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O ?$R meas%red 2al%e;
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O mean H!I 2al%e for all samples;
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O la' reference
2al%e for t3e it3 sample#
&#D# &ECK
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O la' reference 2al%e for t3e it3 sample;
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O ?$R meas%red 2al%e; ?O
n%m'er of samples, RO n%m'er of =a2elent3s %sed in an eC%ation; &#D#O standard
de2iation#
63e statistics s3o=n in eC# 1 and eC# 2 i2e a more realistic estimate of t3e applica'ilit!
of ?$R& to t3e anal!sis t3an t3ose of t3e e<ternal 2alidation, as cross-2alidation a2oids
t3e 'ias prod%ced =3en a lo= n%m'er of samples representin t3e f%ll rane are
selected as 2alidation set (&3enE and Qester3a%s, 1881; Qilliams and &o'erin, 1881)#
11
63e &ECK met3od is 'ased on an iterati2e alorit3m =3ic3 selects samples from a
sample set pop%lation to de2elop t3e cali'ration eC%ation and t3en predicts on t3e
remainin %nselected samples# 63is statistic indicates an estimate of t3e standard error
of prediction (&E") t3at ma! 3a2e 'een fo%nd in an e<ternal 2alidation (QorEman,
1882), and as occ%rred =it3 &E" is calc%lated as t3e sC%are root of t3e mean sC%are of
t3e resid%als for ?-1 derees of freedom, =3ere t3e resid%al eC%als t3e act%al min%s t3e
predicted 2al%e#
,#1# &pectr%m of B. napus leaf and modified partial least sC%are reression loadins
63e M"@& loadin plots of t3e first t3ree factors enerated from t3e M"@& reression
(2, 9, 9, 2; &?K7D6) for t-/&@ and also t3e indi2id%al l%cosinolates, =ere o'tained#
M"@& reression constr%cts its factors capt%rin as m%c3 of t3e 2ariation in t3e spectral
data as possi'le '! %sin t3e reference 2al%es acti2el! d%rin t3e decomposition of t3e
spectral data# 63e loadin plots s3o= t3e reression coefficients of eac3 =a2elent3 to
t3e parameter 'ein cali'rated for eac3 factor of t3e eC%ation# Qa2elent3s represented
in t3e loadin plots as more 3i3l! participatin in t3e de2elopment of eac3 factor, are
t3ose of more 2ariation and 'etter correlated to t3e compo%nd in t3e cali'ration set#
63e deri2ati2e spectr%m of t3e B. napus leaf %sed in t3is =orE =as o'tained '!
transformin t3e oriinal a'sor'ance 2al%es of all samples at eac3 =a2elent3 (ra=
optical data from ,-- to 29-- nm, e2er! 2 nm) to t3eir second deri2ati2e# $n addition,
t3e &?K pl%s D6 alorit3ms =ere applied# $n t3e second step, t3e a2erae spectr%m =as
calc%lated# 63e second order deri2ati2e transformation of t3e oriinal spectr%m res%lted
in a spectral pattern displa! of a'sorption peaEs pointin do=n=ard#
63e information i2en '! t3e second deri2ati2e of t3e spectr%m, toet3er =it3 t3at
information s3o=n '! t3e loadins for t3e factors of t3e different eC%ations, =ere %sed
1:
to identif! some of t3e a'sor'ers emplo!ed in modellin t3ese components# $n t3is =orE
=e %sed 'and assinments from literat%re, to relate some maDor a'sorption 'ands in t3e
spectr%m of na'icol lea2es =it3 t3e main =a2elent3s %sed '! M"@& to constr%ct t3e
first t3ree M"@& terms of t3e l%cosinolate eC%ations#
Ac&nowledgements
Qe t3anE /loria FernZndeJ Marn ($A&, C&$C, Crdo'a, &pain) for t3e performance of
t3e H"@C anal!ses# 63is =orE 3as 'een s%pported '! t3e "roDect MC[6 nT A/@ 2--0-
-1011 of t3e &panis3 /o2ernment#
1.
!eferences
An%s, U#F#, /ardner, "#A#, RirEeaard, U#A#, Desmarc3elier, U#M#, 188,#
Biof%miation4 isot3ioc!anates released from Brassica roots in3i'it ro=t3 of t3e taEe-
all f%n%s# "lant &oil 112, 1-:-112#
Barnes, R#U#, D3anoa, M#&#, @ister, &#U#, 18.8# &tandard normal 2ariate transformation
and de-trendin of near-infrared diff%se reflectance spectra# Appl# &pectrosc# ,0, ::2-
:::#
Bell, U#M#, 1889# Meal and '!-prod%cts %tiliJation in animal n%trition# $n4 Rim'er, D#&#,
Mc/reor, D#$#, (Eds#), Brassica *ilseeds# "rod%ction and StiliJation, CAB
$nternational, Qallinford, pp# 0-1-00:
Biston, R#, Dardenne, "#, C=iEo=sEi, M#, Marlier, M#, &e2erin, M#, Qat3elet, U#"#,
18..# Fast anal!sis of rapeseed l%cosinolates '! near infrared reflectance spectroscop!#
U# Am# *il# C3em# &oc# 19, 1988-11--#
Cartea, M#E#, &oenas, "#, "icoaa, A#, *rdZs, A#, 2--, Relations3ips amon Brassica
napus ermplasm from &pain and /reat Britain as determined '! RA"D MarEers# /en#
Res# Crop E2ol%tion Hin pressI#
ClarE, D#H#, Car!, E#E#, Ma!land, H#F#, 18.8# Anal!sis of trace elements in foraes '!
near infrared reflectance spectroscop!# Aron# U# .1, 81-89#
Da%n, U#R#, Clear, R#M#, Qilliams, "#, 188,# Comparison of t3ree =3ole seed near-
infrared anal!Jers for meas%rin C%alit! components of canola seed# U# Am# *il# C3em#
&oc# :1, 1-10-11-.#
18
Do=ne!, R#R#, RG''elen, /#, 18.8# Brassica species# $n4 RG''elen /#, Do=ne!#, R#R#,
As3ri, A#, (Eds#), *il Crops of t3e Qorld, Mc/ra=-Hill, ?e= [orE, pp# 008-
012#
Ettiner, M#/#, RDaer, A#, 181.# &%lp3%r compo%nds in plants# $n4 Ma'r!, 6#U#, Alston,
R#E#, R%necEles, K#C# (Eds#), Recent Ad2ances in "3!toc3emistr!, Kol# 1# Appleton-
Cent%r!-Crofts, ?e= [orE, pp# .8-1,,#
Fa3e!, U#Q#, \alcmann, A#6#, 6alala!, "#, 2--1# 63e c3emical di2ersit! and distri'%tion
of l%cosinolates and isot3ioc!anates amon plants# "3!toc3emistr! 91, 9-91#
Fen=icE, R#/#, Heane!, R#R#, M%llin, Q#U#, 18.0a# /l%cosinolates and t3eir 'reaEdo=n
prod%cts in food and food plants# C#R#C# Critical Re2ie=s in Food &cience and
?%trition 1., 120-2-1#
Fen=icE, R#/#, /riffit3s, ?#M#, Heane!, R#R#, 18.0'# Bitterness in Br%ssels spro%ts
(Brassica oleracea @# 2ar# gemmifera)4 t3e role of l%cosinolates and t3eir 'reaEdo=n
prod%cts# U# &ci# Food Ar# 0,, :0-.-#
Font, R#, Del Ro-Celestino, M#, K]leJ, D#, De Haro-Bailn, A#, Montoro, R#, 2--,a#
Kisi'le and near-infrared spectroscop! as a tec3niC%e for screenin t3e inoranic
arsenic content in t3e red cra!fis3 (Procambarus clarkii /irard)# Anal# C3em# :1, 0.80-
0.8.#
Font, R#, Del Ro, M#, FernZndeJ-MartneJ, U#M#, De Haro, A#, 2--,'# Sse of near-
infrared spectroscop! for screenin t3e indi2id%al and total l%cosinolate content in
$ndian m%stard seed (Brassica juncea @# CJern# ^ Coss#)# U# Ari# Food C3em# 92,
0910-0918#
/isl%m, R#, MicElander, E#, ?ielsen, U#"#, 2--,# V%antification of nitroen
concentration in perennial r!erass and red fesc%e %sin near-infrared reflectance
spectroscop! (?$R&) and c3emometrics# Field Crops Researc3 Hin pressI
2-
/ottlie', D#M#, &c3%ltJ, U#, Br%%n, &#Q#, Uaco'sen, &#, &_nderaard, $#, 2--,#
M%lti2ariate approac3es in plant science# "3!toc3emistr! Hin pressI
@o%da, &#, Mole, &#, 1881# /l%cosinolates4 c3emistr! and ecolo!# $n4 Rosent3al, /#A#,
Berem'a%m, M#R#, (Eds#), Her'i2ores4 63eir $nteractions =it3 &econdar! "lant
Meta'olites, Kol# 1# Academic "ress, ?e= [orE, pp# 120-11,#
Martens, H#, ?aes, 6#, 18.8# M%lti2ariate cali'ration# Uo3n Qile! ^ &ons, ?e= [orE#
M%rra!, $#, Qilliams, "#C#, 18.:# C3emical principles of near-infrared tec3nolo!# $n4
Qilliams, "#, ?orris, R#, (Eds#), ?ear-$nfrared 6ec3nolo! in t3e Aric%lt%ral and Food
$nd%stries, American Association of Cereal C3emists, $nc#, &t# "a%l, pp# 1:-0,#
*s'orne, B#/#, Fearn, 6#, Hindle, "#H#, 1880# "ractical ?$R spectroscop! =it3
applications in food and 'e2erae anal!sis# @onman &cientific ^ 6ec3nical, Esse<#
Rodr%eJ, K#M#, "adilla, /#, Cartea, M#E#, *rdZs, A#, 2--0# E2al%acin de 2ariedades
alleas de na'icol (B. napus 2ar# pabularia) en siem'ra precoJ# Actas de Hortic%lt%ra
08, 12--121#
Rosa, E#, 188:# /l%cosinolates from flo=er '%ds of "ort%%ese Brassica crops#
"3!toc3emistr! ,,, 1,19-1,18#
Rosa, E#A#&#, Heanc!, R#R#, Fen=icE, /#R#, "ortas, C#A#M#, 188:# /l%cosinolates in
crop plants# Hort# Re2# 18, 88-219#
&3apiro, 6#A#, Fa3e!, U#Q#, Qade, R#@#, &tep3enson, R#R#, 6alala!, "#, 2--1#
C3emoprotecti2e l%cosinolates and isot3ioc!anates of Broccoli spro%ts4 meta'olism
and e<cretion in 3%mans# Cancer Epidemiolo!, BiomarEers ^ "re2ention 1-, 9-1-9-.#
&3enE, U#&#, Qester3a%s, M#*#, 1889# Anal!sis of aric%lt%ral and food prod%cts '! near
infrared reflectance spectroscop!# $nfrasoft $nternational, "ort Matilda#
21
&3enE, U#&#, Qester3a%s, M#*#, 1881# Cali'ration t3e $&$ =a!# $n4 Da2ies, A#M#C#,
Qilliams, "#C#, (Eds#), ?ear $nfrared &pectroscop!4 63e F%t%re Qa2es, ?ir
"%'lications, C3ic3ester, pp# 18.-2-2#
&orensen, H#, 188-# /l%cosinolates4 str%ct%re, properties, f%nction# $n4 &3a3idi, F#,
(Ed#), Canola and Rapeseed# "rod%ction, c3emistr!, n%trition and processin
tec3nolo!, Kan ?ostrand Rein3old, ?e= [orE, pp# 1,8-1:2#
6Eac3%E, R#, R%Jina, F#D#, 18.2# C3lorop3!ll anal!sis of =3ole rapeseed Eernels '!
near infrared reflectance# Can# U# "lant &ci# 12, .:9-..,#
Kelasco, @#, BecEer, H#C#, 188.# Anal!sis of total l%cosinolate content and indi2id%al
l%cosinolates in Brassica spp# '! near-infrared reflectance spectroscop!# "lant
Breedin 11:, 8:-1-2#
Qilliams, "#, 18.:# Karia'les affectin near-infrared reflectance spectroscop! anal!sis#
$n4 Qilliams, "#, ?orris, R# (Eds#), ?ear-$nfrared 6ec3nolo! in t3e Aric%lt%ral and
Food $nd%stries, American Association of Cereal C3emists, $nc#, &t# "a%l, pp# 1,0-11:#
Qilliams, "#C#, &o'erin, D#C#, 1881# Ho= do =e do it4 a 'rief s%mmar! of t3e met3ods
=e %se in de2elopin near infrared cali'rations# $n4 Da2ies, A#M#C#, Qilliams, "#C#,
(Eds#), ?ear $nfrared &pectroscop!4 63e F%t%re Qa2es, ?ir "%'lications, C3ic3ester,
pp# 1.9-1..#
QorEman, Ur# U#U#, 1882# ?ir spectroscop! cali'ration 'asics# $n4 B%rns, D#A#, Ci%rcJaE,
E#Q#, (Eds#), Hand'ooE of ?ear-$nfrared Anal!sis, DeEEer $nc#, ?e= [orE, pp# 2,:-
2.-#
22
'itae
#r. !. (ont) Researc3er of t3e $nstit%te of &%staina'le Aric%lt%re (C&$C, Crdo'a,
&pain)# His =orE deals =it3 t3e %se of t3e ?ear-$nfrared &pectroscop! and its
application to different fields, incl%din plant 'reedin and en2ironmental researc3#
#r. *. del !+o-Celestino) Researc3er of t3e $nstit%te of &%staina'le Aric%lt%re (C&$C,
Crdo'a, &pain)# &3e 3as participated in n%mero%s researc3 proDects dealin =it3 plant
'reedin concernin Brassicas and also, s3e is an e<pertise in p3!toremediation#
#r. %lena Cartea) Researc3er of t3e Misin Biolica of /alicia (C&$C, "onte2edra,
&pain)# Her =orE deals =it3 plant 'reedin of Brassicas#
#r. A. de ,aro--ail.n). Head of t3e Aronom! and "lant Breedin Department of t3e
$nstit%te for &%staina'le Aric%lt%re (C&$C, Crdo'a, &pain)# His =orE 3as dealt for
!ears in t3e impro2ement of t3e C%alit! of different Brassica species and ot3er crops,
leadin different national and international researc3 proDects# &ince 188., 3e is also
leader of different proDects concernin t3e %se of plants for decontaminatin poll%ted
en2ironments '! trace elements#
20
(igure captions
(igure 1. Basic str%ct%re of l%cosinolates#
(igure . FreC%enc! distri'%tion plots of total l%cosinolates (a), l%conapin ('),
l%co'rassicanapin (c), prooitrin (d), l%co'rassicin (e) and l%coal!ssin (f) for t3e
samples %sed in t3is =orE (nO 119) (Lmol
-1
d=)#
(igure ". Ra= spectra (@o 1+R) of t3e leaf samples of Brassica napus 2ar# pabularia
%sed in t3is =orE (nO 119), in t3e rane from ,-- to 29-- nm#
(igure $. &econd deri2ati2e spectra (2, 9, 9, 2; &?K7D6) of t3e ra= optical data in t3e
rane from ,-- to 29-- nm#
(igure /. Cross-2alidation scatter plots of la'orator! 2s# predicted 2al%es '! ?$R& for
total l%cosinolates (a), l%conapin ('), l%co'rassicanapin (c), prooitrin (d),
l%coal!ssin (e) and l%co'rassicin (f) (nO 119) (Lmol
-1
d=)#
(igure 0. M"@& loadin spectra for total l%cosinolates in t3e second deri2ati2e (2, 9,
9, 2; &?K7D6) transformation# From t3e top to 'ottom, panels represent loadins for
factors 1, 2 and 0, respecti2el!#
2,
1ables
1able 1. A''re2iations, tri2ial names and side-c3ain str%ct%res of t3e l%cosinolates
considered in t3is =orE#
Abbreviation 1rivial name Chemical structure
Alip3atic
0-B%ten /l%conapin (/?A) CH
2
OCH-CH
2
-CH
2
-
,-"enten /l%co'rassicanapin
(/B?)
CH
2
OCH-CH
2
-CH
2
-CH
2
-
2-*H-0-B%ten "rooitrin ("R*) CH
2
OCH-CH(*H)-CH
2
-
9-M&" /l%coal!ssin (/@A) CH
0
-&*-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-
$ndole
0-$M /l%co'rassicin (/B&)
1able . Cali'ration and cross-2alidation statistics for t3e different eC%ations
de2eloped for l%cosinolates (nO 119) (Pmol
-1
d=)#
29
calibration cross-validation
glucosinolate range mean 2.#.
g
2%C
h
!
i
2.#. 2%C'
-13
r
&
nt
l
t-/&@
a
1#-1-
,8#1.
18#.9 11#-
0
1#.. -#8
:
2#81 -#.
.
8
/?A
'
--1#.. 2#:1 1#9, -#11 -#.
,
1#8, -#:
0
9
/B?
c
-#01-
21#-:
.#-0 9#1 1#,: -#8
1
2#01 -#.
1
:
"R*
d
-#1--
10#-0
9#11 0#2. -#8. -#8
1
2#11 -#:
.
.
/A@
e
--,#-- 1#-1 1#19 -#.- -#9
-
1#2: -#0
:
0
/B&
f
-#-1-0#,9 1#-1 -#.0 -#98 -#9
-
1#28 -#,
1
0
a
total l%cosinolates#
'
l%conapin#
c
l%co'rassicanapin#
d
prooitrin#
e
l%coal!ssin#
f
l%co'rassicin#