O]+) and M ([H–CO]+) is associated with the hydroxyl group at C‐3 and C‐3′, whereas product ions N ([D–MeOH]+) and O ([N–MeOH]+) indicate a methoxyl group at the same positions. Finally, product ions F ([A–C2H2O]+), Q ([A–C3H6O2]+), I ([A–C6H6O]+), and J ([I–MeOH]+) for DBNs and product ion G ([B–C2H2O]+)
for BNs diagnose a saturated bond between C‐7′ and C‐8′. We used these
structure‐fragmentation relationships in combination with deuterium
exchange experiments, MSn data, and Computational Chemistry
to elucidate the gas‐phase fragmentation pathways of these compounds.
These results could help to elucidate DBN and BN metabolites in in vivo and in vitro studies on the basis of electrospray ionization ESI‐CID‐MS/MS data only.
KW - benzofuran
KW - computational chemistry
KW - dihydrobenzofuran
KW - fragmentation mechanisms
KW - neolignans
UR - http://www.scopus.com/inward/record.url?scp=85060152044&partnerID=8YFLogxK
U2 - 10.1002/jms.4304
DO - 10.1002/jms.4304
M3 - Article (Academic Journal)
C2 - 30362641
AN - SCOPUS:85060152044
SN - 1076-5174
VL - 54
SP - 35
EP - 46
JO - Journal of Mass Spectrometry
JF - Journal of Mass Spectrometry
IS - 1
ER -