Synthesis of Active Strigolactone Analogues Based on Eudesmane- And Guaiane-Type Sesquiterpene Lactones

Article abstract of DOI:10.1021/acs.jafc.0c02361

Strigolactones are natural products that are exuded by plants and stimulate parasitic weed germination. Their use in herbicides is limited since they are produced in small quantities, but the synthesis of bioactive analogues provides an alternative source. In this work, eleven analogues have been synthesized. Among them, nine compounds belong to a novel family named eudesmanestrigolactones. The procedure is short (3-6 steps), the starting materials are isolated on a multigram scale, and global yields are up to 8%, which significantly enhance isolated yields. In bioassay, the compounds germinated high percentages of Phelipanche ramosa, Orobanche cumana, and Orobanche crenata seeds, even at nanogram doses (100 nM). Bioactivity was stereochemistry-dependent, and it was discussed in terms of the presence and geometry of the enol ether, orientation of the butenolide, and unsaturation of ring A. The reported compounds provide a set of readily obtained allelochemicals with potential applications as preventive herbicides.

Full text of DOI:10.1021/acs.jafc.0c02361

Subscriber access provided by University of Wollongong Library
Agricultural and Environmental Chemistry
Synthesis of active strigolactone analogs based on
eudesmane- and guaiane-type sesquiterpene lactones
Jesús G. Zorrilla, Antonio Cala, Carlos Rial, Francisco J. R. Mejías,
José M. G. Molinillo, Rosa M. Varela, and Francisco A. Macías
J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.0c02361 • Publication Date (Web): 14 Aug 2020
Downloaded from pubs.acs.org on August 14, 2020
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 37
Journal of Agricultural and Food Chemistry
!
!"#$%&'& () *+#',% &#-'.(/*+#("% *"*/(.& 0*&%1 (" %21%&3*"%4 *"1
.2*'*"%4#!5% &%&62'#%-5%"% /*+#("%&
"
#
7%&8& 9: ;(--'//*< A"#("'( =*/*< =*-/(& >'*/< ?-*"+'&+( 7: >: @%AB*&< 7(&C @: 9: @(/'"'//(< >(&*
@: D*-%/*< ?-*"+'&+( A: @*+B*&E
$
%
&
'
A//%/(5*#$! 9-(25< F%5*-#3%"# () G-.*"'+ =$%3'&#-!< H"&#'#2#% () I'(3(/%+2/%& JHKIHGL<
=*352& =MHAN< +$((/ () +'%"+%< O"',%-&'#! () =*1'P< =Q >%520/'+* *$*-*2'< R< SSTSU4
V2%-#( >%*/ J=W1'PL< 5*'"
(
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 2 of 37
)
A !"#A$"
!
"
#
$
%
&
'
(
!)
!
#-'.(/*+#("%& *-% "*#2-*/ 5-(12+#& #$*# *-% %X21%1 0! 5/*"#& *"1 &#'32/*#% 5*-*&'#'+ Y%%1
.%-3'"*#'(": Z$%'- 2&% '" $%-0'+'1%& '& /'3'#%1 &'"+% #$%! *-% 5-(12+%1 '" &3*// 62*"#'#'%& 02# #$%
&!"#$%&'& () 0'(*+#',% *"*/(.& 5-(,'1%& *" */#%-"*#',% &(2-+%: H" #$'& Y(-[ %/%,%" *"*/(.& $*,%
0%%" &!"#$%&'P%1: A3(". #$%3< "'"% +(35(2"1& 0%/(". #( * "(,%/ )*3'/! "*3%1
%21%&3*"%&#-'.(/*+#("%&: Z$% 5-(+%12-% '& &$(-# JN\] &#%5&L< #$% &#*-#'". 3*#%-'*/& *-% '&(/*#%1
(" * 32/#'.-*3 &+*/% *"1 ./(0*/ !'%/1& *-% 25 #( ^_< Y$'+$ &'."')'+*"#/! %"$*"+%& '&(/*#%1 !'%/1&:
H" 0'(*&&*! #$% +(35(2"1& .%-3'"*#%1 $'.$ 5%-+%"#*.%& () !"#$%&'(!" )&*+,&< -)+.&'(!"
(/*&'& *"1 -)+.&'(!" ()"'&0& &%%1&< %,%" *# "*"(.-*3 1(&%& JSUU "@L: I'(*+#','#! Y*&
&#%-%(+$%3'&#-!41%5%"1%"# *"1 '# '& 1'&+2&&%1 '" #%-3& () #$% 5-%&%"+% *"1 .%(3%#-! () #$% %"(/
%#$%-< (-'%"#*#'(" () #$% 02#%"(/'1% *"1 2"&*#2-*#'(" () -'". A: Z$% -%5(-#%1 +(35(2"1& 5-(,'1%
* &%# () -%*1'/! (0#*'"%1 *//%/(+$%3'+*/& Y'#$ 5(#%"#'*/ *55/'+*#'("& *& 5-%,%"#',% $%-0'+'1%&:
!!
!"
%&'()*+,- &%&62'#%-5%"% /*+#("%< %21%&3*"(/'1%< +(&#2"(/'1%< 1%$!1-(+(&#2&/*+#("%<
&#-'.(/*+#("% *"*/(.< 5*-*&'#'+ Y%%1< -)+.&'(!"< !"#$%&'(!":
!
ACS Paragon Plus Environment

Page 3 of 37
Journal of Agricultural and Food Chemistry
!#
./"#012$".0/
!$
!%
!&
!'
!(
")
"
"!
""
"#
"$
"%
!"#$%&'(!" )&*+,&< -)+.&'(!" (/*&'& *"1 -)+.&'(!" ()"'&0& *-% $(/(5*-*&'#'+
0-((3-*5% &5%+'%& *1*5#%1 #( 5*-*&'#'P% * 0-(*1 -*".% () +2/#',*0/% 5/*"# &5%+'%&: 1 )&*+,& +*"
5-(12+% * &'."')'+*"# 1%+-%*&% '" #$% 5-(12+#'(" () #(3*#(< ('/&%%1 -*5%< 02+[Y$%*#< #(0*++( *"1
$%35 +-(5&: Z$'& Y%%1 '& 3*'"/! /(+*#%1 '" M2-(5%< K(-#$ A)-'+* *"1 `%&#%-" A&'* 02# '# $*& */&(
0%%" '"#-(12+%1 '" A3%-'+* *"1 A2&#-*/'* *"1 '& #$% 3(&# Y'1%&5-%*1 0-((3-*5% &5%+'%&:S -1
(/*&'& '& * &5%+')'+ 5*-*&'#'+ &5%+'%& )(- &2")/(Y%- J2"#$&'0!/, &''//, a:L *"1 '# +*" 5-(12+%
&%-'(2& !'%/1 /(&&%& )(- #$'& &(2-+% () &%%1& *"1 ('/:b -1 ()"'&0& '& #$% 3(&# 1*3*.'". Y%%1 )(-
#%35%-*#% /%.23%& *-(2"1 #$% @%1'#%--*"%*" 0*&'" *"1 @'11/% M*&#:N 72&# ("% &'"./% 0-((3-*5%
5/*"# +*" 1'&&%3'"*#% #$(2&*"1& () &%%1& #$-(2.$ Y'"1 *"1 *.-'+2/#2-*/ 3*+$'"%-! 12% #( #$%
&3*// &'P% *"1 Y%'.$# () #$% &%%1&: H" *11'#'("< 5*-*&'#'+ &%%1& +*" -%3*'" 1(-3*"# '" &('/ )(-
*/3(&# bU !%*-&:c Z$%&% 5*-*&'#'+ &5%+'%& *-% * &%-'(2& #$-%*# #( *.-'+2/#2-% *"1 #$2& 5-%,%"#'(" '&
'35%-*#',%:
"&
"'
"(
#)
#
#!
#"
##
#$
#%
#&
Z$% 2&% () +/*&&'+*/ $%-0'+'1%&< 0*&%1 (" +(35(2"1& Y'#$ /(". $*/)4/')%< #( +("#-(/ Y%%1
'")%&#*#'("& -*'&%& &%,%-% '&&2%& Y'#$ -%&5%+# #( #$% +$%3'+*/ 5-(5%-#'%&: (3% $%-0'+'1%& $*,%
5-(,%" #( 0% %))%+#',%< &2+$ *& ./!5$(&*#% (- '3'1*P(/'"("%&< 02# #$% "%Y -%&#-'+#'("& (" #$%'- 2&%
'" 1%,%/(5%1 +(2"#-'%&T /'3'# #$%'- 5(#%"#'*/ *& * +("#-(/ &#-*#%.!: A"(#$%- 1'&*1,*"#*.% ()
+/*&&'+*/ $%-0'+'1%& +(3%& )-(3 #$% $'.$ *1*5#*0'/'#! () 5*-*&'#'+ Y%%1&< Y'#$ '"+-%*&'"./!
-%&'&#*"# 5(52/*#'("& *)#%- #$% 2&% () *.-(+$%3'+*/& #$*# $*,% * /'3'#%1 -*".% () 3(1%& () *+#'("<]
Y$'+$ -%12+%& #$%'- %))%+#',%"%&& '" #$% "%X# &%*&(": A2#$(-'P%1 &5%+')'+ $%-0'+'1%& 3*! +*2&%
*11'#'("*/ '&&2%&< %:.:< #$% *++232/*#'(" () #(X'+ *"1 +*-+'"(.%"'+ -%&'12%& '" #$% &('/ *"1
$*-,%&#%1 5-(12+#& 1%&#'"%1 )(- $23*" +("&235#'(":R Z$% /*##%- *+62'-%& &5%+'*/ -%/%,*"+% *& #$%
1%3*"1 )(- d0'(e 5-(12+#& '"+-%*&%& Y'#$ #'3%: ?2-#$%-3(-%< &(3% +$%3'+*/& $*,% 0%%" 5-(,%"
#( *++232/*#% )(- 1%+*1%& '" #$% &('/< &2+$ *& 5%&#'+'1%& 0*&%1 (" +$/(-'"*#%1 $!1-(+*-0("&:^
#'
#(
$)
Z$% &#-*#%.! ["(Y" *& d&2'+'1*/ .%-3'"*#'("e< Y$'+$ '& */&( +*//%1 #$% d$("%!5(#
&#-*#%.!e< %"*0/%& #$% 5-%,%"#'(" () 5*-*&'#'+ Y%%1 '")%&#*#'("&: Z$'& &#-*#%.! -%62'-%& #$% 2&% ()
&5%+')'+ +(35(2"1& #$*# *-% +$%3'+*//! -%+(."'P*0/% 0! 5*-*&'#'+ &%%1& *"1 *-% *55/'%1 #( #$% &('/
"
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 4 of 37
$
$!
0%)(-% &(Y'".< #$2& #-'..%-'". .%-3'"*#'(" '" #$% *0&%"+% () $(&# 5/*"#& *"1 2/#'3*#%/! /%*1'". #(
#$% 1%*#$ () (0/'.*#% 5*-*&'#%& 0! &#*-,*#'(" *)#%- )%Y 1*!&:f
$"
$#
$$
$%
$&
#-'.(/*+#("%& *-% ["(Y" *& * )*3'/! () "*#2-*/ 5-(12+#& #$*# &#'32/*#% #$% .%-3'"*#'("
() 5*-*&'#'+ -)+.&'(!" *"1 !"#$%&'(!" &%%1& '" "*#2-%< *"1 #$%! *-% %X21%1 0! $(&# 5/*"#&:SU
Z$%&% +(35(2"1& *+# *& 5$!#($(-3("%& *"1 #$%! *-% '",(/,%1 '" #$% -%.2/*#'(" () 1%,%/(53%"#
5-(+%&&%& /'[% &$((# 0-*"+$'".< #$%! *+# *& 5$!#($(-3("%&:SS Z$% &#-2+#2-% () &#-'.(/*+#("%& '&
-%/*#%1 #( #$*# () &#-'.(/ J3$4/)" 5L:
$'
$(
%)
%
%!
%"
%#
%$
%%
g(Y%,%-< "*#2-*/ &#-'.(/*+#("%& *-% "(# 2&%)2/ )(- #$% )(-32/*#'(" () *.-(+$%3'+*/& 0*&%1
(" &2'+'1*/ .%-3'"*#'(" &'"+% #$%'- '&(/*#'(" )-(3 "*#2-*/ &(2-+%& .',%& /(Y !'%/1& J'&(/*#'(" ()
&%,%-*/ 3'+-(.-*3& -%62'-%& #$(2&*"1& () 5/*"#&LSb *"1 #$%'- $'.$ 1%.-%% () +$'-*/'#! -%62'-%& *
+(35/%X #(#*/ &!"#$%&'& Y'#$ 32/#'5/% &#%5&: #-'.(/*+#("% *"*/(.& *-% 1%&'."%1 #( &'35/')! #$%
&!"#$%&'& () #$%&% .%-3'"*#'(" %/'+'#(-& *"1 #$'& *55-(*+$ '& 0*&%1 (" #$% &%3'&!"#$%&'& )-(3
&#-2+#2-*//! -%/*#%1 "*#2-*/ 5-(12+#& #$*# +*" 0% (0#*'"%1 (" * 32/#'.-*3 &+*/% )-(3 "*#2-*/
&(2-+%&: Z$% &%*-+$ )(- "%Y 0'(*+#',% &#-'.(/*+#("% *"*/(.& '& * $(# #(5'+ #$*# '& 0%'". '",%&#'.*#%1
0! "23%-(2& -%&%*-+$ .-(25& *-(2"1 #$% Y(-/1:SN\S] Z$% 3*'" *'3 () #$% &#21! -%5(-#%1 $%-% Y*&
#( *+$'%,% #$% %))'+'%"# &!"#$%&'& () &#-'.(/*+#("% *"*/(.&:
%&
%'
%(
&)
&
&!
&"
%&62'#%-5%"% /*+#("%& &$*-% &#-2+#2-*/ &'3'/*-'#'%& Y'#$ &#-'.(/*+#("%& *"1 +*" &#'32/*#%
#$% .%-3'"*#'(" () 5*-*&'#'+ Y%%1 &%%1&: a*+#("%& +(&#2"(/'1% J3L *"1 1%$!1-(+(&#2&/*+#("% J4L
J3$4/)" 6L +*" 0% '&(/*#%1 (" * 32/#'.-*3 &+*/% )-(3 *" %X#-*+# () 7&/,,/)"& (+,0/, *"1 #$%&% Y%-%
-%5(-#%1 #( 0% #$% 3*'" +(35(2"1& -%&5("&'0/% )(- 5*-*&'#'+ -%+(."'#'(" () &2")/(Y%- 0! -1
(/*&'&:SR '"+% #$%&% +(35(2"1& 5(&&%&& * /*+#("% 3('%#! J=4-'". '" &#-'.(/*+#("%&L< #$%
*11'#'(" () *" %X#-* 02#%"(/'1% -'". +(""%+#%1 0! *" %"(/ %#$%- 0("1 #( 3 *"1 4 *//(Y&
&#-'.(/*+#("% *"*/(.& #( 0% (0#*'"%1:S^
&#
&$
&%
Z$% 3*'" (0A%+#',% () #$% Y(-[ -%5(-#%1 $%-% Y*& #$% 5-%5*-*#'(" () "%Y &#-'.(/*+#("%
*"*/(.& 0! #$% *11'#'(" () #$% 02#%"(/'1% -'". #( #$% $!1-(X!/*#%1 1%-',*#',%& () 5< 6< 7 J3$4/)"
6&L *"1 4 J3$4/)" 6(L: Z$'& '& #$% )'-&# #'3% #$*# &#-'.(/*+#("% *"*/(.& 0*&%1 (" %21%&3*"(/'1%&
#
ACS Paragon Plus Environment

Page 5 of 37
Journal of Agricultural and Food Chemistry
&&
&'
&(
')
'
$*,% 0%%" -%5(-#%1: A// () #$% &#-'.(/*+#("% *"*/(.& Y%-% #%&#%1 '" * 5*-*&'#'+ &%%1 .%-3'"*#'("
0'(*&&*! '" (-1%- #( %,*/2*#% #$%'- 5(#%"#'*/ 2&% *& 5-%,%"#',% *.-(+$%3'+*/& )(- 0-((3-*5%
+("#-(/: 1 )&*+,&< -1 (/*&'& *"1 -1 ()"'&0& Y%-% #$% &5%+'%& +$(&%" )(- #%&#'". #( '1%"#')! #$%
3(&# 5-(3'&'". 5-(12+#& )(- #$% 5-%5*-*#'(" () 5-%4%3%-.%"+! $%-0'+'1%& #$-(2.$ #$% $("%!5(#
&#-*#%.!: Z$% /'[%/! &#-2+#2-%4*+#','#! -%/*#'("&$'5& J A>L *-% */&( 1'&+2&&%1:
'!
8A"9#.A:! A/1 89";01!
'"
'#
'$
'%
'&
''
'(
()
(
(!
("
(#
($
(%
(&
<&=&*>? 9@A&*BC&=D>? E*)F&+G*&,H Z$% 52-'#! () %*+$ +(35(2"1 Y*& *&&%&&%1 0! Sg
K@> &5%+#-(&+(5! 5-'(- #( #$% 0'(*+#','#! #%&#&: Z$% &#-2+#2-*/ 1%#%-3'"*#'(" () *// +(35(2"1&
Y*& +*--'%1 (2# 0! +(30'"'". SF4 JSg< SN=L *"1 bF4K@> JSg4Sg =G h< KGM h< Sg4SN= g i=
*"1 g@I=L %X5%-'3%"#& */(". Y'#$ &5%+')'+ -(#*#'("< OD< ?ZH> *"1< '" 5*-#'+2/*-< @ #(
S
1%#%-3'"% #$% 3(/%+2/*- )(-32/*%: g K@> *"1 SN= K@> &5%+#-* Y%-% -%+(-1%1 (" A.'/%"#
&5%+#-(3%#%-& *# cUU *"1 TUU @gP 2&'". =F=/N J@*."' (/,j< @%-+[L *& &(/,%"#: Z$% -%&'12*/
&(/,%"# 5%*[& Y%-% 2&%1 *& '"#%-"*/ -%)%-%"+% Jk R:b] 553 '" Sg *"1 k RR:U 553 '" SN= K@> )(-
=F=/NL: =G h< g i=< g@I= *"1 KGM h %X5%-'3%"#& Y%-% 5%-)(-3%1 2&'". D*-'*" ,"3-A
3'+-(5-(.-*3&: MX*+# 3*&&%& Y%-% 3%*&2-%1 (" * OVa=4iZG? M H J`*#%-& !"*5# 9b<
@*"+$%&#%-< OlL $'.$4-%&(/2#'(" 3*&& &5%+#-(3%#%- Jg>ZG?M H@ L: @*&& &5%+#-* Y%-%
-%+(-1%1 '" #$% "%.*#',%4 (- 5(&'#',%4'(" 3(1% '" #$% -*".% *Q8 SUU\bUUU< Y'#$ * 3*&& -%&(/2#'("
() bU<UUU *"1 *" *++%/%-*#'(" ,(/#*.% () U:R [D: ?ZH> &5%+#-* Y%-% (0#*'"%1 (" V%-['"\M/3%-
5%+#-23 Z`G H> &5%+#-(5$(#(3%#%-: @*A(- *0&(-5#'("& '" #$% '")-*-%1 *-% .',%" *&
Y*,%"230%-& m '" +3\S: G5#'+*/ -(#*#'("& Y%-% 3%*&2-%1 '" =g=/N (" * 7A =G V4bUUU
5(/*-'3%#%-:
('
((
=(/23" +$-(3*#(.-*5$! J==L Y*& 5%-)(-3%1 (" &'/'+* .%/ J@%-+[< 9%12-*"n ' ]U<
U:U]N\U:bUU 33L: Z$% -%*.%"#& *"1 gVa= 62*/'#! &(/,%"#& Y%-% &255/'%1 0! %'#$%- '.3*4
A/1-'+$ =(: J #: a(2'&< @'&&(2-'L< @%-+[ JF*-3&#*1#< 9%-3*"!L (- A/)* A%&*- J`*-1 g'//<
@*&&*+$2&%##&L: gVa= Y*& +*--'%1 (2# (" * @%-+[4g'#*+$' F4RUUU &!&#%3 JZ([!(< 7*5*"L Y'#$
* -%)-*+#',% '"1%X 1%#%+#(- JM/'#% a*=$-(3 a4bcfUL: A &%3'5-%5*-*#',% a'=$-(&5$%- bTU\SU '
))
)
)!
$
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 6 of 37
)"
)#
]U JSU o3L +(/23" J@%-+[L *"1 *" *"*/!#'+*/ a'=$-(=A>Z bTU4c ' ]U JT o3L +(/23" J@%-+[L
Y%-% %35/(!%1 Y'#$ * )/(Y -*#% () N 3aQ3'" *"1 S 3aQ3'"< -%&5%+#',%/!:
)$
)%
)&
)'
)(
)
!
"
!'=DI&,B, )J +&*BK>DBK&,H #-'.(/*+#("% *"*/(.& Y%-% &!"#$%#'P%1 )-(3 %21%&3*"(/'1%&
5< 6 *"1 7< *"1 .2*'*"(/'1% 4 J3$4/)" 6L: Z$% &#*-#'". 3*#%-'*/& 3 *"1 4 Y%-% '&(/*#%1 )-(3 * "*#2-*/
&(2-+%< ':%:< * 7&/,,/)"& (+,0/, -((# %X#-*+#< *"1 %21%&3*"(/'1%& 5 *"1 6 Y%-% (0#*'"%1 0!
-%*+#'(" () 3 2"1%- *+'1'+ +("1'#'("& )(//(Y'". #$% 5-(+%12-% -%5(-#%1 '" #$% /'#%-*#2-%<Sf Y$'/%
%21%&3*"(/'1% 7 Y*& &!"#$%#'P%1 )-(3 +(35(2"1 6 J3$4/)" 6&L: Z$% &#-2+#2-%& () %21%&3*"(/'1%&
5\L Y%-% +(")'-3%1 0! +(35*-'&(" () #$% %X5%-'3%"#*/ 1*#* Y'#$ #$(&% -%5(-#%1 '" #$%
/'#%-*#2-%:bU< bS Z$% Sg *"1 SN= K@> &5%+#-* )(- 5 Y%-% '"+/21%1 '" (2- 5-%,'(2& &#21!< *"1 &5%+#-*
*"1 %X5%-'3%"#*/ K@> 1*#* )(- +(35(2"1& 6 *"1 L *-% '"+/21%1 '" #$% &255(-#'". '")(-3*#'("
)(- +(35/%#%"%&&:
#
$
%
&
'
!'=DI&,B, )J &G+&,C>=)?B+& 7H ?(//(Y'". #$% 5-(+%12-% -%5(-#%1 5-%,'(2&/! )(-
&*"#*3*-'"%<bb +(35(2"1 6 JU:ST 33(/L Y*& #-%*#%1 Y'#$ %X+%&& JU:RT 33(/L b<N41'+$/(-(4T<]4
1'+!*"(4S<c40%"P(62'"("% JFFiL '" =gb=/b 2"1%- -%)/2X Jbc $L #( (0#*'" 7 '" ]R_ !'%/1: Z$%
&#-2+#2-% () 7 Y*& +(")'-3%1 0! +(35*-'". #$% Sg *"1 SN= K@> &5%+#-* Y'#$ #$(&% -%5(-#%1 )(-
N41%(X!0-*+$!/*%"(/'1%bN *"1 #$%&% *-% '"+/21%1 '" #$% &255(-#'". '")(-3*#'(" )(- +(35/%#%"%&&:
(
!)
!
!!
!"
!#
!$
!%
!'=DI&,B, )J >?F)I)?, MN 35N 36 >=+ 3LH Z$% #Y(4&#%5 &!"#$%#'+ 5-(+%12-% -%5(-#%1 #(
(0#*'" */+($(/& M *"1 35 J3$4/)", 6& *"1 6(L< ':%:< @'+$*%/ *11'#'(" () N43%#$(X!0%"P!/ */+($(/
*"1 &20&%62%"# (X'1*#'(" Y'#$ FFi< Y*& *55/'%1 #( (0#*'" M *"1 35< *"1 */&( #( #-*"&)(-3 6 *"1
7 '"#( #$% "%Y %#$%-& 3O Jcb_L *"1 33 JcU_L< -%&5%+#',%/!< *"1 #$%" '"#( #$% "%Y */+($(/& 36
J^]_L *"1 3L J^R_L< -%&5%+#',%/!: Z$'& 5-(+%12-% Y*& *55/'%1 '" * 5-%,'(2& &#21! #( (0#*'" 35
)-(3 5Sf *"1 #$% !'%/1 )(- #$% &%+("1 &#%5 Y*& '35-(,%1 )-(3 ]b_ #( RT_ 0! +*--!'". (2# #$%
-%*+#'(" () P Y'#$ FFi Y'#$(2# Y*#%-: Z$% &5%+#-* *"1 %X5%-'3%"#*/ 1*#* )(- "%Y +(35(2"1& *-%
5-(,'1%1 '" #$% &255(-#'". '")(-3*#'(":
!&
!'
!'=DI&,B, )J >?+&I'+&, 34N 3Q >=+ 3MH =(35(2"1 35 JcR:T 3.< U:Sf 33(/L Y*&
1'&&(/,%1 '" =gb=/b JT 3aL *"1 *11%1 #( * -(2"140(##(3%1 )/*&[ +("#*'"'". F%&&\@*-#'"
%
ACS Paragon Plus Environment

Page 7 of 37
Journal of Agricultural and Food Chemistry
!(
")
"
"!
""
"#
"$
"%
5%-'(1'"*"% J]R:] 3.< U:bR 33(/L: Z$% 3'X#2-% Y*& &#'--%1 )(- N $ *# -((3 #%35%-*#2-%< 62%"+$%1
Y'#$ &*#2-*#%1 *62%(2& K*g=GN JSU 3/L *"1 %X#-*+#%1 Y'#$ M#GA+ JN p SU 3/L: Z$% +(30'"%1
(-.*"'+ /*!%-& Y%-% Y*&$%1 Y'#$ 0-'"% *"1 1-'%1 (,%- *"$!1-(2& K*b Gc: Z$% &(/,%"# Y*&
%,*5(-*#%1 2"1%- ,*+223 #( (0#*'" * +-21% 5-(12+#< Y$'+$ Y*& 52-')'%1 0! +(/23"
+$-(3*#(.-*5$! Y'#$ * .-*1'%"# () SqUrNqb '4$%X*"%qM#GA+ #( .',% NU:S 3. () 34 J]S_ !'%/1L:
Z$% &*3% 5-(+%12-% Y*& +*--'%1 (2# (" 36 *"1 3L #( (0#*'" 3Q *"1 3M '" ]b_ *"1 TT_ !'%/1<
-%&5%+#',%/!: Z$% &5%+#-* *"1 %X5%-'3%"#*/ 1*#* )(- "%Y +(35(2"1& *-% 5-(,'1%1 '" #$%
&255(-#'". '")(-3*#'(":
"&
"'
"(
#)
#
#!
#"
##
#$
#%
#&
#'
#(
$)
!'=DI&,B, )J &G+&,C>=&,D*BR)?>FD)=&, S91!:,T 37U5QH Z$% *11'#'(" () #$% 02#%"(/'1%
)-*.3%"# #( */1%$!1%& 34\3M Y*& +*--'%1 (2# 2&'". JsL4T40-(3(4N43%#$!/4bJT2L4)2-*"("%< Y$'+$
Y*& &!"#$%&'P%1 *++(-1'". #( #$% 5-%,'(2&/! 1%&+-'0%1 3%#$(1:bc =(35(2"1 34 JTU:U 3.< U:b
33(/L Y*& *11%1 #( * 1-! -(2"140(##(3%1 )/*&[ +("#*'"'". #%#-*$!1-()2-*" JZg?L Jb 3aL 2"1%-
A- *"1 5(#*&&'23 0")0402#(X'1% JU:b 3a () * S:U @ &(/2#'(" '" 0")0402#*"(/< U:b 33(/L Y*&
'"#-(12+%1 Y'#$ +((/'". J'+% 0*#$L *"1 #$% 3'X#2-% Y*& &#'--%1 )(- SU 3'": ?-%&$/! &!"#$%&'P%1
JsL4T40-(3(4N43%#$!/4bJT2L4)2-*"("% JU:^ 33(/L Y*& *11%1 *"1 #$% -%*+#'(" 3'X#2-% Y*&
&#'--%1 )(- S $: `*#%- JS 3aL Y*& *11%1 *"1 #$% 5-(12+# Y*& %X#-*+#%1 JpNL Y'#$ M#GA+ JT 3aL
*"1 1-'%1 (,%- *"$!1-(2& @.b Gc: Z$% &(/,%"# Y*& %,*5(-*#%1 2"1%- ,*+223 #( .',% * +-21%
5-(12+#< Y$'+$ Y*& 52-')'%1 0! +(/23" +$-(3*#(.-*5$! Y'#$ * .-*1'%"# () SqUrNqb '4
$%X*"%qM#GA+: @'X#2-%& () %5'3%-& 37\3P *"1 5O\53 Y%-% +(//%+#%1 *"1 #$%" 52-')'%1 0! gVa=
(" * @%-+[ g'#*+$' F4RUUU gVa= &!&#%3 '" '&(+-*#'+ 3(1% %62'55%1 Y'#$ * &%3'5-%5*-*#',%
a'=$-(=A>Z bTU4SU ' ]U JSU o3L +(/23"< 2&'". '4$%X*"%qM#GA+ Nqb *& %/2%"#: h'%/1& )(-
'&(/*#%1 %5'3%-& Y%-% S]_ J37L< bc_ J3PL< ]_ J5OL *"1 T_ J53L:
$
$!
$"
$#
$$
A/1%$!1%& 3Q *"1 3M Y%-% #-%*#%1 2"1%- #$% &*3% +("1'#'("& *& */1%$!1% 34: Z$% -%*+#'("
() 3Q /%# #( (0#*'" 5-(12+#& 55 J3'X#2-% () %5'3%-&L *"1 56 '" N^_ *"1 f_ !'%/1< -%&5%+#',%/!t
Y$'/% -%*+#'(" () 3M /%# #( (0#*'" 5-(12+#& 5L *"1 54 '" ]_ *"1 SU_ !'%/1< -%&5%+#',%/!: M,'1%"+%
)(- #$% )(-3*#'(" () #$% %5'3%- () 56< 5L (- 54 Y*& "(# (0&%-,%1 12-'". #$% &!"#$%#'+ *"1
+$-(3*#(.-*5$'+ 5-(+%12-%&: G"+% (0#*'"%1 #$% #*-.%# MF a& J37V54L< #$% 02#%"(/'1% )-*.3%"#
&
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 8 of 37
$%
$&
$'
$(
Y*& *11%1 #( #$% */+($(/ 35 0! 2&'". #$% &*3% +("1'#'("&< #( .',% 1'$!1-(4MF a 5Q J3$4/)" 6&L
'" Tc_ !'%/1: M,'1%"+% )(- #$% )(-3*#'(" () #$% %5'3%- () 5Q Y*& "(# (0&%-,%1 12-'". #$% &!"#$%#'+
*"1 +$-(3*#(.-*5$'+ 5-(+%12-%&: Z$% &5%+#-* *"1 %X5%-'3%"#*/ 1*#* )(- "%Y +(35(2"1& *-%
5-(,'1%1 '" #$% &255(-#'". '")(-3*#'(":
%)
%
%!
%"
%#
%$
%%
%&
%'
%(
&)
!'=DI&,B, )J +BI'+*)RG>B>=&,D*BR)?>FD)=&, S5MU57TH =(35(2"1 M JRT 3.< U:NUU 33(/L
Y*& 1'&&(/,%1 '" Zg? JS 3aL 2"1%- *" A- *#3(&5$%-% J3$4/)" 6(L: Z$% &(/2#'(" Y*& *11%1 #( *
-(2"140(##(3%1 )/*&[ +("#*'"'". K*g JbS:] 3.< N %6L 2"1%- A- Y'#$ +((/'". J'+% 0*#$L< Z$%
3'X#2-% Y*& &#'--%1 )(- SU 3'": A &(/2#'(" () )-%&$/! &!"#$%&'P%1 JsL4T40-(3(4N43%#$!/4bJT2L4
)2-*"("% '" 1-! Zg? Jb 3aL Y*& *11%1 JS:b 33(/L *"1 #$% 3'X#2-% Y*& &#'--%1 )(- ]c $: Z$%
-%*+#'(" Y*& 62%"+$%1 Y'#$ &*#2-*#%1 *62%(2& Kgc=/ JbU 3aL *"1 #$% *62%(2& /*!%- Y*&
%X#-*+#%1 Y'#$ M#GA+ JN p bU 3aL: Z$% +(30'"%1 (-.*"'+ /*!%-& Y%-% 1-'%1 (,%- *"$!1-(2&
K*b Gc *"1 #$% &(/,%"# Y*& %,*5(-*#%1 2"1%- ,*+223 #( (0#*'" * +-21% 5-(12+#< Y$'+$ Y*&
52-')'%1 0! +(/23" +$-(3*#(.-*5$! Y'#$ * .-*1'%"# () '4$%X*"%QM#GA+ cqS\Nqb *& %/2%"#: Z$-%%
3*A(- )-*+#'("& Y%-% (0#*'"%1 *& )(//(Y&q NS 3. () #$% 3'X#2-% () %5'3%-& 5M *"1 57 JNU_L< b^
3. () -%+(,%-%1 M JNR_L *"1< 2"%X5%+#%1/!< bf 3. () +(35(2"1 5P JS]_L:
&
&!
&"
&#
&$
&%
&&
Z$% %5'3%-'+ 3'X#2-% () 5M *"1 57 Y*& &%5*-*#%1 (" * @%-+[ g'#*+$' F4RUUU gVa=
&!&#%3 '" '&(+-*#'+ 3(1% %62'55%1 Y'#$ *" *"*/!#'+*/ a'=$-(=A>Z bTU4c ' ]U JT o3L +(/23"
*"1 * 3'X#2-% () '4$%X*"%qJ=gNLb=G ^TqST *& %/2%"#: Z$% 1'3%- 5P Y*& 52-')'%1 2&'". #$% &*3%
gVa= &!&#%3 %62'55%1 Y'#$ * &%3'5-%5*-*#',% a'=$-(=A>Z bTU4SU ' ]U JSU o3L +(/23"<
2&'". '4$%X*"%qM#GA+ Scq] *& %/2%"#: H"A%+#'("& () U:SU\U:bU 3. $*1 #( 0% +*--'%1 (2# '" (-1%-
#( *,('1 +(%/2#'(" () #$% +(35(2"1& 12% #( #$% &'3'/*-'#! '" #$% 5(/*-'#! () #$% #Y( +(35(2"1&:
5%+#-* *"1 %X5%-'3%"#*/ 1*#* )(- 5M\5P *-% 5-(,'1%1 '" #$% &255(-#'". '")(-3*#'(":
&'
&(
')
'
'!
$B*FG?>* +BFI*)B,C &@A&*BC&=D,H H" (-1%- #( '1%"#')! #$% *0&(/2#% &#%-%(+$%3'&#-! ()
+(35(2"1& 37\53 *"1 56\57< %*+$ +(35(2"1 Y*& 1'&&(/,%1 '" @%Gg *"1 #$% &5%+#-* Y%-%
(0#*'"%1 (" * 7A =G 74STUU '"&#-23%"# J3$4/)" 9L: Z$% #$%(-%#'+*/ M=F Y%-% (0#*'"%1 2&'".
9*2&&'*" S] Y'#$ INahVQ]4NSS. J1<5L (5#'3'P%1 .%(3%#-'%&: H" %*+$ +*&%< #$% 5(/*-'P*0/%
+("#'"223 3(1%/ Y'#$ 3%#$*"(/ Y*& %35/(!%1 #( (0#*'" *++2-*#% #$%(-%#'+*/ =F &5%+#-*: Z$%
'
ACS Paragon Plus Environment

Page 9 of 37
Journal of Agricultural and Food Chemistry
'"
'#
'$
+(")(-3%-& %35/(!%1 Y%-% 3'"'323 %"%-.!< */&( (0#*'"%1 Y'#$ INahVQ]4NSS. J1<5L: Z$%
*0&(/2#% +(")'.2-*#'(" Y*& 1%#%-3'"%1 0! +'-+2/*- 1'+$-('&3 0! +(35*-'&(" () #$% #$%(-%#'+*/
+*/+2/*#'("& Y'#$ %X5%-'3%"#*/ 1*#*:
'%
'&
''
'(
()
(
(!
("
B)>,,>'H Z$% &#-'.(/*+#("% *"*/(.& 37\57< *& Y%// *& #$% 1'3%-'+ 0!5-(12+# 5P< Y%-%
#%&#%1 '" #$% 0-((3-*5% &%%1 .%-3'"*#'(" 0'(*&&*! (" #$-%% &5%+'%&< "*3%/! -)+.&'(!" (/*&'&<
-)+.&'(!" ()"'&0& *"1 !"#$%&'(!" )&*+,&< '" #$% +("+%"#-*#'(" -*".% SU4c\SU4R @: Z$% 3(&#
*+#',% +(35(2"1& J3P *"1 5L )(- -1 (/*&'& *"1 5O< 53< 56< 5L< 57 *"1 5P )(- 1 )&*+,&L Y%-%
#%&#%1 '" #$% +("+%"#-*#'(" -*".% SU4c\SU4Sb @ #( (0#*'" )2// '"$'0'#'(" +2-,%&: Z$% &!"#$%#'+
+(35(2"1 9>bc Y*& '"+/21%1 *& * 5(&'#',% +("#-(/ )(- #$% 0-((3-*5% 0'(*&&*! *"1 1%'("'P%1
&#%-'/'P%1 Y*#%- Y'#$ S_ ,Q, *+%#("% Y*& 2&%1 *& * "%.*#',% +("#-(/< Y$%-% &5("#*"%(2&
.%-3'"*#'(" Y*& "(# (0&%-,%1:
(#
($
(%
(&
('
Z$% 5-(+%12-% )(- #$% 0'(*&&*! $*& 0%%" -%5(-#%1 5-%,'(2&/!Sf *"1 '# '& '"+/21%1 '" #$%
&255(-#'". '")(-3*#'(": %%1& () -1 :/*&'& Y%-% 5-(,'1%1 0! F-: a%("*-1( D%/*&+( JH"&#'#2#(
1% A.-'+2/#2-* (&#%"'0/%< = H=< O"',%-&'#! () =(-1(0*< 5*'"L *"1 &%%1& () -1 ()"'&0& *"1 1
)&*+,& Y%-% 5-(,'1%1 0! F-: @*2-'P'( D2--( JH"&#'#2#% () +'%"+%& () ?((1 V-(12+#'("< K*#'("*/
=(2"+'/ () >%&%*-+$< I*-'< H#*/!L:
((
!))
!)
!)!
!)"
$>?FG?>DB)= )J 9$4O K>?G&,H Z$% +(35(2"1& #$*# .*,% 3'"'323 *+#','#'%& () TU_ *"1
Y%-% *+#',% *# 3(-% #$*" ("% +("+%"#-*#'(" Y%-% &#*#'&#'+*//! *"*/!P%1 )(- #$%'- M=TU ,*/2% 2&'".
#$% 9-*5$V*1 V-'&3 ,:T:UU &()#Y*-% 5*+[*.% J9-*5$V*1 ()#Y*-%< H"+:< *" F'%.(< O AL: Z$%
0'(*+#','#! 1*#* Y%-% )'##%1 #( * &'.3('1*/ 1(&%4-%&5("&% 3(1%/ Y'#$ +("&#*"# &/(5%: Z$% -%&2/#&
() #$'& *"*/!&'& *-% &$(Y" '" 0&.#" 5:
!)#
!)$
!)%
!)&
!)'
#9!2:"! A/1 1.!$2!!.0/
M21%&3*"(/'1%& 5< 6 *"1 7 J3$4/)" 6&L Y%-% +$(&%" *& #*-.%#& )(- #$% &!"#$%&'& () "(,%/
&#-'.(/*+#("% *"*/(.& "*3%1 %21%&3*"%&#-'.(/*+#("%& JMF a&L: =(35(2"1& 5 *"1 6 Y%-%
(0#*'"%1 0! +!+/'P*#'(" () +(&#2"(/'1% J3L< * .%-3*+-*"%4#!5% &%&62'#%-5%"% /*+#("% '&(/*#%1
#(.%#$%- Y'#$ +(35(2"1 4 '" .-*3 &+*/% )-(3 7&/,,/)"& (+,0/, -((#&: =(35(2"1 7 Y*& */&(
(
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 10 of 37
!)(
! )
+("&'1%-%1 *& '# '& *" *))(-1*0/% %21%&3*"(/'1% (0#*'"%1 0! -%*+#'(" () 6 Y'#$ %X+%&& FFi: Z$%
3%#$(1 5-%&%"#%1 $%-%'" #( (0#*'" 7 )-(3 u4+!+/(+(&#2"(/'1% J6L '& -%5(-#%1 )(- #$% )'-&# #'3%:
!
! !
! "
! #
! $
G2- -%+%"# -%&2/#& 1%3("&#-*#%1 #$*# +(35(2"1 5 &#'32/*#%& .%-3'"*#'(" () -: (/*&'&
*"1 1 )&*+,& &%%1& &'."')'+*"#/! J&'."')'+*"+% /%,%/ () U:UTL< Y'#$ M=TU ,*/2%& () R:NSvSU4] @
*"1 wSU4R @< -%&5%+#',%/!<Sf 02# (#$%- &#21'%& Y%-% "(# )(2"1 '" #$% /'#%-*#2-% -%.*-1'".
&#-'.(/*+#("% *"*/(.& 0*&%1 (" %21%&3*"(/'1%&: g(Y%,%-< &#-'.(/*+#("% *"*/(.& 0*&%1 (" 4 Y%-%
1%&'."%1 *"1 #%&#%1 5-%,'(2&/! *"1 5-(3'&'". -%&2/#& Y%-% (0#*'"%1:c
! %
! &
! '
! (
!!)
A"*/(.& Y%-% &!"#$%&'P%1 0! *11'". * 02#%"(/'1% -'". #( #$% $!1-(X!/*#%1 1%-',*#',%& *#
=4SN () 5< 6< 7 JMF a&< 3$4/)" 6&L *"1 4 J1'$!1-(49Ma&< 3$4/)" 6(L: Z$%&% */+($(/& J+(35(2"1&
35V3L *"1 ML Y%-% &!"#$%&'P%1 '" #Y( &#%5& )-(3 #$% &#*-#'". %21%&3*"(/'1% J5< 6 (-
7LQ.2*'*"(/'1% J4L< *"1 #$% 5-(+%12-% #( *11 #$% 02#%"(/'1% -'". -%62'-%1 #$% 5-'(- )(-3*#'(" ()
*/1%$!1%& *# =4SN J34V3ML #( *+$'%,% &#-'.(/*+#("%& Y'#$ *" %"(/ %#$%- 0("1 J37V54L:
!!
!!!
!!"
!!#
!!$
!!%
!!&
!!'
A
5-%,'(2& &#-*#%.! '",(/,%1 $!1-(X!/*#'(" *# =4SN Y'#$ #$% 2&% ()
$%X*3%#$!/5$(&5$(-*3'1% J* $'.$/! #(X'+ -%*.%"#L< /(". -%*+#'(" #'3% JT 1*!&L *"1 $'.$
#%35%-*#2-% J^U x=L< *"1 '# 5-(12+%1 *" 2"1%&'-%1 1'$!1-(X!/*#%1 0!5-(12+#:c A& -%5(-#%1
-%+%"#/!< Y% &2++%%1%1 '" $!1-(X!/*#'". 5 *"1 4 '" #Y( &#%5& 0! @'+$*%/ *11'#'(" () c4
3%#$(X!0%"P!/ */+($(/ *# =4SN )(//(Y%1 0! (X'1*#'(" Y'#$ FFi< Y'#$ $'.$ !'%/1& (0#*'"%1 )(-
0(#$ #*-.%# +(35(2"1& 35 JRS_L *"1 M JTc_L:Sf H" #$% 5-%&%"# &#21!< #$'& 5-(+%12-% Y*& '35-(,%1
*"1 *55/'%1 #( +(35(2"1& 6 *"1 7 )(- #$% )'-&# #'3% #( (0#*'" %#$%-& 3O *"1 33< *"1 #$%" */+($(/&
36 *"1 3L< -%&5%+#',%/!: ?2-#$%-3(-%< #$% !'%/1 )(- #$% )(-3*#'(" () 35 Y*& '35-(,%1:
!!(
!")
!"
!"!
!""
!"#
!'=DI&,B, )J &DI&*, >=+ 364I'+*)@' +&*BK>DBK&,H Z$% @'+$*%/ *11'#'(" () c4
3%#$(X!0%"P!/ */+($(/ #( =4SN () 6 *"1 7 Y*& &2++%&&)2//! 5-(+%%1%1 #( .',% %#$%-& 3O *"1 33
'" cb_ *"1 cU_ !'%/1< -%&5%+#',%/! J3$4/)" 6&L: M#$%-& Q J]N_L *"1 P Jc]_L Y%-% &!"#$%&'P%1 '"
(2- 5-%,'(2& Y(-[ 0! )(//(Y'". #$% &*3% 5-(+%12-% *"1 #$% &5%+#-(&+(5'+ 1*#* Y%-% +("&'&#%"#
Y'#$ /'#%-*#2-% 1*#*:Sf H" * &'3'/*- Y*! #( +(35(2"1 P< #$% Sg K@> &5%+#-* () 5-(12+#& 3O *"1 33
&$(Y%1 * "%Y &'."*/ )(- g4SS *# k b:cf *"1 k b:TN< -%&5%+#',%/!< *"1 #$%&% +(--%/*#%1 Y'#$ =4SS
)
ACS Paragon Plus Environment

Page 11 of 37
Journal of Agricultural and Food Chemistry
!"$
!"%
!"&
!"'
!"(
!#)
!#
!#!
!#"
*# k c]:] *"1 k c]:f '" #$% SN= K@> &5%+#-*: Z$%&% &'."*/& 3*#+$ Y'#$ &5b &'."*/& #$*# *-% *0&%"#
'" +(35(2"1& 6 *"1 7: ?2-#$%-3(-%< &'."*/& )(- g4SN '" #$% Sg K@> &5%+#-* '" 0(#$ +*&%& Y%-%
&$')#%1 )-(3 /(Y%- )'%/1 #( $'.$%- )'%/1 Y$%" +(35*-%1 Y'#$ 6 J)-(3 k ]:U] *"1 k T:N^ #( k N:RR
*"1 k N:RSL *"1 7 J)-(3 k ]:SU *"1 k T:cb #( k N:R^ *"1 k N:RbL: Z$% "%Y Sg &'."*/& *# k R:bc *"1
k ]:^^ J+(--%&5("1'". #( * 0%"P!/ -'". 1'&20&#'#2#%1 '" #$% %&)&45(&'#'("&L< *& Y%// *& #$% "%Y
&'."*/ *# k N:^U< +(")'-3%1 #$% 5-%&%"+% () #$% 3%#$(X!0%"P!/ 3('%#! '" 3O *"1 33: =(25/'".
+("&#*"# ,*/2% 0%#Y%%" Sb:] *"1 Sb:^ gP 0%#Y%%" g4R *"1 g4SS +(")'-3%1 #$% &#%-%(+$%3'&#-!
() #$% +(35(2"1&: Z$% SN= &'."*/& Y%-% *&&'."%1 Y'#$ %*+$ () #$%'- Sg &'."*/& *"1 #$% 5(&'#'(" '"
#$% 3(/%+2/% Y*& '1%"#')'%1 0! +(--%/*#'("& (0&%-,%1 '" #$% bF K@> %X5%-'3%"#&:
!##
!#$
!#%
!#&
!#'
!#(
!$)
!$
!$!
!$"
!$#
!$$
?(//(Y'". #$% 5-(+%12-% -%5(-#%1 #( (0#*'" */+($(/& M *"1 35< +(35(2"1& 3O *"1 33 Y%-%
&20&%62%"#/! (X'1'P%1 2&'". FFi #( .',% */+($(/& 36 *"1 3L '" ^]_ *"1 ^R_ !'%/1< -%&5%+#',%/!
J3$4/)" 6&L: A& '" #$% +*&% () #$% %#$%-&< #$% K@> &5%+#-* () "%Y 5-(12+#& J36 *"1 3LL Y%-% ,%-!
&'3'/*- #( #$(&% () 5-%,'(2&/! &!"#$%#'P%1 35: Z$% /(&& () #$% 3%#$(X!0%"P!/ 3('%#! Y*&
%,'1%"+%1 0! #$% *0&%"+% () *-(3*#'+ *"1 3%#$(X! &'."*/& '" #$% &5%+#-* () 36 *"1 3LN Y$%"
+(35*-%1 Y'#$ #$% &5%+#-* () %#$%-& 3O *"1 33: ?2-#$%-3(-%< g4SN &'."*/& Y%-% &$')#%1 #( /(Y%-
)'%/1< )-(3 k N:RR *"1 k N:RS #( k N:fR *"1 k N:R^ '" #$% +*&% () 36< *"1 )-(3 k N:R^ *"1 k N:Rb #(
k N:ff *"1 k N:^U '" #$% +*&% () 3L: Z$% ?ZH> &5%+#-* &$(Y%1 * 0-(*1 0*"1 *# NcTU +3\S *"1 #$'&
'"1'+*#%& #$% 5-%&%"+% () * $!1-(X!/ .-(25 '" #$% 3(/%+2/%: G"+% *.*'"< +(25/'". +("&#*"# ,*/2%&
0%#Y%%" Sb:^ *"1 SN:U gP 0%#Y%%" g4R *"1 g4SS +(")'-3%1 #$% &#%-%(+$%3'&#-! () #$%
+(35(2"1&: SN= &'."*/& Y%-% *&&'."%1 Y'#$ -%/*#%1 Sg &'."*/& *"1 #$% 5(&'#'("& '" #$% 3(/%+2/%
Y%-% '1%"#')'%1 0! +(--%/*#'("& (0&%-,%1 '" #$% bF K@> %X5%-'3%"#&:
!$%
!$&
!$'
!$(
!%)
!%
!'=DI&,B, )J >?+&I'+&,H Z$% %21%&3*"(/'1% */+($(/& 35\3L Y%-% (X'1'P%1 #( #$%
+(--%&5("1'". */1%$!1%& 5-'(- #( #$% *11'#'(" () #$% 02#%"(/'1% -'". #( (0#*'" #$% &#-'.(/*+#("%
*"*/(.& J3$4/)" 6&L: V-'3*-! */+($(/& *-% #!5'+*//! (X'1'P%1 #( */1%$!1%& 2"1%- 3'/1 +("1'#'("&
Y'#$ F%&&\@*-#'" 5%-'(1'"*"%:bT Z$% */1%$!1%& -%&2/#'". )-(3 #$% (X'1*#'(" () #$% %21%&3*"%
*/+($(/& J35< 36< 3LL *-% -%5(-#%1 $%-%'" )(- #$% )'-&# #'3%< Y'#$ !'%/1& () ]S_< ]b_ *"1 TT_
(0#*'"%1 )(- 34< 3Q *"1 3M< -%&5%+#',%/!:
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 12 of 37
!%!
!%"
!%#
!%$
2++%&& '" #$% &!"#$%&'& () 34\3M Y*& ,%-')'%1 0! #$% Sg K@> &5%+#-* *)#%- (0&%-,'". *
"%Y &'."*/ +%"#%-%1 *# k f:^R< Y$'+$ '& #!5'+*/ () *" */1%$!1% *"1 Y*& *&&'."%1 #( g4SN: A "%Y
&'."*/ *# k Sf]:U '" #$% SN= K@> &5%+#-*< *&&'."%1 #( =4SN 0! +(--%/*#'("& (0&%-,%1 '" #$% bF
K@> %X5%-'3%"#&< +(")'-3%1 #$% 5-%&%"+% () *" */1%$!1% .-(25:
!%%
!%&
!%'
!%(
!&)
!&
!&!
!'=DI&,B, )J ,D*BR)?>FD)=& >=>?)R, A #(#*/ () "'"% MF a& Y%-% &!"#$%&'P%1 )-(3 #$%
*/1%$!1%& 34\3M JMF a& 37\54L *"1 */+($(/ 35 JMF a 5QL J)'.2-% b0L: Z$'& /*&# &#%5 -%62'-%1
#$% )(-3*#'(" () #$% %"(/*#% () #$% &#*-#'". */1%$!1%Q*/+($(/ 0! -%*+#'(" Y'#$ 5(#*&&'23 0")04
02#(X'1%: Z$%"< )(2- %62',*/%"#& () 0-(3'"*#%1 )2-*"("% J* +(35(2"1 Y'#$ /(Y &#*0'/'#! #$*# Y*&
(0#*'"%1 '33%1'*#%/! 5-'(- #( 2&%Lbc Y%-% *11%1 J3$4/)" 6&L: A "2+/%(5$'/'+ &20&#'#2#'(" Y*&
+*--'%1 (2# '" Y$'+$ #$% "2+/%(5$/'/+ (X!.%" () #$% %"(/*#% 0("1& Y'#$ #$% )2-*"("%< )(-3'".
MF a& 37V5Q *"1 lI- 5-%+'5'#*#%1 *& +("&%62%"+%:
!&"
!&#
!&$
!&%
!&&
!&'
!&(
!')
!'
!'!
!'"
!'#
!'$
!'%
!'&
>%*+#'(" () */1%$!1% 34 .*,% )(2- '&(/*#%1 MF a& J37\53L *)#%- +(/23" +$-(3*#(.-*5$!
*"1 gVa= 52-')'+*#'(" () #$% +-21% 5-(12+#&: =(")'-3*#'(" () #$% '&(/*#'(" () 52-% %5'3%-& Y*&
%,'1%"+%1 0! K@> &5%+#-(&+(5!< &'"+% 5-'(- #( gVa= &%5*-*#'("< #$% &5%+#-* &$(Y%1 125/'+*#%1
&'."*/&: `$%" #$%&% )-*+#'("& Y%-% 52-')'%1< #Y( 1'))%-%"# 5%*[& Y%-% +(//%+#%1 )-(3 %*+$
)-*+#'("< *"1 K@> &5%+#-* () %*+$ 5%*[ &$(Y%1 #$*# &'."*/& Y%-% "(# 125/'+*#%1: '"+% #$%
&#*-#'". 3*#%-'*/ J3L Y*& %"*"#'(3%-'+*//! 52-%< #$%&% +(35(2"1& &$(2/1 */&( 0% 52-%
%"*"#'(3%-&: Z$% !'%/1& (0#*'"%1 Y%-% ST_ J37L< bN_ J3PL *"1 T_ J5O *"1 53L: Z$% 3(/%+2/*-
)(-32/*% 1%#%-3'"%1 0! @ J=bUgbcGTL Y%-% +("&'&#%"# Y'#$ #$% #*-.%# +(35(2"1&: Z$% Sg *"1
SN= K@> &5%+#-* () #$% +(35(2"1& &$(Y%1 #$% &'."*/& +(--%&5("1'". #( #$% "%Y/! '"#-(12+%1
02#%"(/'1% -'".q g4by Jk ]:U^L< g4Ny J0%#Y%%" k ]:fU *"1 k ]:^RL *"1 g4Sz J0%#Y%%" k b:UU *"1 k
S:fTL: Z$% 5-%&%"+% () #$% =4SS\=4SN 1(20/% 0("1 #$*# )(-3& #$% %"(/ %#$%- Y*& %,'1%"+%1 '" #$%
Sg K@> 0! #$% *0&%"+% () * &'."*/ )(- g4SS *"1 0! #$% "%Y &$')# () g4SN< Y$'+$ +$*".%1 )-(3
k f:^] #( k R:N] J37L< k R:NT J3PL< k ]:TU J5OL *"1 k ]:TS J53L: KGM hSF %X5%-'3%"#& Y%-% 2&%1
#( *&&'." #$% .%(3%#-! () #$% 1(20/% 0("1< Y$%-% g4SN () 37\3P &$(Y%1 *" KGM %))%+# Y'#$ g4
R< #$2& %,'1%"+'". #$%'- 5-(X'3'#! '" &5*+% *"1< #$%-%)(-%< #$% SS; .%(3%#-! J3$4/)" 9L:
!
ACS Paragon Plus Environment

Page 13 of 37
Journal of Agricultural and Food Chemistry
!''
!'(
=(35(2"1& 5O\53 Y%-% '1%"#')'%1 *& SS< &#%-%('&(3%-&: Z$% !'%/1& )(- SS; 5-(12+#& JN^_L Y%-%
$'.$%- #$*" #$(&% )(- SS< 5-(12+#& JSU_L:
!()
!(
!(!
A0&(/2#% +(")'.2-*#'(" Y*& 1%#%-3'"%1 0! %X5%-'3%"#*/ *"1 #$%(-%#'+*/ M=F &5%+#-* )(-
MF a& J3$4/)" =&L *"1 #$% &#%-%(+$%3'&#-! () =4b{ *"1 =4SS Y*& 1%#%-3'"%1 0! +(35*-'&(" Y'#$
#$% %X5%-'3%"#*/ ,*/2%&:
!("
!(#
!($
!(%
!(&
!('
!((
"))
")
")!
MF a 3P &$(Y%1 #Y( 0*"1& *# bSU "3 *"1 bbT "3 Y'#$ * &'." +$*".% '" #$% -(#*#'("
*"./% \ '" +("#-*&# #( 37< Y$'+$ &$(Y%1 #$% &*3% #Y( 0*"1& *# 5(&'#',% *"./%&< */0%'# Y'#$ *
0*#$(+$-(3'+ %))%+#: A++(-1'". #( #$% 1'))%-%"+%& 0%#Y%%" 37 *"1 3P< #$% > *"1 7 +(")'.2-*#'("
*# =4b{ '& %X+'#%1 '" #$% -*".% bbT\bcU "3: H" #$'& +*&%< #$% #(#*/ +(")'.2-*#'("& +*" 0% *&&'."%1
*& c<ST4JSS;L4Jb{>L4%21%&3*"%&#-'.(/*+#("% J37L *"1 c<ST4JSS;L4Jb{7L4%21%&3*"%&#-'.(/*+#("%
J3PL: M5'3%-& 5O *"1 53 &$(Y%1 #$% &*3% 3*X'323 *0&(-5#'(" 0*"1 *& #$%'- ; +(2"#%-5*-#& J37
*"1 3PL< 02# 1'))%-%"+%& 0%#Y%%" #$%'- M=F Y%-% 3(-% 5-("(2"+%1: =$*".%& )-(3 5(&'#',% #(
"%.*#',% *"./%& *-% 1'&5/*!%1 '" 53 02# A2&# ("% 5(&'#',% 0*"1 *# bbT "3 Y*& (0&%-,%1 )(- 5O<
Y'#$ #$'& +2-,% $*,'". #$% 0%&# )'# '" #$%(-%#'+*/ +*/+2/*#'("&: A++(-1'". #( #$% +*/+2/*#%1 &5%+#-*<
*&&'."3%"# 0%+(3%& %*&! 0%#Y%%" #$%&% %5'3%-&< Y$%-% c<ST4SS<4b{>4 %21%&3*"%&#-'.(/*+#("%
")"
+(--%&5("1& #( 5O *"1 c<ST4SS<4b{74%21%&3*"%&#-'.(/*+#("% +(--%&5("1& #( 53:
")#
")$
")%
")&
>%*+#'(" () */1%$!1%& 3Q *"1 3M /%# #( (0#*'" #Y( MF a& )-(3 %*+$ */1%$!1%< "*3%/!
+(35(2"1& 55\56 *"1 5L\54< -%&5%+#',%/!: A2#$(-& &2..%&# #$*# *// 5(&&'0/% %5'3%-& Y%-%
&!"#$%#'P%1< 02# #$(&% Y'#$ /(Y%&# !'%/1& +(2/1 "(# 0% 1%#%+#%1 12-'". #$% +$-(3*#(.-*5$'+
52-')'+*#'(" 5-(+%12-%&: '3'/*- &#-2+#2-*/ %/2+'1*#'(" Y*& +*--'%1 (2# *& '" #$% +*&%& () 37\53:
")'
")(
" )
"
" !
" "
=(35(2"1 55 Y*& (0#*'"%1 '" N^_ !'%/1 *& * 3'X#2-% () %5'3%-& *# =4by J%,'1%"+%1 0!
#$% 125/'+'#! () &'."*/& *# K@> &5%+#-*L 02# #$% 52-')'+*#'(" () #$%&% %5'3%-& 0! gVa= Y*&
5-(,%1 #( 0% 1'))'+2/#: g(Y%,%-< #$'& +(35(2"1 Y*& +("&'1%-%1 #( 0% SS; 12% #( #$% KGM %))%+#
(0&%-,%1 0%#Y%%" g4SN *"1 g4R J3$4/)" 9L: =(35(2"1 56 Y*& (0#*'"%1 '" f_ !'%/1 *"1 Y*&
*&&'."%1 *& #$% SS< +(2"#%-5*-#: H# '& "(#%Y(-#$! #$*# #$% $'.$%- !'%/1 (0#*'"%1 '" #$% &!"#$%&'& ()
SS; +(35(2"1& J55L */&( (++2--%1 Y'#$ MF a& 37\53: >%.*-1'". #$% *0&(/2#% +(")'.2-*#'(" ()
"
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 14 of 37
" #
" $
" %
56< #$% %X5%-'3%"#*/ +'-+2/*- 1'+$-('&3 &5%+#-23 &$(Y%1 * "%.*#',% 0*"1 *# bNU "3 *)#%- #$% -'&%
() * 5(&'#',% 0*"1 *# bSU "3: Z$'& )'".%-5-'"# '& +("&'&#%"# Y'#$ JSS<L4J=4by>L4MF a *& '# '&
(55(&'#% #( #$% +*/+2/*#%1 M=F &5%+#-23 () JSS<L4J=4by7L4MF a J3$4/)" =&L:
" &
" '
" (
"!)
"!
"!!
MF a& 5L *"1 54< 0(#$ (0#*'"%1 0! -%*+#'(" () 3M '" T_ *"1 f_ !'%/1< -%&5%+#',%/!< Y%-%
&203'##%1 #( #$%(-%#'+*/ M=F: Z$% -%&2/#& &$(Y #$*# #$% >4%5'3%-& Y%-% &%/%+#',%/! &!"#$%&'P%1:
Z$% %X5%-'3%"#*/ &5%+#-23 () 5L &$(Y%1 #Y( 3*X'323 5(&'#',% *0&(-5#'(" 0*"1& *# bUT "3 *"1
bNU "3 *"1 #$%&% *-% +("&'&#%"# Y'#$ #$% +*/+2/*#%1 &5%+#-23 )(- S<b< c<ST4JSS;L4Jby>L4MF a: H"
#$% +*&% () 54< ("/! ("% $'.$ 5(&'#',% 0*"1 *55%*-%1 *# bNT "3< &'3'/*- #( #$*# )(2"1 '" #$%
+*/+2/*#%1 &5%+#-23 () S<b< c<ST4JSS<L4Jby>L4MF a Y'#$ * 0*#$(+$-(3'+ %))%+#:
"!"
"!#
"!$
"!%
"!&
H" (-1%- #( +(35/%#% #$% &#21! *"1 +(35*-% #$% %))%+# () #$% *0&%"+% () =4SS\=4SN 1(20/%
(" #$% *+#','#!< #$% SS<SN41'$!1-(4MF a 5Q Y*& &!"#$%&'P%1 0! 1'-%+#/! *11'". #$% 02#%"(/'1%
)-*.3%"# #( */+($(/ 35: Z$% -%*+#'(" +("1'#'("& Y%-% #$% &*3% *& #$(&% 2&%1 )(- #$% &!"#$%&'& ()
MF a& 37\54 J3$4/)" 6&L: Z$2&< 35 Y*& #-%*#%1 Y'#$ 5(#*&&'23 0")0402#(X'1% *"1 0-(3'"*#%1
)2-*"("% #( .',% 5Q '" Tc_ !'%/1:
"!'
"!(
"")
""
""!
"""
""#
""$
""%
""&
""'
Z$% K@> &5%+#-* () 5Q Y%-% ,%-! &'3'/*- #( #$(&% () 5-%,'(2& MF a&< Y'#$ #$% &*3%
5*##%-" )(- #$% 02#%"(/'1% )-*.3%"# *"1 +$*".%& &5%+')'+*//! )(- g4SN *"1 =4SN: H" #$% *0&%"+% ()
#$% 1(20/% 0("1< #$% g4SN &'."*/ &$')#%1 #( $'.$%- )'%/1 *"1 Y*& (0&%-,%1 *& #Y( ?? *# k N:f] *"1
k N:Rf \ '" +("#-*&# Y'#$ MF a&< Y$%-% '# *55%*-%1 0%#Y%%" k R:Nf *"1 k ]:cf: Z$% /*+[ () *
1(20/% 0("1 '& */&( %,'1%"+%1 0! #$% *11'#'("*/ &'."*/ )(- g4SS Jk b:TNL< Y$'+$ '& *0&%"# )(-
MF a& 37\54: A" KGM %))%+# 0%#Y%%" g4SS *"1 g4] +(")'-3%1 #$% SS> &#%-%(+$%3'&#-! () 5Q
J3$4/)" 9L< Y$'/% #$% *0&(/2#% &#%-%(+$%3'&#-! *# =4b{ Y*& *"*/!P%1 0! M=F: Z$% %X5%-'3%"#*/
&5%+#-23 &$(Y%1 * 5(&'#',% 0*"1 *# bbU "3 *"1 * "%.*#',% 0*"1 *# b^U "3< Y$'+$ *-% +("&'&#%"#
Y'#$ #$% =4by> %5'3%- -*#$%- #$*" #$% =4by7 %5'3%-< Y$'+$ &$(Y%1 (55(&'#% 1%.-%%& J3$4/)" =.L:
Z$% %5'3%- *# =4b{ Y*& "(# (0&%-,%1 '" #$'& -%*+#'(": Z$'& -%&2/# &2..%&#& #$*# #$% =46{7 *11'#'("
() #$% 02#%"(/'1% -'". '& $'.$/! '35%1%1 0! &#%-'+ %))%+#&:
#
ACS Paragon Plus Environment

Page 15 of 37
Journal of Agricultural and Food Chemistry
""(
"#)
"#
"#!
"#"
"##
"#$
H" *11'#'(" #( MF a&< '" #$'& &#21! #$% 02#%"(/'1% -'". Y*& *11%1 #( +(35(2"1 M *"1 #$%
%5'3%-& Y%-% 52-')'%1 *"1 %,*/2*#%1 &%5*-*#%/! )(- #$% )'-&# #'3% J3$4/)" 6(L< &'"+% #$% %5'3%-& *#
=4by< ':%:< 3'X#2-% () 5MW57< (0#*'"%1 )-(3 M Y%-% 5-%,'(2&/! )(2"1 #( 0% 0'(*+#',%:c A &(/2#'("
() M '" 1-! Zg? Y*& *11%1 #( * 1-! -(2"140(##(3%1 )/*&[ Y'#$ +((/'". J'+% 0*#$L *"1 #$%
0-(3'"*#%1 )2-*"("% Jc %62',*/%"#&L Y*& *11%1: Z$% 0*&% K*g JN %62',*/%"#&L Y*& *11%1:
=(35(2"1& 5MW57 Y%-% (0#*'"%1 JNU_L */(". Y'#$ #$% 2"%X5%+#%1 0!5-(12+# 5P JS]_L *"1
2"-%*+#%1 &#*-#'". 3*#%-'*/ M JNR_L:
"#%
"#&
"#'
"#(
"$)
"$
"$!
H" *" %))(-# #( '35-(,% #$% !'%/1& () 5M\57< #$% 2&% () (#$%- 0*&%& #$*" K*g Y*& %,*/2*#%1
02# "("% () #$%3 &$(Y%1 #( 0% 3(-% )*,(-*0/%: G" 2&'". lg * !'%/1 () SN_ Y*& (0#*'"%1 )(- #$%
3'X#2-% 5MW57< c_ )(- #$% 3'X#2-% () #$%'- %5'3%-& *# =4SS *"1 ]U_ -%+(,%-%1 &#*-#'". 3*#%-'*/:
G" 2&'". #$% *)(-%3%"#'("%1 +("1'#'("& *"1 #-%*#'". M Y'#$ I2a'< 1'3%- 5P Y*& (0#*'"%1 '" ]_
!'%/1 *"1 5M (- 57 Y%-% "(# (0&%-,%1: '"+% ("/! K*g 5-(,'1%1 #$% #*-.%# +(35(2"1& '" .((1
!'%/1&< #$% *2#$(-& &2..%&# #$*# #$% &'P% () #$% +(2"#%-'(" Jl| } K*|}a'|L +(2/1 $'"1%- #$% -%*+#'("<
*"1 #$% &'P% () K*| %"+(2-*.% #$% -%*+#'(" 5*#$Y*!:
"$"
"$#
"$$
"$%
"$&
"$'
Z$% Sg *"1 SN= K@> &5%+#-* () %*+$ %5'3%- Y%-% &'3'/*- #( #$(&% () #$% 3'X#2-% -%5(-#%1
'" #$% /'#%-*#2-%< Y'#$ #$% %X+%5#'(" () g4SN< Y$'+$ .*,% * 32/#'5/%# *# k c:SU )(- 5M *"1 #Y( Y%//4
-%&(/,%1 ?? *# k N:f^ *"1 k N:^] )(- 57: Z$% 0("1'". () #$% 02#%"(/'1% -'". Y*& %,'1%"+%1 0! #$%
5-%&%"+% () &'."*/& )(- g4by Jk T:^c )(- 5M *"1 k T:^f )(- 57L< g4Ny Jk ]:^S )(- 5M *"1 k ]:^] )(-
57L *"1 g4Sz Jk S:fT )(- 5M *"1 k S:fR )(- 57L< Y$'+$ *-% &'3'/*- #( #$(&% '" #$% Sg K@> &5%+#-*
() 37\5Q 02# *-% *0&%"# )-(3 #$% &5%+#-23 () M:
"$(
"%)
"%
"%!
"%"
Z$% *0&(/2#% +(")'.2-*#'(" () =4by Y*& 1%#%-3'"%1 0! %/%+#-("'+ +'-+2/*- 1'+$-('&3: Z$%
%X5%-'3%"#*/ M=F &5%+#-23 () 5M &$(Y%1 * "%.*#',% 3'"'323 *# bcN "3 *"1 * 5(&'#',%
3*X'323 *# bSb "3< Y$'/% 57 .*,% * 5(&'#',% 3*X'323 *# bcT "3 *"1 * "%.*#',% 3'"'323 *#
bUT "3: Z$%&% %X5%-'3%"#*/ -%&2/#& *-% '" *.-%%3%"# Y'#$ #$% #$%(-%#'+*/ &5%+#-* *"1 5M Y*&
*&&'."%1 *& =4by7 Y$'/% 57 +(--%&5("1%1 #( #$% =4by> %5'3%- J3$4/)" =.L:
$
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 16 of 37
"%#
"%$
"%%
"%&
"%'
"%(
"&)
"&
"&!
"&"
"&#
"&$
"&%
"&&
"&'
?'"*//!< &5%+#-(&+(5'+ *"*/!&'& () #$% 2"%X5%+#%1 5-(12+# 5P +(")'-3%1 #$*# #$'& Y*& *"
%&#%- () M< Y$'+$ 3'.$# 0% )(-3%1 0! #$% (5%"'". () #$% 02#%"(/'1% -'". *)#%- #$% "2+/%(5$'/'+
&20&#'#2#'(" 12% #( #$% &#-("./! 0*&'+ +("1'#'("& 2&%1: Z$% 3(/%+2/*- )(-32/* 1%#%-3'"%1 0! @
S
Y*& =NTgcbG^ *"1 #$'& +(--%&5("1& #( #$% 1'3%-'+ +(35(2"1 5P: H" #$% g K@> &5%+#-23< *
62*-#%# *# k T:^^ J,'"!/ 5-(#("< g4SRL *"1 * 1(20/%# *# k b:U^ Jg4bUL '"1'+*#%1 #$% )(-3*#'(" () *
1'3%-: ZY( 3*A(- +/2%& Y%-% (0#*'"%1 (" *"*/!P'". #$% SN= &5%+#-23q #$%-% Y%-% #Y( %X#-* &'."*/&
)(- +*-0("!/ .-(25& Y$%" +(35*-%1 Y'#$ M Jk S]c:c *"1 k S]^:cL *"1 */3(&# *// () #$% &'."*/&
Y%-% 125/'+*#%1 Y$%" +(35*-%1 Y'#$ #$% (-'.'"*/ +(35(2"1< Y'#$ #$% %X+%5#'(" () #$% )(//(Y'".q
k S]c:c J=4S]L< k SbU:b J=4SRL< k Sc]:N J=4S^L< k S]^:c J=4SfL< k bU:R J=4bUL< *// () Y$'+$ Y%-%
"%Y &'."*/&: A// () #$%&% &'."*/& +(--%&5("1%1 #( #$% "%Y /'"%*- +$*'" +(""%+#%1 #( =4SN: A)#%- *
S
+*-%)2/ *"*/!&'& () #$% g K@> &'."*/&< '# Y*& )(2"1 #$*# 3(&# () #$%3 Y%-% #Y( (,%-/*55'".
&'."*/& #$*# '"#%.-*#%1 )(- 1(20/% #$% ,*/2% () #$% &'3'/*- &'."*/& () M: ?'"*//!< *" KGM %))%+# Y*&
(0&%-,%1 0%#Y%%" g4SR Jk T:^RL *"1 g4bU Jk b:URL< Y$'+$ %,'1%"+%1 #$%'- 5-(X'3'#! '" &5*+% *"1
+(")'-3%1 #$% ; +(")'.2-*#'(" () #$% =4SR\=4S^ 1(20/% 0("1 J3$4/)" 9L< #$2& +(")'-3'". #$%
&#-2+#2-% () +(35(2"1 5P:
"&(
"')
"'
"'!
"'"
"'#
"'$
"'%
"'&
"''
"'(
"()
*))C*>A& ,&&+ R&*CB=>DB)= XB)>,,>'H Z$% &!"#$%&'P%1 &#-'.(/*+#("% *"*/(.& J37\57L
*"1 #$% 1'3%- 5P Y%-% #%&#%1 '" #$% 0-((3-*5% &%%1 .%-3'"*#'(" 0'(*&&*!< Y$'+$ %,*/2*#%& #$%
*0'/'#! () +(35(2"1& #( &#'32/*#% #$% .%-3'"*#'(" () 5*-*&'#'+ 5/*"# &%%1&: Z$% &5%+'%& #%&#%1 Y%-%
1 )&*+,&< -1 (/*&'& *"1 -1 ()"'&0&: !"#$%#'+ &#-'.(/*+#("% 9>bc J3$4/)" 5L Y*& 2&%1 *& *
5(&'#',% +("#-(/ *"1 1%'("'P%1 &#%-'/% Y*#%- Y'#$ S_ ,Q, *+%#("% Y*& 2&%1 *& * "%.*#',% +("#-(/:
9>bc $*& * $'.$ .%-3'"*#'". *+#','#! (" &%%1& () #$%&% #$-%% &5%+'%& *"1 '# '& Y'1%/! 2&%1 *& *
-%)%-%"+% +("#-(/ '" #$'& *-%* () -%&%*-+$:b] Z$% 3*'" .(*/ () #$'& 0'(*&&*! Y*& #( (0#*'"
'")(-3*#'(" '" (-1%- #( &%/%+# #$% 0%&# +*"1'1*#%& )(- #$% 1%&'." () *.-(+$%3'+*/& #( #-%*#
0-((3-*5% '")%&#*#'("& (" +-(5& #$-(2.$ #$% $("%!5(# &#-*#%.!: Z$% -%&2/#& *-% -%5-%&%"#%1 '"
3$4/)" @ )(- * -*".% () +("+%"#-*#'("& )-(3 SU4c @ #( #$% 3'"'323 &'."')'+*"# 1(&% () %*+$
+(35(2"1 J25 #( SU4SU @L< *& #$% 3%*" 5%-+%"#*.% () &%%1& #$*# .%-3'"*#%1 '" %*+$ 5/*#%: Z$%
"%.*#',% +("#-(/ 1'1 "(# +*2&% &'."')'+*"# &5("#*"%(2& .%-3'"*#'(":
%
ACS Paragon Plus Environment

Page 17 of 37
Journal of Agricultural and Food Chemistry
"(
"(!
A// () #$% +(35(2"1& #%&#%1 Y%-% *+#',% (" 1 )&*+,& *"1 -1 (/*&'& *"1 #$% MF a&
37\5O *"1 55\54 Y%-% */&( &'."')'+*"#/! *+#',% (" -1 ()"'&0&:
"("
"(#
"($
"(%
"(&
"('
"((
#))
Z$% 5-()'/%& () *// () #$% #%&#%1 +(35(2"1& &$(Y%1 &'."')'+*"# *+#','#! *# *//
+("+%"#-*#'("& #%&#%1 (" 1 )&*+,& J3$4/)" @L: A# #$% $'.$%&# +("+%"#-*#'("< 5O< 53< 56\5Q< 57 *"1
5P &#'32/*#%1 #$% .%-3'"*#'(" () 3(-% #$*" ^U_ () &%%1&< Y'#$ 5%-+%"#*.%& () SUU_ *+$'%,%1 '"
&(3% +*&%&: =(35(2"1& 5O< 53< 56< 5L< 57 *"1 5P *-% "(#%Y(-#$! &'"+% #$% *+#','#! /%,%/& Y%-%
-%#*'"%1 *# #$% /(Y%&# +("+%"#-*#'("& *"1 Y%-% %,%" $'.$%- #$*" #$*# () #$% 5(&'#',% +("#-(/ 9>bc:
=*/+2/*#'(" () #$% M=TU .*,% ,*/2%& () /%&& #$*" SU4R @ J0&.#" 5L: Z$2&< #$%&% /*&# -%*1'/! (0#*'"%1
+(35(2"1& +(2/1 0% .-%*# *.-(+$%3'+*/& #( 5-%,%"# 1 )&*+,& 5%&#&< 0%'". * 0%##%- (5#'(" #$*"
9>bc '" #%-3& () (0#*'"'". (- *+#','#! /%,%/&:
#)
#)!
#)"
#)#
#)$
?-(3 * &#-2+#2-*/ 5('"# () ,'%Y -%.*-1'". ;Q< +(")'.2-*#'("< 0%##%- &#'32/*#'(" Y*&
5-(,'1%1 0! SS<4MF a& J5O< 53 *"1 56L Y$%" +(35*-%1 Y'#$ SS;4MF a& J37< 3P *"1 55L (" 1
)&*+,& &%%1&< Y'#$ 1'))%-%"+%& *& .-%*# *& ]U_ () &%%1 .%-3'"*#'(": H" #$% +*&% () MF a& Y'#$
#Y( 1(20/% 0("1& *# -'". A J5L *"1 54L< #$% SS< &#%-%('&(3%- J54L $*1 &/'.$#/! /(Y%- *+#','#! *#
#$% #Y( /(Y%&# +("+%"#-*#'("&< Y$'/% 5L -%#*'"%1 * $'.$ RR_ *+#','#! *# SU4R @:
#)%
#)&
#)'
#)(
# )
#
G" +(35*-'". &#%-%(+$%3'&#-! *# =4by< +(35(2"1 57 J=4by>L< Y$'+$ $*& #$% &*3%
&#%-%(+$%3'&#-! *& &#-'.(/< Y*& 3(-% *+#',% #$*" '#& %5'3%- 5M J=4by7L: '."')'+*"# 1'))%-%"+%&
Y%-% "(# (0&%-,%1 '" #$% +*&%& () MF a& 37\53: >%.*-1'". #$% 5-%&%"+% () *" %"(/ %#$%- 0("1<
#$% *0&%"+% () * 1(20/% 0("1 0%#Y%%" =4SS *"1 =4SN 1'1 "(# &%%3 #( $*,% * &'."')'+*"# %))%+#
J&%% 37\53 ,& 5QL< *& 5Q -%*+$%1 f^_ .%-3'"*#'(" *# #$% $'.$%&# +("+%"#-*#'("< */#$(2.$ #$'&
5%-+%"#*.% 1%+-%*&%1 -*5'1/! *# /(Y%- +("+%"#-*#'("&:
# !
# "
# #
# $
# %
A// () #$% +(35(2"1& &#'32/*#%1 #$% .%-3'"*#'(" () -1 (/*&'& &%%1&: H" 5*-#'+2/*-<
MF a& 37\5Q Y%-% $'.$/! %))%+#',% '" &#'32/*#'". &%%1& () #$'& 5-(0/%3*#'+ &5%+'%&< Y'#$
&#'32/*#'(" ,*/2%& (,%- fU_ )(- 3(&# () #$% $'.$%- +("+%"#-*#'("&: A# SU4T @< *// MF a *"*/(.&
J37\5QL -%*+$%1 *# /%*&# RU_ .%-3'"*#'(": Z$%'- 5-()'/%& *-% &'3'/*- (- %,%" 0%##%- #$*" #$*# ()
9>bc< &( #$%&% -%*1'/! (0#*'"%1 &#-'.(/*+#("% *"*/(.& +(2/1 0% .-%*# *.-(+$%3'+*/& #( 5-%,%"# -1
&
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 18 of 37
# &
# '
# (
#!)
#!
#!!
#!"
#!#
#!$
(/*&'& 5%&#&< 0%'". * 0%##%- (5#'(" #$*" 9>bc '" #%-3& () (0#*'"'". (- *+#','#! /%,%/&: M&5%+'*//!<
+(35(2"1& 3P *"1 5L -%#*'"%1 &#'32/*#(-! *+#','#! %,%" *# /(Y%- 1(&%&< Y'#$ R^_ *"1 ^T_
.%-3'"*#%1 &%%1& -%&5%+#',%/! *# SU4R @ *"1 &'."')'+*"# *+#','#! *# SU4^ @< &( 0(#$ +(2/1 0% #$%
3(&# &2'#*0/% *.-(+$%3'+*/ +(35(2"1&< *& #$%! +*" 0% *55/'%1 *# /(Y%- 1(&%&< -%12+'". #$%
%",'-("3%"#*/ '35*+#: 9%-3'"*#'(" Y*& "(# 1%#%+#%1 )(- 54 *# #$% $'.$%&# +("+%"#-*#'("< Y$'/%
,*/2%& (,%- fU_ Y%-% (0&%-,%1 *# SU4T @: Z$'& 5$%"(3%"(3 $*& 0%%" (0&%-,%1 5-%,'(2&/!Sf *"1
+*" 0% %X5/*'"%1 0! #$% 5$!#(#(X'+'+'#! () 54 (" -1 (/*&'& *# $'.$ 1(&%& J3$4/)", @ *"1 AL:
F'$!1-(49Ma& J5M\57L *"1< '" 5*-#'+2/*-< #$% 1'3%- 5P */&( &$(Y%1 &'."')'+*"# *+#','#! *# #$% #Y(
$'.$%&# +("+%"#-*#'("&:
#!%
#!&
#!'
#!(
#")
#"
#"!
#""
#"#
>%.*-1'". #$% &#%-%(+$%3'&#-! () #$% %"(/ %#$%- 0("1< #$% (55(&'#% #-%"1 #( 1 )&*+,&
Y*& )(2"1 '" -1 (/*&'&< Y'#$ #$% SS;4MF a& J37< 3P< 55< 5LL 0%'". 3(-% *+#',% #$*" #$% SS<4
MF a J5O< 53< 56< 54L &#%-%('&(3%-&< %&5%+'*//! *# /(Y%- +("+%"#-*#'("&: A& )*- *& #$% (-'%"#*#'("
() =4by '& +("+%-"%1< #$% 5-()'/%& )(- 37\53 &$(Y #$*# #$% =4by7 (-'%"#*#'(" J3P *"1 53L '& 0%##%-
#$*" > J37 *"1 5OL< %&5%+'*//! *# #$% /(Y%&# +("+%"#-*#'("&: H" )*+#< +(35(2"1 3P -%#*'"%1 * ,*/2%
() R^_ *+#','#! *# SU4R @< Y$'/% '#& %5'3%- 37 .*,% * ,*/2% () ("/! cN_: '."')'+*"# 1'))%-%"+%&
Y%-% "(# (0&%-,%1 0%#Y%%" #$% #Y( 1'$!1-(49Ma %5'3%-& J5M\57L< */#$(2.$ #$%'- *+#','#! /%,%/&
Y%-% /(Y%- #$*" #$(&% () #$% MF a& #%&#%1: >%.*-1'". #$% %"(/ %#$%- 0("1< #$% *0&%"+% () * 1(20/%
0("1 J5QL 1'1 "(# /%*1 #( * &'."')'+*"# *+#','#! 1%+-%*&% Y$%" +(35*-%1 Y'#$ +(35(2"1& 37\53:
#"$
#"%
#"&
%%1& () -1 ()"'&0& $*,% 5-(,%" #( 0% $'.$/! &%/%+#',% #( +(35(2"1& #$*# &#'32/*#% #$%'-
.%-3'"*#'("< *& "2// (- ,%-! /(Y 5%-+%"#*.%& () .%-3'"*#%1 &%%1& Y%-% (0#*'"%1 '" 5-%,'(2&
&#21'%&:bb<bc<bR
#"'
#"(
##)
##
##!
##"
Z$% -%&2/#& 5-%&%"#%1 '" 3$4/)" @ &$(Y #$*# "%*-/! *// MF a& J37\5QL &#'32/*#%1
.%-3'"*#'(" () -1 ()"'&0& &'."')'+*"#/! *# #$% $'.$%&# +("+%"#-*#'(": H# '& Y(-#$ $'.$/'.$#'".
+(35(2"1& 55 *"1 54 *& #$%&% *-% #$% ("/! %X*35/%& #$*# &$(Y%1 &'."')'+*"# *+#','#! *# SU4T @
JcR *"1 cT_< -%&5%+#',%/!L: =(35(2"1& 5Q\5P< Y$'+$ /*+[ #$% =4SS\=4SN 1(20/% 0("1<
5-%&%"#%1 "2// .%-3'"*#'(" )(- #$'& &5%+'%&< #$2& 1%3("&#-*#'". #$% +-'#'+*/ -(/% () #$% %"(/ %#$%-
&!&#%3 '" #$% 3%+$*"'&3& '",(/,%1 '" #$'& 5*-*&'#% -%+(."'#'(" )(- .%-3'"*#'(": Z$% ;Q<
'
ACS Paragon Plus Environment

Page 19 of 37
Journal of Agricultural and Food Chemistry
###
##$
##%
##&
+(")(-3*#'(" () #$% %"(/ %#$%- 0("1< *& Y%// *& #$% >Q7 (-'%"#*#'(" () =4by< 1'1 "(# *55%*- #( 0%
+-'#'+*/ )*+#(-& #( .%"%-*#% &'."')'+*"# 1'))%-%"+%& '" *+#','#! 5-()'/%&< Y$%-%*& 2"&*#2-*#'(" () -'".
A /%1 #( *" '35-(,%3%"# '" *+#','#! '" #$% +*&%& () 55 *"1 54< Y$'+$ *-% 1%-',*#',%& () 6 *"1 7<
-%&5%+#',%/!< Y$%" +(35*-%1 Y'#$ 37\53< Y$'+$ *-% 1%-',*#',%& () 5:
##'
##(
#$)
#$
#$!
#$"
#$#
#$$
#$%
#$&
#$'
#$(
#%)
#%
#%!
#%"
#%#
#%$
?'"*//!< #$% *+#','#! () MF a& J3$4/)", 6.L Y'// 0% +(35*-%1 Y'#$ #$-%% () #$% 3(&#
-%/%,*"# "*#2-*/ &#-'.(/*+#("%& #$*# *-% .%-3'"*#'(" &#'32/*"#&< "*3%/! &#-'.(/< (-(0*"+$(/ *"1
&(-.(/*+#("%:b^ Z$% %"(/ %#$%- 0("1 '" #$%&% 3(/%+2/%& $*& *" < .%(3%#-! *"1 #$% +(")'.2-*#'("
() =4by '& >: Z$2&< '# '& -%*&("*0/% #( +("&'1%- #$*# #$% 3(&# *+#',% +(35(2"1& Y(2/1 $*,% #$%&%
'&(3%-'+ )%*#2-%&: Z$% 3(/%+2/%& &#21'%1 '" #$% 0'(*&&*! -%5(-#%1 $%-%'" *//(Y%1 2& #( %,*/2*#%
Y$%#$%- 1'))%-%"# '&(3%-'&3 #( #$*# () "*#2-*/ &#-'.(/*+#("%& Y(2/1 5-(,'1% * $'.$%- &#'32/*#'("
*+#','#! (" &%%1 .%-3'"*#'(": MF a& 5O *"1 54 $*,% #$% &*3% &#%-%(+$%3'&#-! *& "*#2-*/
&#-'.(/*+#("%&: ?(- 1 )&*+,&< +(35(2"1 5O Y*& #$% 3(&# *+#',% () #$% MF a& &!"#$%&'P%1 )-(3
~4+!+/(+(&#2"(/'1% J37\53L< Y$'+$ ,%-')'%& #$% *)(-%3%"#'("%1 $!5(#$%&'&: g(Y%,%-<
2"&*#2-*#'(" *# -'".4A &%%3& #( 5/*! * [%! -(/%< *& +(35(2"1 5L &$(Y& $'.$%- *+#','#! #$*" '#&
&#%-%('&(3%- 54: MF a& 5O *"1 54 *-% #$% 3(&# *+#',% +(35(2"1& )(- -1 (/*&'& *# #$% $'.$%&#
+("+%"#-*#'(" #%&#%1 Y$%" +(35*-%1 Y'#$ #$% 3(/%+2/%& Y'#$ Y$'+$ #$%! &$*-% #$% &*3% -'".4A<
Y'#$ #$% *11'#'("*/ *1,*"#*.% #$*# 54 &$(Y& * 5$!#(#(X'+ %))%+#: H# '& -%3*-[*0/% #$*# 3P< Y$'+$
$*& #$% (55(&'#% &#%-%(+$%3'&#-! #( #$% "*#2-*/ &#-'.(/*+#("%&< '& ("% () #$% 3(&# *+#',% +(35(2"1&
#%&#%1: H" #$% +*&% () -1 ()"'&0&< +(35(2"1 54 $*& *" '35-(,%1 5-()'/% Y$%" +(35*-%1 #( '#&
*"*/(. 5L: g(Y%,%-< +(35(2"1 5O &$(Y%1 ,%-! &'3'/*- -%&2/#& #( 37 *"1 3P: Z$2&< '# $*& 0%%"
&$(Y" #$*# */#%-"*#',% &#%-%(+$%3'+*/ )%*#2-%& Y$%" +(35*-%1 #( "*#2-*/ &#-'.(/*+#("%& *-% */&(
+*5*0/% () .%"%-*#'". &'3'/*- 5-()'/%& )(- -1 ()"'&0& .%-3'"*#'(":
#%%
#%&
#%'
#%(
#&)
Z$% *+#','#! 5-()'/%& )-(3 #$% 0'(*&&*! /%1 2& #( +("+/21% #$*# 1'))%-%"# &#-2+#2-*/ )%*#2-%&
+*" .',% 0%##%- -%&2/#& 1%5%"1'". (" #$% 5*-*&'#'+ &5%+'%&q (" 1 )&*+,& *"1 -1 (/*&'& #$%
&#%-%(+$%3'&#-! () #$% %"(/ %#$%- 0("1 %X5/*'"& 1'))%-%"+%& '" *+#','#!< Y$'/% -1 (/*&'& 5-()'/%&
Y%-% */&( *))%+#%1 0! #$% 5-%&%"+% () %21%&3*"(/'1% (- .2*'*"(/'1% &#-2+#2-%&< Y'#$ 0%##%- 5-()'/%&
(0#*'"%1 )(- %21%&3*"(/'1% 1%-',*#',%&: H" #$% +*&% () -1 ()"'&0&< #$% /*+[ () *" %"(/ %#$%- 0("1
(
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 20 of 37
#&
#&!
#&"
#&#
'" #$% &#-'.(/*+#("% *"*/(.& /%1 #( #$% #(#*/ *0&%"+% () *+#','#!: Z$% 2"&*#2-*#'(" *# -'". A ()
MF a& *))%+#%1 #$% *+#','#! )(- #$% #$-%% &5%+'%& #%&#%1: Z$% 0%&# +(35(2"1& #( &#'32/*#% #$%
.%-3'"*#'(" () 1 )&*+,& *-% 5O< 53< 56< 5L< 57 *"1 5Pt '" #$% +*&% () -1 (/*&'& #$%! *-% 3P *"1
5Lt Y$'/% #$% 0%&# )(- -1 ()"'&0& *-% 55 *"1 54:
#&$
#&%
#&&
#&'
#&(
#')
#'
#'!
#'"
#'#
#'$
#'%
#'&
H" +("+/2&'("< #$% $!5(#$%&'& (" Y$'+$ #$'& Y(-[ Y*& 0*&%1 $*& 0%%" ,%-')'%1: K%Y
&#-'.(/*+#("% *"*/(.& 0*&%1 (" "*#2-*/ 5-(12+#& Y%-% &!"#$%&'P%1 *"1 #$% 3%#$(1 #( (0#*'" #$%
&#-'.(/*+#("%& '& 32+$ 3(-% %))'+'%"# #$*" '&(/*#'(" )-(3 5/*"# 3*#%-'*/< Y$'+$ -%62'-%& #$(2&*"1&
() 5/*"#& #( (0#*'" &%,%-*/ 3'+-(.-*3& () &#-'.(/*+#("%& &2+$ *& &#-'.(/ (- &(-.(/*+#("%:Sb G2-
3%#$(1 *//(Y& #$% &!"#$%&'& () &#-'.(/*+#("%& Y'#$ ./(0*/ !'%/1& 25 #( ^_< #$% &#*-#'". 3*#%-'*/
+*" 0% '&(/*#%1 (" * 32/#'.-*3 &+*/% *"1 ("/! N\] )*+'/% &#%5& *-% -%62'-%1: Z$% "%Y +(35(2"1&
&#'32/*#% #$% .%-3'"*#'(" () 5*-*&'#'+ Y%%1& *"1 #$%! *-% ,%-! *+#',% *"1 +(",%"'%"# )(- 2&% *&
/%*1& '" 5-%,%"#',% $%-0'+'1%& )(- #$% $("%!5(# &#-*#%.!: Z$% *+$'%,%3%"# () $'.$ *+#','#! 5-()'/%&
*# #$% /(Y%&# +("+%"#-*#'("& *))'-3%1 #$*# ("/! &3*// 1(&%& () +(35(2"1& Y(2/1 0% -%62'-%1 '"
$%-0'+'1% )(-32/*#'("&: =(35(2"1& Y'#$ 1'))%-%"# &#%-%(+$%3'+*/ )%*#2-%& #( #$% "*#2-*/
&#-'.(/*+#("%& &$(Y%1 0%##%- *+#','#! 5-()'/%& '" &(3% +*&%& #$*" #$(&% Y'#$ #$% &*3%
&#%-%(+$%3'&#-!: Z$2&< &#-2+#2-*/ )%*#2-%& 32&# 0% +("&'1%-%1 #( &%/%+# #$% 0%&# +*"1'1*#%& )(- %*+$
5*-*&'#'+ &5%+'%& #%&#%1:
#''
#'(
!2EE0#"./< ./Y0#8A".0/ 19!$#.E".0/
#()
#(
255(-#'". H")(-3*#'(" A,*'/*0/%q ÄSg *"1 SN=K@> () &!"#$%&'P%1 +(35(2"1&Å: Z$'& 3*#%-'*/
'& *,*'/*0/% )-%% () +$*-.% ,'* H"#%-"%# *# $##5qQQ520&:*+&:(-.
#(!
#("
#(#
#($
A2";0# ./Y0#8A".0/
$)**&,A)=+B=R AGDI)*
EM\3*'/q )*3*+'*&Ç2+*:%&: Z%/q |Nc\fT\]US]NRU:
YG=+B=R
!)
ACS Paragon Plus Environment

Page 21 of 37
Journal of Agricultural and Food Chemistry
#(%
#(&
A// &'32/*#'("& Y%-% 5%-)(-3%1 2&'". +(352#*#'("*/ )*+'/'#'%& )-(3 d %-,'+'( 1%
25%-+(352#*+'É" () Ñ-%* 1% '&#%3*& 1% H")(-3*+'É"e () #$% O"',%-&'#! () =W1'P:
#('
#((
Z$'& -%&%*-+$ Y*& &255(-#%1 0! #$% d@'"'&#%-'( 1% M+("(3B*< H"12&#-'* ! =(35%#'#','1*1e
J@HKMH=GL< 5*'"< V-(A%+# A9abUSR4^^4U^N4>:
$))
$)
?:7:>:@: #$*"[& #$% O"',%-&'#! () =W1'P )(- 5-%1(+#(-*/ &255(-# 2"1%- .-*"# bUS^4UUfQVOQMVH?4
?VH4=ZQ=V:
$)!
$)"
/)D&,
Z$% *2#$(-& 1%+/*-% "( +(35%#'". )'"*"+'*/ '"#%-%&#:
!
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 22 of 37
$)#
$)$
#9Y9#9/$9!
* +
a% =(--%< D:t >%'0%/< =:t 9'0(#4a%+/%-+< : F%,%/(53%"# () @'+-(&*#%//'#% @*-[%-& '" #$%
I-*"+$%1 I-((3-*5% !"#$%&'(!" >&*+,& a: JV(3%/L *"1 M,'1%"+% )(- g(&#4A&&(+'*#%1
9%"%#'+ F',%-.%"+%: B'01 C1 D+#1 7($1 5O3L< ST JSL< ffc\SUUb:
$##5&qQQ1(':(-.QSU:NNfUQ'A3&STUSUffc:
$)%
$)&
$)'
$)(
$ )
$
$ !
JbL
h*".< =:t Ö2< a:t ;$*".< K:t H&/*3< ?:t (".< `:t g2< a:t a'2< F:t Ö'%< Ö:t ;$(2< `:
'Z>Ai4I*&%1 V-(#%(3'+& () 2")/(Y%- =2/#',*-& F'))%-'". '" >%&'&#*"+% #( V*-*&'#'+
`%%1
$##5&qQQ1(':(-.QSU:SUUbQ53'+:bUSRUUUUf:
>20'*/%&< F:t ?%-"W"1%P A5*-'+'(< @: H""(,*#'("& '" V*-*&'#'+ `%%1& @*"*.%3%"# '"
a%.23% =-(5&: >%,'%Y: A4)+'1 7/,0&$'1 E"F1 5O35< Nb JbL< cNN\cNf:
-)+.&'(!"
:/*&'&:
)+0"+*$(,
5O3M<
SR
JSN\ScL<
S\TS:
$ "
$ #
$ $
JNL
JcL
A
$##5&qQQ1(':(-.QSU:SUURQ&SNTfN4USS4UUcT4X:
$ %
$ &
$ '
$ (
@*+B*&< ?: A:t 9*-+B*4FB*P< @: F:t VC-%P4F%4a262%< A:t >20'*/%&< F:t 9*/'"1(< 7: =: 9:
K%Y =$%3'+*/ =/2%& )(- I-((3-*5%4 2")/(Y%- g(&# 4 V*-*&'#% H"#%-*+#'("&q !"#$%&'& ()
92*'*"%&#-'.(/*+#("%&: C1 A4)$(1 G++? :!"*1 5OOP< TR JSNL< T^TN\T^]c:
$##5&qQQ1(':(-.QSU:SUbSQA)fUU^RUA:
$!)
$!
$!!
JTL
J]L
JRL
I-(([%&< 9:t Z*$%-'5(2-< ?:t Z!"%-< `: M: Z$% =("#-'02#'(" () 9/!5$(&*#% #( A.-'+2/#2-%
*"1 V(#%"#'*/ H35*+# () >%&#-'+#'("& (" O&% *# #$% 9/(0*/ a%,%/: HD :)+%1 G++? 5O3M< ^
JcL< bS]\bb^: $##5&qQQ1(':(-.QSU:SU^UQbS]cT]f^:bUSR:SNfU]NR:
$!"
$!#
$!$
='33'"(< A:t @*&'< @:t >20'*/%&< F:t M,'1%"#%< A:t ?%-"W"1%P4A5*-'+'(< @: A//%/(5*#$!
)(- V*-*&'#'+ V/*"# @*"*.%3%"#: I&01 )+?1 :+**/': 5O37< SN JNL< b^f\bfc:
$##5&qQQ1(':(-.QSU:SSRRQSfNcTR^XS^USNUUNUR:
$!%
$!&
$!'
Ö2< 7:t 3'#$< :t 3'#$< 9:t `*".< `:t a'< h: 9/!5$(&*#% =("#*3'"*#'(" '" 9-*'"& *"1
?((1&q
A"
G,%-,'%Y:
G++?
:+'0)+#
5O3P<
SU]
J72"%L:
$##5&qQQ1(':(-.QSU:SUS]QA:)((1+("#:bUSf:SU]RSU:
!!
ACS Paragon Plus Environment

Page 23 of 37
Journal of Agricultural and Food Chemistry
$!(
$")
J^L
JfL
g%1'"< V: A: K%Y =("+%5#& *"1 Z-%"1& '" V%&#'+'1% =$%3'&#-!: C1 A4)$(1 G++? :!"*1
3P75< NU JbL< bUS\bST: $##5&qQQ1(':(-.QSU:SUbSQA)UUSSU*UUS:
$"
$"!
$""
;Y*"%"02-.< I:t @Y*[*0([(< A: :t l*""*"< =: 2'+'1*/ 9%-3'"*#'(" )(- V*-*&'#'+
`%%1
=("#-(/:
",0
D&'&41
7($1
5O3Q<
Rb
JSSL<
bUS]\bUbT:
$##5&qQQ1(':(-.QSU:SUUbQ5&:cbbb:
$"#
$"$
$"%
JSUL
JSSL
JSbL
JSNL
I%&&%-%-< A:t V2%+$4V*.Ü&< D:t l'%)%-< V:t 9(3%P4>(/1*"< D:t 7*2"%*2< A:t >(!< :t
V(-#*'&< 7:4=:t >(2X< =:t IC+*-1< 9:t CA*/("4F%/3*&< K: #-'.(/*+#("%& #'32/*#%
A-02&+2/*- @!+(--$'P*/ ?2".' 0! A+#',*#'". @'#(+$("1-'*: J+7 K$+# 5OOQ< c JRL< %bb]:
$"&
$"'
$"(
=*-1(&(< =:t >2!#%-4 5'-*< =:t I(2Y3%%&#%-< g: 7: #-'.(/*+#("%& *"1 >((# H")%&#*#'("
0! V/*"#4V*-*&'#'+ 70)$4&< -)+.&'(!" *"1 !"#$%&'(!" 55: #&'0 7($1 5O33< S^U JNL< cSc\
cbU: $##5&qQQ1(':(-.QSU:SUS]QA:5/*"#&+':bUSU:SS:UUR:
$#)
$#
$#!
g235$-%!< A: 7:t 9*/&#%-< A: @:t I%*/%< @: g: #-'.(/*+#("%& '" =$%3'+*/ M+(/(.!q
`*&#% V-(12+#& (- D'#*/ A//%/(+$%3'+*/&á I&01 )+?1 >"%1 5OOQ< bN JcL< Tfb\]Sc:
$##5&qQQ1(':(-.QSU:SUNfQ0TSbRR]*:
$#"
$##
$#$
$#%
a*+$'*< @:t `(/)< g: =:t F% @%&3*%[%-< A: !"#$%&'& () #-'.(/*+#("%& A"*/(.2%& 0!
H"#-*3(/%+2/*- Äb|bÅ =!+/(*11'#'(" () l%#%"%4H3'"'23 */#& #( G/%)'"& *"1 Z$%'-
A+#','#! (" -)+.&'(!" :/*&'& %%1&: K$++)4&'$( D"?1 :!"*1 J"001 5O3L< bc JfL< bSbN\
bSb^: $##5&qQQ1(':(-.QSU:SUS]QA:03+/:bUSc:UN:Ucc:
$#&
$#'
$#(
$$)
JScL
JSTL
a(30*-1'< =:t A-#2&(< M:t 9-*"1'< M:t a(//'< @:t 5'-*[!&< ?:t V-'(/*< M:t V-*"1'< =: >%+%"#
A1,*"+%& '" #$% !"#$%&'& () A"*/(.2%& () V$!#($(-3("%& #-'.(/*+#("%& Y'#$ >'".4
=/(&'". @%#*#$%&'& *& * l%! #%5: -)41 K$+*+#1 :!"*1 5O3M< SR J+L< ^bS^\^bNS:
$##5&qQQ1(':(-.QSU:SUNfQ=RGIUSfSR=:
$$
$$!
$$"
@Y*[*0([(< A: :t ;Y*"%"02-.< I: #-'.(/*+#("% A"*/(.2%& Y'#$ * F4>'". @(1')'%1 *#
=4b:
</)+%"&'
C1
-)41
:!"*1
5O3Q<
JbSL<
NcfT\Ncff:
$##5&qQQ1(':(-.QSU:SUUbQ%A(+:bUS]UUTR]:
!"
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 24 of 37
$$#
$$$
$$%
JS]L
JSRL
Z*"*[*< @:t 2.'3(#(< h:t l2&%< @:t Z*['[*Y*< g: !"#$%&'& () R4GX(4T4F%(X!&#-'.(/<
* R4GX!.%"*#%1 #-'.(/*+#("% A"*/(.: K$+,($1 K$+0"(!'+#1 K$+(!"*1 5O36< RR JcL< ^Nb\
^NT: $##5&qQQ1(':(-.QSU:SbRSQ000:SNUUbU:
$$&
$$'
$$(
$%)
=*/*< A:t @(/'"'//(< 7: @: 9:t ?%-"W"1%P4A5*-'+'(< @:t A!2&(< 7:t Ñ/,*-%P< 7: A:t >20'*/%&<
F:t @*+B*&< ?: A: =(35/%X*#'(" () %&62'#%-5%"% a*+#("%& Y'#$ =!+/(1%X#-'"&q !"#$%&'&
*"1 M))%+#& (" Z$%'- A+#','#'%& (" V*-*&'#'+ `%%1&: -)41 K$+*+#1 :!"*1 5O3M< ST JNSL<
]TUU\]TSU: $##5&qQQ1(':(-.QSU:SUNfQ+R(0USNfc*:
$%
$%!
$%"
JS^L
JSfL
V%-%'-*< >: 9:t =*/*< A:t ?%-"W"1%P A5*-'+'(< @:t @(/'"'//(< 7: @:t I(*,%"#2-*< @: A:t
@*+B*&< ?: A: 9'00%-%//'+ *"1 l*2-%"('+ g!0-'1 #-'.(/*+#("% @'3'+& )(- %%1
9%-3'"*#'(" () V*-*&'#'+ `%%1&: ",0 D&'&41 7($1 5O3M< RN< bTbfrbTNR:
$%#
$%$
$%%
$%&
=*/*< A:t ;(--'//*< 7: 9:t >'*/< =:t @(/'"'//(< 7: @: 9:t D*-%/*< >: @:t @*+B*&< ?: A: M*&!
A++%&& #( A/[(X!< A3'"(< =*-0*3(!/< g!1-(X!< *"1 Z$'(/ F%-',*#',%& () %&62'#%-5%"%
a*+#("%& *"1 M,*/2*#'(" () Z$%'- I'(*+#','#! (" V*-*&'#'+ `%%1&: C1 A4)$(1 G++? :!"*1
5O3P< ]R JN^L< SUR]c\SURRN: $##5&qQQ1(':(-.QSU:SUbSQ*+&:A*)+:f0UNUf^:
$%'
$%(
$&)
$&
JbUL
AP*-[%"< >:t 92%--*< ?: @:t @(-%"(4F(-*1(< ?: 7:t 7(-.%< ;: F:t @*&&*"%#< 9: @:
20&#'#2%"# M))%+#& '" #$% Z-*"&*""2/*- =!+/'P*#'("& () 9%-3*+-*"%&: !"#$%&'& () ]4M5'4
=(&#2"(/'1% *"1 ?',% K*#2-*/ #%'-*+#'"(/'1%&: L"0)&!"?)+' 5OO7< ]c Jc^L< SU^f]\SUfUT:
$##5&qQQ1(':(-.QSU:SUS]QA:#%#:bUU^:Uf:USR:
$&!
$&"
JbSL
JbbL
l-*2#< a:t @2%&< >:t '34 '3< @: %&62'#%-5%"% a*+#("%& *"1 N4I%"P!/5$#$*/'1%& )-(3
G)/##&'$& D/,($(+#&: !M0+(!"*$,0)M 3PPL< NR JTL< SNNR\SNc]:
$&#
$&$
$&%
$&&
;(--'//*< 7: 9:t >'*/< =:t D*-%/*< >: @:t @(/'"'//(< 7: @: 9:t @*+B*&< ?: A: ?*+'/% !"#$%&'&
() A"$!1-(A21*'+'" *"1 SS<SN4F%$!1-(*"$!1-(A21*'+'"< ZY( M21%&3*"(/'1%4 [%/%#("
a*+#("%& Y'#$ V(#%"#'*/ A//%/(5*#$'+ A+#','#!: !M0+(!"*1 J"001 5O3P< NS J?%0-2*-!L<
bbf\bN]: $##5&qQQ1(':(-.QSU:SUS]QA:5$!#(/:bUSf:Uc:USc:
!#
ACS Paragon Plus Environment

Page 25 of 37
Journal of Agricultural and Food Chemistry
$&'
$&(
$')
$'
JbNL
JbcL
9("P*/%P =(//*1(< H:t 9(3%P @*1%-(< 7:t @*-#'"%P @*&&*"%#< 9:t >(1-'.2%P a2'&< ?:
V*-#'*/ !"#$%&'& () %&62'#%-5%"% a*+#("%&q
A
>(2#% #( R<SS4M"%4SN4
g!1-(X!%21%&3*"(/'1%&: C1 -)41 :!"*1 3PP3< T] JSSL< NT^R\NTfS:
$##5&qQQ1(':(-.QSU:SUbSQA(UUUSS*UbT:
$'!
$'"
$'#
$'$
=*/*< A:t 9$((-*!< l:t ?%-"W"1%P4A5*-'+'(< @:t @(/'"'//(< 7: @:t 9*/'"1(< 7: =:t
>20'*/%&< F:t @*+B*&< ?: A: V$#$*/'3'1%4F%-',%1 #-'.(/*+#("% @'3'+& *& 9%-3'"*#'".
A.%"#& )(- %%1& () V*-*&'#'+ `%%1&: ",0 D&'&41 7($1 5O3Q< Rb JSSL< bU]f\bU^S:
$##5&qQQ1(':(-.QSU:SUUbQ5&:cNbN:
$'%
$'&
$''
JbTL
Jb]L
`*,-'"< a:t D'*/*< 7: =/%*" *"1 M))'+'%"# GX'1*#'(" () g(3(*//!/'+ *"1 g(3(5-(5*-.!/'+
A/+($(/& '"#( ~<à4O"&*#2-*#%1 A/1%$!1%& 0! #$% F%&&4@*-#'" V%-'(1'"*"%: 7M'0!",$,
5OO5< ] JNL< Nb]\NNU: $##5&qQQ1(':(-.QSU:SUTTQ&4bUUb4bUUbf:
$'(
$()
$(
$(!
@*/'[< g:t >2#A%&< ?: V: 7: Z:t ;Y*"%"02-.< I: A K%Y M))'+'%"# !"#$%&'& () 9>bc *"1
F'3%#$!/ A4>'". A"*/(.2%&< 9%-3'"*#'". A.%"#& )(- %%1& () #$% V*-*&'#'+ `%%1&
70)$4& *"1 -)+.&'(!" 55: L"0)&!"?)+' 5O3O< ]] JNTL< RSf^\RbUN:
$##5&qQQ1(':(-.QSU:SUS]QA:#%#:bUSU:U]:URb:
$("
$(#
$($
$(%
JbRL
Jb^L
>'*/< =:t 9É3%P< M:t D*-%/*< >: @:t @(/'"'//(< 7: @: 9:t @*+B*&< ?: A: M+(/(.'+*/
>%/%,*"+% () #$% @*A(- A//%/(+$%3'+*/& '" JM(+%"),$(+' <,(/#"'0/* >((#& *"1
MX21*#%&:
C1
A4)$(1
G++?
:!"*1
5O37<
]]
JS^L<
c]N^\c]cc:
$##5&qQQ1(':(-.QSU:SUbSQ*+&:A*)+:^0USTUS:
$(&
$('
$((
%))
@*#2&(,*< >:t >*"'< l:t D%-&#*55%"< ?: `: A:t ?-*"&&%"< @: =: >:t I%*/%< @: g:t
I(2Y3%%&#%-< g: 7: Z$% #-'.(/*+#("% 9%-3'"*#'(" #'32/*"#& () #$% V/*"#4V*-*&'#'+
70)$4& *"1 -)+.&'(!" 55: A-% F%-',%1 )-(3 #$% =*-(#%"('1 V*#$Y*!: #&'0 !M,$+#1
5OO4< SNf JG+#(0%-L< fbU\fNc: $##5&qQQ1(':(-.QSU:SSUcQ55:SUT:U]SN^b:fbU:
!$
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 26 of 37
%)
%)!
YBRG*& $>ADB)=,
?'.2-% S: K*#2-*/ &#-'.(/*+#("% &#-'.(/ *"1 &!"#$%#'+ &#-'.(/*+#("% 9>bc< #$% /*##%- '& +(33("/!
2&%1 *& * 5(&'#',% +("#-(/ '" 0'(*&&*!& *& -*+%3*#%:
%)"
%)#
%)$
%)%
?'.2-% b: J*L !"#$%#'+ 5-(+%12-% #( (0#*'" %21%&3*"%&#-'.(/*+#("%& JMF a&< 37\5QL )-(3
+(&#2"(/'1% J3L: J0L #-2+#2-% () &!"#$%#'P%1 MF a&: J+L !"#$%#'+ 5-(+%12-% #( (0#*'"
1'$!1-(.2*'*"%&#-'.(/*+#("%& J1'$!1-(49Ma&< 5M< 57L *"1 %&#%- 1'3%- J5PL:
%)&
%)'
?'.2-% N: KGM %))%+#& (0&%-,%1 #( +(")'-3 #$% SS; +(")'.2-*#'(" () MF a& 37< 3P *"1 55< =4SS>
(-'%"#*#'(" () 5Q *"1 SR; +(")'.2-*#'(" () 5P:
%)(
% )
?'.2-% c: J*L MX5%-'3%"#*/ *"1 #$%(-%#'+*/ M=F &5%+#-* () MF a& 37\55 *"1 56\5Q: J0L
MX5%-'3%"#*/ *"1 #$%(-%#'+*/ M=F &5%+#-* () 1'$!1-(.2*'*"%&#-'.(/*+#("%& 5M *"1 57:
%
% !
% "
% #
?'.2-% T: >%&2/#& () 5*-*&'#'+ Y%%1 0'(*&&*! )(- +(35(2"1& 37\5P *"1 #$% 5(&'#',% +("#-(/ 9>bc:
D*/2%& Y'#$ &#*#'&#'+*/ &'."')'+*"+% $*,% 0%%" '"+/21%1 )(- 3(&# *+#',% +(35(2"1&: ?(- %*+$
+("+%"#-*#'(" '" #$% 0-((3-*5% 0'(*&&*!< E '"1'+*#%& 1'))%-%"+%& () %*+$ +(35(2"1 +(35*-%1
Y'#$ #$% "%.*#',% +("#-(/ JS_ ,Q, *+%#("% '" Y*#%-L< *& *&&%&&%1 0! F2""%##â& #%&# *# #$% U:UT /%,%/:
% $
% %
% &
?'.2-% ]: a%)#< &*35/% () -1 (/*&'& Y'#$ *55/'+*#'(" () 54 *# SU4c @ *# #$% %"1 () #$% 0'(*&&*!<
Y$%-% .%-3'"*#%1 &%%1& Y%-% "(# (0&%-,%1: >'.$#< &*35/% () -1 (/*&'& Y'#$ *55/'+*#'(" () 54 *#
SU4T @< Y$%-% 3(-% #$*" fU_ () .%-3'"*#%1 &%%1& Y%-% (0&%-,%1:
ACS Paragon Plus Environment

Page 27 of 37
Journal of Agricultural and Food Chemistry
% (
?'.2-%& *"1 *-#Y(-[
#
#
#
#
#
!
A
#
#
#
#$
"
#
#
%&'()*+,-./
0123
%!)
%!
YBRG*& 3
!
ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry
Page 28 of 37
<3
<
<3
?
?
<
3
<@
8
>
(45#$
>
2
:
2
<@
$
$
$
$
$
$
#
$
#
$
#
&
&
8
=
=
:
<:
$2 /26 +*6 3 7
;
<<
;
<<
<:
3
$
$
#
#
#
#
<2
<8
<8
<2
#
#
!
"
%;9'
%829'
%:39'
""A
$2 /26 +BC/DE
$
$
#
$
#
$
%;=9'
# $:
$
#
$
$
#
$
#
""A
$2 /2
3(FB#!G#$
"!M
!
6
$
.+
$
#$
$
#
#
# #! #"
6 .+
% #& ##
6
.+
"B55(FH+*,G
$2 /2
#
#
!+
#
#
$
#
$
#
<:
$
$
$
#
#
2L
<<
$
!(!D#I6 4$J
#
$
<LL
#
@ K
:L
#
#$* '
#' #( #)
6
.+
#
!+
#
$
#
$
#
#
#
$
!(!D#I6 4$J
#
@ K
(
!"#$ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
%"!ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
% # #' #$
#%
&
#
%<<%6 (2L$'
6
6
6
6
%<<"6 (2L#'6
%<<"6 (2L$'6
%<<%6 (2L#'6
! #& #! #(
!
%<<%6 (2L#'
6
6
6
6
%<<"6 (2L#&$'6
#"&
!"#$ꢀꢀꢀꢀꢀꢀ
ꢀ"ꢀ
$ ## #" #) "
'
%<<%6 (2L#'
6
6
6
6
%<<"6 (2L#'6
%!!
%!"
YBRG*& 5 S>T
"
ACS Paragon Plus Environment

Page 29 of 37
Journal of Agricultural and Food Chemistry
#
<
#
2
:
#
#
$
$
A
!
#
!"
%
%
#
#
<:
3
2L
"
<<
#
#
#"
!"
#
#
&
$
<8
#
#
#
#
#$
#%
&
#
#
#
#
#
$
#
!"
%
#
#"
#
#
#
!$#"
&
$
&
$
#
#
#
#
#
#
!
#
#
#
$
#
#
%
!"
#
#
!"
#
!"
#
#
&
!"
$
#
#
#
#
#
(
"
'
%!#
%!$
YBRG*& 5 SXT
#
ACS Paragon Plus Environment