Professional Documents
Culture Documents
Luan Van Thac Si Cua HIEN
Luan Van Thac Si Cua HIEN
Luan Van Thac Si Cua HIEN
M U.........................................................................................................
Chng 1. TNG QUAN..............................................................................
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Chng 4. KT LUN................................................................................
TI LIU THAM KHO...........................................................................
PH LC......................................................................................................
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M U
Theo d bo ca U ban Dn s v Pht trin ca Lin hp quc, vo gia
th k XXI dn s th gii s tng thm 03 t ngi. Dn s ngy cng tng nhanh
to ra gnh nng cho nn sn xut nng nghip lng thc, v cng vi mt din
tch canh tc nht nh v ang c xu hng b thu hp li phi cung cp s
lng lng thc cho s u ngi lun gia tng. tng nng sut lao ng,
ngi ta s dng nhiu bin php an xen nh: thm canh tng v, ci tin
ging...; mt trong nhng bin php khng th thiu l s dng thuc bo v thc
vt. [9]
Thuc bo v thc vt c coi l mt v kh c hiu qu ca con ngi
trong vic phng chng dch hi, bo v cy trng. Bn cnh u im l bo v
nng sut cy trng, thuc bo v thc vt cn gy ra nhiu tc tc hi khc nh lm
nhim mi trng, gy c cho ngi v gia sc, tng chi phi sn xut, v nht l
li tn d trong nng sn gy nh hng n cht lng nng sn v sc khe
ngi tiu dng. Tc ng tiu cc ca thuc bo v thc vt cng tr nn nghim
trng khi con ngi s dng khng ng cch v qu lm dng vo thuc.
Ha cht bo v thc vt c nhiu nhm ha cht khc nhau, trong c bn
nhm chnh l: ln hu c, clo hu c, carbamat v pyrethroid. Nhm clo hu c
b cm s dng, nhm pyrethroid vn ang c s dng nhng c tnh thp, t c
kh nng gy nhim c cho ngi s dng. Cn li 2 nhm: ln hu c v
carbamat ang c dng rng ri trong nng nghip , c c tnh cao v l nguyn
nhn chnh ca phn ln cc v ng c do n rau qu nhim ha cht bo v thc
vt nc ta hin nay.
Vi nhng l do trn, chng ti la chn ti: Xc nh ha cht bo
v thc vt carbamat trong mt s loi rau qu bng phng php sc k lng khi
ph (LC-MS).
10
Quc gia
Nht Bn
Vit Nam
i tng
Carbofuran
Carbayl Propoxur
(mg/kg)
(mg/kg)
(mg/kg)
(mg/kg)
0,3
3,0
1,0
0,3
5,0
3,0
Xoi
To, nho, l
(Quyt nh
46/2007/Q-
C chua, c rt
0,1
Tri cy
0,1
0,05
BYT)
EU
Fenobucarb
11
0,05
Trong phng php ny, ngi ta phn cc in cc git thy ngn bng
mt in p mt chiu bin thin tuyn tnh vi thi gian nghin cu cc qu
trnh kh cc ca cht phn tch trn in cc . V vy, thit b cc ph gm hai
phn chnh l my cc ph v h in cc bao gm in cc git thu ngn v in
cc so snh. ng cc ph biu din s ph thuc ca chiu cao cng dng
vi nng cht phn tch. xc nh cc lng nh cht thng dng cc ph
c in (10-3 n.10-5). xc nh cc lng cht cc nh thng dng cc phng
php cc ph hin i nh cc ph sng vung, cc ph xung vi phn. [5]
A. Guiberteau , T. Galeano Diz, F. Salinas v J.M. Ortiz [12] xc nh
carbaryl v carbofuran bng phng php cc ph xung vi phn. Phng php c
ng dng xc nh cc mu nc sng. Cc mu nc sau khi x l s c xc
nh bng phng php cc ph xung vi phn vi cc iu kin sau: tc qut
20mV/s (bc nhy th: 5mV, khong thi gian 0,25s), bin xung 50mV trong
khong t + 0,4V n + 0,8V. Khong tuyn tnh ca carbaryl t 5.10-7
10-4M v
12
13
x ca nguyn t, tnh cht hunh quang, s thay i chit sut, tnh cht in ha.
ng vi mi tnh cht ngi ta c mt loi detector. [4]
Tc gi Ana M. Garca-Campana v cng s [23] pht trin phng php
mi xc nh carbaryl trong thc phm thc vt v nc t nhin bng k thut
phn tch dng chy. i vi mu nc, lc qua mng lc 0,45m ri tin hnh
phn tch. i vi mu qu, tin hnh chit mu bng etylacetat v lm sch qua
cc loi ct chit pha rn nh nhm oxit, SAX, C18, silica. Hiu sut chit tt nht
khi s dng ct nhm oxit. Carbayl ch pht hunh quang khi c ca cht oxi ha
KMnO4 trong mi trng kim nh. H thng phn tch dng chy xc nh
carbaryl gm 3 knh cha 3 dung dch khc nhau: NaOH, luminol v KMnO4. Ti
cc iu kin ti u, khong tuyn tnh carbaryl t 5 100ng/ml v gii hn pht
hin l 4,9ng/ml. y l mt phng php n gin, nhanh v d dng kt hp vi
phng php sc k lng xc nh ng thi mt s carbamat.
Mt phng php xc nh carbaryl bng k thut phn tch dng chy s
dng detector UV Vis c cc tc gi Karim D. Khalaf, A. Morales-Rubio v
M. de la Guardia [25] nghin cu. Mu c chit vi xylen v bm vo h thng
phn tch dng chy. Ti y, carbaryl s phn ng vi naphtholate v dung dch paminophenol 50pg/ml trong s c mt ca dung dch KIO4 0,004M to thnh hp
cht mang mu iodophenol. Cht ny c xc nh bng detector UV Vis ti
bc sng 596nm. H thng phn tch dng chy gm 4 knh: p-aminophenol, IO4-,
H2O v NaOH. Phng php c gii hn pht hin 26,5ng/ml vi tn sut bm mu
110 ln/gi. thu hi carbaryl trn cc nn mu khc nhau kh cao t 95 102%.
Mt phng php phn tch dng chy s dng detector hunh quang xc
nh carbofuran c cp. Phng php da trn phn ng ca carbofuran
vi KMnO4 v luminol trong mi trng kim nh s t thnh hp cht mu.
Carbofuran b oxi ha to thnh anion 3-aminophthalate dng kch thch bn v
c xc nh bng detector hunh quang. Khong tuyn tnh ca carbofuran t
14
0,06 0,5g/ml, gii hn pht hin 0,02g/ml. Phng php ng dng thnh
cng xc nh d lng carbofuran trong mu rau dip.[24]
Phng php phn tch dng chy c u im l nhanh, thit b phn tch d
kim v r tin. Tuy nhin, phng php khng th xc nh ng thi cc cht
carbamat. Do vy, phng php cng t c ng dng phn tch carbamat.
1.3.4. Phng php in di mao qun
Ling Wang v cng s [34] tch v xc nh d lng thuc tr su
carbamat bng phng php in di mao qun ng p. Ct mao qun c ng
knh 75m c nhi ht ODS 3m. Pha ng bao gm 30% acetonitril v 70%
dung dch m
15
16
17
18
loi thuc tr su, trn 30% mu cn li cha nhiu loi thuc tr su. Tuy nhin,
tt c cc nng thuc tr su tm thy u thp hn gii hn cho php.[29]
Xc nh d lng carbamat trong rau qu bng phng php khuch tn
trn nn pha rn v sc k lng khi ph. Mu c chit trn nn cc pha rn khc
nhau: C8, C18, NH2, CN v phenyl. Hiu sut chit tt nht trn nn pha rn C8 t t
64 106% vi RSD 5 15%. Gii hn pht hin ca phng php t 0,001
0,01mg/kg, thp hn gii hn cho php ca chu u t 10 100 ln. Phng php
c ng dng xc nh carbamat trong cc mu rau qu ti cc ch
Valencian.[30]
Phng php sc k lng khi ph l mt k thut mi c pht trin trong
nhng nm gn y. V c bn, n l phng php sc k lng s dng b phn
pht hin l detector khi ph. Phng php ny tuy mi ra i nhng n c ng
dng rng ri phn tch ng thi cc thuc tr su c bit l nhm carbamat.
Phng php c th phn tch ng thi t hng chc n hng trm cc loi thuc
tr su khc nhau. Phng php c nhiu u im nh chn lc cao, gii hn
pht hin thp, thi gian phn tch nhanh, c th nh lng ng thi cc cht c
thi gian lu ging nhau m phng php sc k lng thng khng lm c.
Vi nhng u im trn, chng ti chn phng php sc k lng khi
ph nghin cu xc nh ng thi cc cht carbamat.
19
20
21
22
23
xyclopentan,
n-pentan,
n-heptan,
n-hexan,
2-chloropropan,
24
25
26
Giai on th hai:
N 2. H 2O N 2 H 2O .
H 2 O H 2 O H 3 O HO
.
Giai on th ba:
H 3O M (M H ) H 2O
27
28
My li tm MIKRO 22R.
Cn phn tch (c chnh xc 0,1mg v 0,01mg).
Cn k thut (c chnh xc 0,01g).
My ct quay chn khng Eyela.
2.3.1.2. Dng c
Pipet: 1, 2, 5, 10, 20ml.
Bnh nh mc: 5, 10, 50, 100ml.
29
ng li tm 50ml
Ct nhi kieselguhr.
Bnh c quay 100ml
Vial loi 1,8ml.
Pipet pasteur.
ng ong, phu, giy lc.
Pietman loi 200l v u cn.
2.3.3. Dung mi, ha cht
Cc loi ho cht s dng u thuc loi tinh khit.
o Chun carbamat gm: carbofuran, propoxur, carbaryl, fenobucarb.
o Methanol.
o n-hexan.
o Diclometan.
o Amoniacetat CH3COONH4.
o NaCl.
o Nc ct 2 ln.
* Chun b dung dch chun
- Dung dch chun gc 1000mg/l: Cn chnh xc 0,1g cht chun ln lt ca
tng carbamat, ho tan cho vo tng bnh nh mc 100ml v nh mc n vch
bng methanol. Chun gc c bo qun nhit t 0 5C.
- Dung dch chun hn hp trung gian 10mg/l: ly chnh xc 1ml dung dch
chun gc ca mi carbamat 1000 mg/l cho vo bnh nh mc 100ml v nh mc
n vch bng methanol.
30
31
Ion m
Carbofuran
221,3
221,98
Propoxur
209,3
210
Carbaryl
201,2
201,84
Fenobucarb
207,3
208,00
32
kscarbaryl
#9 0 0
RT: 11.92
T: +cE SI F ull ms[110.00-210.00]
AV:
NL:
4.60E6
201.84
100
Phkhiioncarbaryl
90
RelativeAbundance
80
70
60
50
40
30
114.95
20
145.22
202.90
10
168.07
124.88
136.24
146.13 179.22
196.18
154.95
167.18
150
160
m/z
0
11 0
120
130
140
173.15
190.07
170
180
190
203.83
200
210
AV:
NL:
2.98E7
221.98
100
Phkhiioncarbofuran
90
RelativeAbundance
80
70
60
50
40
30
20
222.97
10
165.26
154.97
168
162.00
173.32
185.14
190.06
196.44 199.35
210.5 213.99
223.94
220.56
1
.23
150
160
170
180
190
m/z
200
210
220
230
AV:
NL:
3.42E6
208.00
100
Phkhiionfenobucarb
RelativeAbundance
90
80
70
60
50
40
30
20
185.22
168.22
196.42
175.26
10
209.07
114.24
118.98
0
11 0
120
130.39
130
144.39
140
152.12
150
158.23
205.01
160
170
180
190
200
210.00
210
220
m/z
33
kspropoxur
#4 7 3
RT: 9.18
T: +cE SI F ull ms[110.00-230.00]
AV:
NL:
3.26E7
209.90
100
Phkhiionpropoxur
90
RelativeAbundance
80
70
60
50
40
30
20
210.92
10
111.16
0
11 0
125.09
120
130.58
130
144.18
8
140
153.15
150
168.17
16 0
196.23
180.2 185.31
170
180
190
200
208.36
226.57
211.93
210
220
230
m/z
Ion m
Ion con
Collision Energy (%)
Carbofuran
222
48
165
Propoxur
210
45
168, 153
Carbaryl
202
45
145
Fenobucarb
208
37
152
34
Carbofuran
#9 5 4
RT: 13.85
AV: 1 NL:
F: +cESIFullm s2222.00@48.00[60.00-230.00]
100
4.38E5
164.90
PhkhiionconcaCarbofuran
90
RelativeAbundance
80
70
60
50
40
30
20
10
70.69
84.38
98.52
113.06
123.21
133.29
149.33
161.09
226.40
4
60
80
100
120
140
m /z
160
180
200
220
1.39E5
151.84
100
PhkhiionconcaFenobucarb
90
RelativeAbundance
80
70
60
50
40
30
20
10
94.94
85.61
60.38 72.81 81.85 105.24 130.65
150.67
119.13
148.35
164.29
192.40 204.72
172.07
216.41
229.31
0
60
80
100
120
140
m/z
160
180
200
220
167.84
100
PhkhiionconcaPropoxur
90
RelativeAbundance
80
70
60
152.78
50
40
30
20
69.75
10
123.42
84.37
110.84
74.65
150.89
99.91
154.66
164.70
196.64
177.28
192.63
204.25
228.11
219.1
0
60
80
100
120
140
m /z
160
180
200
220
35
Carbaryl
#1002
RT: 14.24
AV: 1 NL:
F: +cESIFullms2202.00@45.00[55.00-230.00]
5.87E4
144.95
100
PhkhiionconcaCarbaryl
90
RelativeAbundance
80
70
60
50
40
30
20
57.90
102.44
66.05
10
76.00
140.14
151.43
198.68
118.97
176.10
166.5
189.65
92.05
218.86
6
60
80
100
120
140
m/z
160
180
200
220
36
CH3COONH4 0,1%
Carbofuran
88164531
62596017
52548096
Propoxur
8023138
7095289
5289116
Carbaryl
8972544
4205380
3950325
Fenobucarb
5076448
2191283
2239988
Nhn xt: S dng pha ng l acid focmic 0,1% cho din tch pic cao nht,
tng nhy ca phng php. Do , chng ti chn pha ng l methanol v
dung dch acid focmic 0,1% trong nc cho cc kho st tip theo.
Trong phng php nghin cu, pha tnh s dng l ct C18, t phn cc nn
pha ng phi l h dung mi phn cc. Cht tan t phn cc s b lu gi trong ct
lu hn cht tan phn cc. Do tnh cht km phn cc ca cc cht nhm carbamat
nn chng ti chn pha ng trn 2 knh:
o Knh A: dung dch acid focmic 0,1% trong nc.
37
Detector: MS/MS.
%A
%B
Carbofuran
Propoxur
Carbaryl
Fenobucarb
10
90
3,83
3,78
4,12
4,34
20
80
4,36
4,30
4,91
5,52
30
70
5,29
5,23
6,43
8,29
40
60
7,19
7,27
9,78
15,53
50
50
11,48
11,49
17,82
Khng thy
Nhn xt: T bng kt qu trn ta thy, khi thnh phn pha ng chy vi
ch ng dng isocractic, t l methanol cng cao, thi gian lu cng gim, cc
cht khng tch ra khi nhau. Hn na, khi cht phn tch ra qu sm, rt d b nh
hng bi cc tp cht. Ngc li, khi lng methanol cng gim th thi gian lu
tng, cc cht tch ra khi nhau nhng thi gian cht gia cc cht cng tng theo,
lm tng thi gian phn tch v tn dung mi. Do , c th va tch c cc
cht, va tit kim c thi gian phn tch v dung mi, chng ti tin hnh chy
pha ng vi ch gradient.
38
Tc dng
(ml/pht)
HCOOH 0,1 %
MeOH
0,5
90
10
1,0
0,5
50
50
6,0
0,5
20
80
12,0
0,5
100
13,0
0,5
100
15,0
0,5
90
10
18,0
0,5
90
10
Tc dng 0,5ml/pht.
Detector MS/MS vi cc thng s bng 3.1 v 3.3.
39
Din tch pc
C (ppb)
Carbofuran
Propoxur
Carbaryl
Fenobucarb
20
1818855
50
4323952
390301
385265
212190
100
8848970
742948
643172
393640
200
17287122
1577384
1181737
814165
500
38708909
3668940
3127832
1923068
1000
75531554
7089406
6399387
4013364
1500
95077738
8595550
8192473
5140543
40
ng chun Fenobucarb
5000000
Dintch
4000000
Dintch
y = 3990x - 5018.5
4500000
6000000
3000000
2000000
1000000
R2 = 0.9994
4000000
3500000
3000000
2500000
2000000
1500000
1000000
500000
0
0
500
1000
1500
2000
500
Nng (ppb)
1000
1500
Nng (ppb)
ng chun Carbaryl
7000000
8000000
6000000
7000000
5000000
6000000
4000000
Dintch
9000000
Dintch
5000000
4000000
y = 6376x - 11658
R2 = 0.9993
3000000
3000000
2000000
2000000
1000000
1000000
0
0
500
1000
1500
2000
200
400
600
800
1000
1200
Nng (ppb)
Nng (ppb)
41
10000000
8000000
9000000
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
0
7000000
y = 7038.3x+ 89642
2
R = 0.9995
6000000
5000000
Dintch
Dintch
ng chun Propoxur
4000000
3000000
2000000
1000000
0
500
1000
1500
2000
200
400
600
800
1000 1200
Nng (ppb)
Nng (ppb)
ng chun Carbofuran
100000000
70000000
80000000
60000000
50000000
Dintch
60000000
Dintch
y = 74735x + 1E+06
R2 = 0.9993
80000000
40000000
40000000
30000000
20000000
20000000
10000000
0
0
0
500
1000
1500
2000
Nng (ppb)
500
1000
1500
Nng (ppb)
42
RT:
0.00-18.04
NL:2.60E6
RT:8.87
MA:38708909
100
TIC F: +cESISR M ms 2
222.00@48.00[
164.50-165.50] M S mix
500ppb
RelativeAbundance
50
1.07
2.82
4.23
9.57
6.15 6.68
10.97 11.85
TIC F: +cESISR M ms 2
210.00@45.00[
152.50-153.50,
167.50-168.50] M S mix
500ppb
MA:3668940
100
50
0.73
2.31
3.01
4.41
5.02 7.13
7.92
12.03 13.35
9.23
16.15
16.77
NL:2.15E5
RT:9.86
MA:3127832
100
TIC F: +cESISR M ms 2
202.00@45.00[
144.50-145.50] M S mix
500ppb
50
0.83
1.88
3.02
4.25
5.04
10.82
12.75
13.97
16.25 16.95
NL:1.36E5
RT:10.93
TIC F: +cESISR M ms 2
208.00@37.00[
151.50-152.50] M S ICISmix
500ppb
AA:1923068
100
50
0
0
8
10
Time(min)
12
14
16
18
43
RT: 0.00-18.04
NL:3.24E5
8.87
100
TICF:+c ESISRMms2
222.00@48.00[
164.50-165.50] MS mix
15ppb
50
RelativeAbundance
6.76 7.46
1.16
2.82 4.40
9.48
8.60
13.86
5.62
11.67
12.37
16.66
14.47
NL:2.04E4
RT:8.96
100
TICF:+c ESISRMms2
210.00@45.00[
152.50-153.50,
167.50-168.50] MS mix
15ppb
16.32
8.79
12.73
50
4.32
3.5
1.08 2.57
6.42 6.69
7.91 11.50
9.49
13.26
15.01
10.28
NL:2.98E4
RT:9.85
100
TICF:+c ESISRMms2
202.00@45.00[
144.50-145.50] MS mix
15ppb
50
7.05
6.08
5.65
3.892.58
1.70
8.80
12.65
0
100
14.23
11.60
17.12 17.47
NL:1.39E4
TICF:+c ESISRMms2
208.00@37.00[
151.50-152.50] MS mix
15ppb
RT:10.92
7.24
50
5.67 6.37
4.00
0.85
7.59
12.33
RT:8.8
13.47
15.22 15.57
2.25
2
0
0
8
10
Time(min)
12
14
16
18
RT: 0.00-18.04
5.285.54
RelativeAbundance
NL:3.62E4
RT:8.87
100
7.20 10.10
50
1.33
4.31
2.12
5.46
6.51
0.82
2.57
17.28
15.27
0
100
50
TICF:+cESISRMms2
222.00@48.00[
164.50-165.50] MSmix
5ppb
11.94 12.99
6.50
6.78
8.97
12.12
10.37
5.2
2.75
3.54
NL:1.15E4
16.85 17.90
13.9
11.42
TICF:+cESISRMms2
210.00@45.00[
152.50-153.50,
167.50-168.50] MSmix
5ppb
14.84
0
4.51
0
100
7.84
6.00
5.47
6.88
1.71
2.49
1.27
4.09
4.25
50
0
100
50
10.38
9.85
13.36
12.40
9.5
15.90
13.62
8.309
6.81
8.74
4.88
0.50
8.45
7.42
2.25 2.78
NL:7.56E3
TICF:+cESISRMms2
208.00@37.00[
14.70
5.85 10.05
13.29
11.10
NL:1.07E4
TICF:+cESISRMms2
202.00@45.00[
17.48 144.50-145.50] MSmix
5ppb
0
0
8
10
Time(min)
12
14
16
18
44
%X
%X tb
%X
i1
(S
tb
CV
S
n
1
S
100
S tb
: s ln o.
S : lch chun.
CV : h s bin ng ca php o.
nh gi sai s v lp li ca php o ta dng ng chun, pha 3 mu
c nng im u, im gia v im cui ca khong tuyn tnh. Thc hin
o mi mu 4 ln. Cc kt qu c ch ra bng 3.8.
Bng 3.8. Sai s v lp li ca php o ti cc nng khc nhau
45
Nng
(ppb)
50
pic St
CV
(%)
Carbofuran
4462544
4479553
4710802
5088066
4864153
6,0
6,2
Propoxur
407756
401130
413389
465694
441555
7,2
7,0
Carbaryl
312599
317887
306848
273725
292517
6,7
6,6
Fenobucarb
213922
185829
207264
212625
194482
7,6
6,4
3911632
3958007
1,6
1,3
39847129
3870890
9
Propoxur
3617105
3727622
3748831
3681568
3668940
1,4
1,6
Carbaryl
3098305
3230757
3206597
3173917
3127832
2,1
1,8
Fenobucarb
1957011
1908327
1961337
1943537
1923068
1,4
1,2
7636070
7443025
1,4
1,6
Carbofuran 76364091
1000
%Xtb
Ln o
Carbofuran 38651499
500
Din tch
74136751
7553155
4
Propoxur
7054760
6944509
6924225
7523589
7089406
2,7
3,9
Carbaryl
6683924
6255124
6552468
6959715
6399389
4,5
4,4
Fenobucarb
4266145
4099357
3972133
4202736
4013364
3,5
3,1
46
Mu /ng li tm 50ml
+ thm chun hn hp 4 carbamat
+ MeOH
ng nht
Lc vortex
Lc / bnh nh mc 50ml
+ nh mc bng NaCl bo ha
Cho 20ml qua ct Kieselguhr
Ra gii
C quay /40C n cn
Ha cn bng 1ml MeOH
LC/MS/MS
47
Carbofura
Propoxur
Carbaryl
Fenobucarb
4483543
665262
240667
310632
Spic
52,5
72,5
41,2
68,9
mtt(ng)
26,3
37,7
20,6
34,5
R (%)
15655765
1690891
1039212
817610
Spic
183,4
191,9
177,8
181,4
mtt(ng)
91,7
95,9
88,9
90,7
R (%)
16414779
1628490
1010188
839404
Spic
192,3
184,8
172,8
186,3
mtt(ng)
96,1
92,4
86,4
93,1
R (%)
13946052
1174001
969756
496001
Spic
163,4
133,2
165,9
110,1
mtt(ng)
81,7
66,6
83,0
55,0
R (%)
1:1
200
2:1
200
3:1
200
4:1
200
R (%)
Carbofuran
Propoxur
60
Carbaryl
Fenobucarb
40
20
MeOH:H
0
1:1
2:1
3:1
4:1
48
2O
Hexan
Diclometan
Etylacetat
mlt (ng)
400
400
Carbofuran
Propoxur
Carbaryl
Fenobucarb
7014554
869221
933158
1371602
Spic
90,8
112,9
178,8
385,1
mtt(ng)
22,7
28,2
44,7
96,3
R (%)
27420193
2582414
1853667
1054473
Spic
354,8
335,3
355,1
296,0
mtt(ng)
88,7
83,8
88,8
74,0
R (%)
Khng ha tan c
400
Nhn xt: T kt qu trn ta thy, khi ra gii carbamat bng 3 loi dung mi
khc nhau, hiu sut thu hi i vi diclometan l tt nht, vi hexan th thp hn
cn etylacetat sau khi c quay xut hin nhiu kt ta bm ln thnh bnh. C th do
dung mi etylacetat ra gii c nhiu cht hn diclometan v hexan. thu hi
ca carbofuran, carbaryl v propoxur tng i cao khi dng diclometan cn
49
1:2
1:1
2:1
3:1
200
200
200
200
Carbofura
Propoxur
Carbaryl Fenobucarb
15265216
1715528
1034817
603147
Spic
187,4
191,8
151,0
158,1
mtt(ng)
93,7
95,9
75,5
79,1
R (%)
15528417
1621848
1257159
718201
Spic
190,7
181,3
183,5
188,3
mtt(ng)
95,3
90,7
91,7
94,1
R (%)
15023256
1592201
992548
493364
Spic
184,5
178,0
144,9
129,3
mtt(ng)
92,2
89,0
72,4
64,7
R (%)
14922541
1430625
1072136
551947
Spic
183,2
160,0
156,5
14,7
mtt(ng)
91,6
80,0
78,2
72,3
R (%)
50
R (%)
100
80
Carbofuran
60
Propoxur
Carbaryl
Fenobucarb
40
20
CH2Cl2:hexan
0
1:2
1:1
2:1
3:1
20
40
mlt (ng)
200
200
Carbofuran
Propoxur
Carbaryl
Fenobucarb
9642540
814612
484553
248305
Spic
118,4
91,1
70,7
65,1
mtt(ng)
59,2
45,5
35,4
32,5
R (%)
14462593
1433329
946380
720286
Spic
51
177,6
160,3
138,1
188,8
mtt(ng)
88,8
80,1
69,1
94,4
R (%)
15174514
1582214
1214988
722391
Spic
186,3
176,9
177,3
189,4
mtt(ng)
93,2
88,4
88,7
94,7
R (%)
15294587
1691354
1164021
636247
Spic
187,8
189,1
169,9
166,8
mtt(ng)
93,9
94,6
84,9
83,4
R (%)
1
0
0
8
0
50
200
60
200
R (%)
60
Carbofuran
Propoxur
40
Carbaryl
Fenobucarb
20
V (ml)
0
0
10
20
30
40
50
60
70
52
(S
tb
CV
S
n
1
S
100
S tb
S : lch chun.
CV : h s bin ng ca php o.
thu hi ca phng php theo cc cng thc sau :
C
C '.V
m
(C mc C m ) m
100
mc
Trong :
C: nng carbamat xc nh c (ng/g)
C': nng carbamat tnh t ng chun (ng/ml)
V: th tch ha cn (V=1ml)
m: khi lng mu (g)
Cm+c : nng carbamat xc nh c trong mu thm chun (ng/g)
Cm: nng carbamat c trong mu (ng/g)
mc: lng carbamat thm vo (ng)
R: thu hi (%)
Bng 3.13. Kt qu lp li v thu hi ca phng php
53
mc
(ng)
100
CV
(%)
4979720
4767493
4689607
5336250
5533186
89,3
5,9
Propoxur
551149
483616
523328
506348
574177
90,0
5,5
Carbaryl
446472
424858
489584
485875
506095
91,2
6,8
Fenobucarb
262141
257556
276491
286139
307509
88,0
4,9
2374753
2353585
92,2
2,7
24981490
2621918
6
Propoxur
2494321
2503822
2324398
2494461
2720697
90,2
3,5
Carbaryl
2185965
2190473
2108417
2285938
2373695
92,4
3,3
Fenobucarb
1212958
1290565
1219670
1237636
1397789
88,7
2,8
4591357
4844647
90,8
2,4
Carbofuran 46861702
1000
pic St
%Rtb
Carbofuran
Carbofuran 24427430
500
Din tch
47829695
5207668
6
Propoxur
5024113
4669544
4872670
5022337
5403847
90,6
3,4
Carbaryl
4419905
4084287
4226059
4592391
4708195
92,0
5,1
Fenobucarb
2395286
2416886
2328485
2340531
2760639
85,9
1,8
54
Mu ( 10g)/ng li tm 50ml
+ thm chun hn hp 4 carbamat
+ 20ml MeOH
ng nht
Lc vortex 5 pht
QUI TRNH CHIT CARBAMAT TRONG RAU QU
Li tm 6000 v/ph, 5 pht
Lc / bnh nh mc 50ml
+ nh mc bng NaCl bo ha
Ht 20ml dung dch cho qua ct Kieselguhr
yn 15 pht
Ra gii bng 50 ml hexan:diclometan = 1:1
C quay /40C n cn
LC/MS/MS
55
STT
Mu
Carbamat
Lng thm
Lng tm
thu
vo (ng)
thy (ng)
hi R%
KPH
250
202,75,9
81,1
KPH
250
203,06,9
81,2
KPH
250
213,54,5
85,4
KPH
250
206,68,7
82,7
KPH
250
211,06,7
84,4
KPH
250
207,77,3
83,1
KPH
Carbofuran
Propoxur
1
Cam
Carbaryl
Fenobucarb
2
To
Carbofuran
Propoxur
Carbaryl
56
Fenobucarb
Carbofuran
Propoxur
3
Fenobucarb
Carbofuran
Propoxur
82,2
KPH
250
215,45,0
86,2
KPH
100
83,33,8
83,3
KPH
100
80,63,1
83,1
KPH
100
80,32,8
80,3
KPH
100
80,32,6
80,3
KPH
200
162,95,4
81,5
KPH
200
160,15,4
80,0
KPH
200
168,94,7
84,5
KPH
200
164,44,9
82,2
KPH
200
167,35,9
83,6
KPH
Nho xanh
Carbaryl
Fenobucarb
205,58,4
Qut
Carbaryl
5
7
250
Carbofuran
Propoxur
Carbaryl
Fenobucarb
200
161,36,4
80,6
KPH
200
162,74,4
81,4
KPH
200
166,25,2
83,1
STT
Mu
Carbamat
Lng thm
Lng tm
thu
vo (ng)
thy (ng)
hi R%
KPH
250
207,28,7
82,9
KPH
250
220,48,2
88,2
KPH
250
205,96,0
83,4
KPH
250
212,97,7
85,2
KPH
500
427,510,3
85,5
KPH
500
418,58,8
83,7
KPH
500
434,713,9
86,9
KPH
Carbofuran
Propoxur
1
Bp ci
Carbaryl
Fenobucarb
2
Ci xanh
Carbofuran
Propoxur
Carbaryl
Fenobucarb
58
500
408,27,8
81,6
KPH
500
416,410,4
83,3
KPH
500
406,410,6
81,3
KPH
500
414,87,5
83,0
KPH
500
414,98,7
83,0
Carbofuran
26,61,4
Carbaryl
KPH
Propoxur
KPH
Fenobucarb
KPH
Carbofuran
8,50,5
Rau mng
Carbaryl
KPH
ti
Propoxur
KPH
Fenobucarb
KPH
Carbofuran
Propoxur
3
Rau rn
Carbaryl
Fenobucarb
Rau cn ty
Nhn xt: Kim tra phn tch trn 30 mu rau qu cc loi, pht hin 2 mu
rau c cha d lng carbofuran nhng u mc thp, cha pht hin c mu
no c cha carbaryl, propoxur v fenobucarb. Hiu sut thu hi cc mu thm
chun u t trn 80%.
59
Chng 4. KT LUN
Trn c s cc kt qu thc nghim nghin cu xc nh d lng ha
cht bo v thc vt nhm carbamat trong mt s loi rau qu bng phng php
sc k lng khi ph, chng ti thu c cc kt qu sau:
1. Nghin cu v ti u ha c cc iu kin chy sc k lng
60
61
s ng ngi.
8. S khoa hc v cng ngh tnh An Giang (2007), D lng thuc tr su
vt v nhng tc ng ca chng.
10.
tch.
11.
B. TING ANH
12.
Carbofuran, http://en.wikipedia.org/wiki/Carbofuran
14.
Conacher HB, Page BD, Lau BP, Lawrence JF, Bailey R, Calway P,
62
Zhang
High-performance
(2005),
thin-layer
Feride Koc, Yusuf Yigit, Yavuz Kursad Das, Yasemin Gurel, Cevdet
63
23.
by
flow-injection
analysis
based
on
the
luminol
Mian Liu, Hui Yang, Hongxia Liu, Po Han, Xie Wang, Shusheng
64
using
4,
4-azo-bis-3,35,5-tetrabromoaniline
in
Urmila Tamrakar,
Wang Peng, Li Jing, Huang Xin, Chu Xiaogang, Zhang Yibin (2004),
Determination of Multiclass Pesticide Residues in Apple Juice by Gas
Chromatography-Mass Selective Detection after Extraction by Matrix
Solid-Phase Dispersion, Journal of AOAC INTERNATIONAL, Volume
87, Issue 4, pp. 972-985.
34.
Chao Yan, Pengyuan Yang, Guonan Chen (2006), Rapid separation and
determination of carbamate insecticides using isocratic elution pressurized
capillary electrochromatography, Electrophoresis, Vol. 27, pp 768-777.
35.
Y.
Koteswara,
K.
Lokanath
Swaroop,
P.
Chiranjeevi,
B.
65
PH LC
1. Kho st thnh phn pha ng ch isocractic (HCOOH 0,1% : MeOH)
66
RT: 0.00-5.86
NL: 5.03E5
3.83
100
TICF:+c ESISRMms2
222.00@45.00[164.50-165.50]
MSmix1000ppb-90%MeOH
RelativeAbundance
50
0.14
0
100
0.80 1.07
4.23
2.78
5.15 5.48
4.62
3.78
3.11
NL: 4.91E4
TICF:+c ESISRMms2
50
3.12
1.93
1.54
0.35
3.65
4.17
0.62
5.55
0
100
50
0.50 0.76
1.09
1.48
0
100
2.08
3.26
3.79
4.34
2.87
5.24
50
0.52 0.85
0
0.0
0.5
1.18
1.0
1.37
1.5
2.23 2.63
2.0
2.5
4.67 5.00
3.28 3.48
3.0
Time(min)
3.5
4.0
4.5
NL: 9.23E4
TICF:+c ESISRMms2
208.00@37.00[151.50-152.50]
MSmix1000ppb-90%MeOH
5.59
5.0
5.5
RT: 0.00-7.68
NL:7.29E5
4.36
100
TICF:+ cESISRMms2
222.00@45.00[164.50-165.50]
MSmix1000ppb-80%MeOH
RelativeAbundance
50
0.28
0
100
1.00
1.72 2.19
2.38
4.75
3.63
4.89
5.41 6.14
7.06
NL:7.29E4
4.30
50
0.68
1.14 1.54
TICF:+ cESISRMms2
210.00@45.00[152.50-153.50,
167.50-168.50] MSmix
1000ppb-80%MeOH
4.63
2.00
3.32
2.72
7.00 7.27
4.90 5.49
3.78
0
100
6.34
4.91
NL:1.07E5
TICF:+ cESISRMms2
202.00@45.00[144.50-145.50]
MSmix1000ppb-80%MeOH
5.10
50
2.60 3.06 3.52
1.68 1.941.29
0.96
4.51
100
7.08
NL:9.78E4
TICF:+ cESISRMms2
208.00@37.00[151.50-152.50]
MSmix1000ppb-80%MeOH
50
0.52 0.85
0
0
1.70
1.97
2
2.76
3.28
3
3.88 4.27
4
Time(min)
4.93
5
6.38 6.90
6
7.37
67
NL: 8.38E5
5.29
100
TICF: + c ESISRMms2
222.00@45.00 [ 164.50-165.50]
MSmix1000ppb-70%MeOH
RelativeAbundance
50
2.32
0.94 1.27
0
100
3.05 3.51
4.69
8.97
NL: 6.95E4
5.23
50
7.27
2.60
TICF: + c ESISRMms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS mix
1000ppb-70%MeOH
4.57
3.26 3.78
8.33 8.72
6.22 6.61
0
100
NL: 8.92E4
TICF: + c ESISRMms2
202.00@45.00 [ 144.50-145.50]
MSmix1000ppb-70%MeOH
6.43
50
0.37
1.16
1.88
6.89 7.22
8.20 8.93 9.32
6.10
4.78
NL: 9.49E4
8.29
8.49
100
TICF: + c ESISRMms2
208.00@37.00 [ 151.50-152.50]
MSmix1000ppb-70%MeOH
50
1.25
0.33
0
0
2.04 2.50
5
Time (min)
9.02
5.40
6
100
NL: 8.30E5
TIC F: + c ESISRM ms2
222.00@45.00 [ 164.50-165.50]
MS mix1000ppb-60%MeOH
RelativeAbundance
50
1.53
0
100
6.08
2.85
13.65 14.37
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS mix
1000ppb-60%MeOH
50
1.28 1.81
0
100
7.47
6.81
3.32 3.98
10.56
9.78
8.00
NL: 7.75E4
TIC F: + c ESISRM ms2
202.00@45.00 [ 144.50-145.50]
MS mix1000ppb-60%MeOH
9.65
50
0.96
2.94 3.73
0
100
5.77
7.15
9.46
9.06
15.40 15.53
15.73
15.21
50
1.71
0
0
3.55
4
5.33
6
8
10
Time (min)
12.44
12
15.86
14.81
14.61
14
16.19
16
18
68
NL: 7.32E5
11.48
100
TICF: + c ESISRMms2
222.00@45.00 [ 164.50-165.50]
MSmix1000ppb-50%MeOH
RelativeAbundance
50
1.34 2.92
0
100
12.13 13.85
11.49
11.36 11.62
TICF: + c ESISRMms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS mix
1000ppb-50%MeOH
50
1.61
11.82 13.13
3.52
18.60 20.64
17.82
100
50
15.51 17.49
100
50
2.24
4.01
7.17 7.44
6.65
6.12
27.03
NL: 7.79E4
TICF: + c ESISRMms2
202.00@45.00 [ 144.50-145.50]
MSmix1000ppb-50%MeOH
18.21
18.48 19.79
23.67
18.08
TICF: + c ESISRMms2
11.06
13.56
17.31
12.31
20.61
0
0
10
15
Time (min)
20
25
30
NL: 2.74E6
RT: 8.83
MA: 62596017
100
50
0.24
RelativeAbundance
2.23 3.00
100
14.58
16.73
50
0.94 2.01
3.93 4.47
6.16
8.07
100
15.44
17.20
NL: 1.68E5
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS mix
1000ppb-acetic
50
0.26
2.33
3.86 4.79
6.17 7.24
8.62
100
50
10.31 12.15
RT: 10.87
AA: 2191283
10.41
1.74
0
0
7.57 8.11
8
10
Time (min)
11.18
12
NL: 2.89E5
14.45
16.37
NL: 9.55E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS ICIS mix
1000ppb-acetic
13.86 14.01
17.24
14
16
18
69
NL: 2.02E6
RT: 8.91
MA: 52548096
100
50
0.47 1.62 2.69
RelativeAbundance
4.30 5.22
100
17.89
NL: 2.26E5
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS mix 1000ppb-NH4Ac
50
8.61
6.92
5.16
9.46 10.84
12.76
13.22
16.75 17.90
NL: 2.00E5
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS ICIS mix
1000ppb-NH4Ac
RT: 9.85
AA: 3950325
100
50
9.54
6.63 7.40 8.47
0
100
15.45 16.68
NL: 1.41E5
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS mix
1000ppb-NH4Ac
50
0.59
0
0
2.35 3.04
2
5.35 6.04
4
6.42 8.41
10.56
8
10
Time (min)
14
16.55
16
18
NL: 3.92E6
RT: 8.75
MA: 88164531
100
50
0.24
RelativeAbundance
100
NL: 3.68E5
10.91 12.14
RT: 9.77
MA: 8972544
NL: 4.78E5
50
2.78
0.79
4.78
6.39 7.23
100
12.60
15.52 16.74
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS mix
1000ppb-NH4OH
50
1.26 1.80
3.33 4.10
9.16
6.55 7.09
100
10.31 12.54
RT: 10.87
MA: 5076448
14.91
17.60
NL: 2.68E5
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS mix
1000ppb-NH4OH
50
0
0
0.36 1.59
3.81
6.57 7.65
6.42
6
10.33
8
10
Time (min)
12.17 13.25
12
15.40 16.55
14
16
18
70
NL:3.62E5
RT:8.87
MA:4416725
100
TICF: +c ESISRMms2
222.00@48.00[
164.50-165.50] MS
MeOH-H2O-1-1
50
RelativeAbundance
1.86
0.37
9.22
6.68 7.73
RT:8.88
MA:654621
3.87 4.49
100
9.92 11.85
50
0.73
0
100
7.31
50
1.53
3.28 4.16
6.35
9.14
NL:1.48E4
RT:9.77
MA:238176
9.94
TICF: +c ESISRMms2
202.00@45.00[
144.50-145.50] MS
MeOH-H2O-1-1
11.87 12.92
8.89
5.0
TICF: +c ESISRMms2
210.00@45.00[
152.50-153.50,
167.50-168.50] MS
MeOH-H2O-1-1
14.06
15.64
17.39
3
0
NL:1.96E4
RT:10.84
MA:295354
100
50
0.59 0.85
7.33 8.12
8.91
TICF: +c ESISRMms2
208.00@37.00[
151.50-152.50] MS
MeOH-H2O-1-1
15.13
11.36 12.68
16.97
0
0
8
10
Time(min)
12
14
16
18
MeOH:H2O = 1:1
100
NL: 3.62E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS
MeOH-H2O-1-1
RelativeAbundance
50
0.37
1.86
9.22
6.68 7.73
RT: 8.88
MA: 654621
3.87 4.49
100
9.92 11.85
50
0.73
100
9.14
NL: 1.48E4
RT: 9.77
MA: 238176
8.89
9.94
0
3.28
7.31
50
1.53
4.16
6.35
11.87 12.92
5.03
MeOH-H2O-1-1
14.06
15.64
17.39
NL: 1.96E4
RT: 10.84
MA: 295354
100
50
0.59 0.85
7.33 8.12
8.91
15.13
11.36 12.68
16.97
0
0
8
10
Time (min)
12
14
16
18
MeOH:H2O = 2:1
71
NL: 1.07E6
RT: 8.86
MA:16042383
100
TIC F: + c ESISRMms2
222.00@48.00 [
164.50-165.50] MS
MeOH-H2O-3-1
50
1.50 2.47
RelativeAbundance
3.78
5.01
100
9.65
6.50 7.37
RT: 8.87
MA: 1605778
16.84
NL: 8.83E4
TIC F: + c ESISRMms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MS
MeOH-H2O-3-1
50
3.44 3.79 4.41
0.73
9.14 9.66
16.32 17.29
NL: 6.74E4
RT: 9.76
MA:970162
100
50
3.89 4.59 6.26 6.70
1.61
TIC F: + c ESISRMms2
202.00@45.00 [
144.50-145.50] MS
MeOH-H2O-3-1
10.29
10.64
8.18
13.35 14.32
15.90 17.12
RT:10.84
MA: 877065
100
NL: 8.37E4
TIC F: + c ESISRMms2
208.00@37.00 [
151.50-152.50] MS
MeOH-H2O-3-1
50
1.55
0
0
6.02
7.59
8.73 10.40
8
10
Time (min)
12.06 14.08
12
16.18
14.69
14
16
18
MeOH:H2O = 3:1
100
NL: 9.18E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS
MeOH-H2O-4-1
50
1.42
RelativeAbundance
100
50
0.64
2.39
3.97 4.76
6.16
8.35
16.14 17.19
9.58
NL: 6.36E4
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MS
MeOH-H2O-4-1
16.59
NL: 6.95E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS
MeOH-H2O-4-1
RT: 9.85
MA: 935970
100
50
1.00
4.86
2.67 3.28
10.29 11.25
13.62
15.11
17.56
NL: 3.26E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS
MeOH-H2O-4-1
RT: 11.01
MA: 434899
100
50
1.02
2.25 2.86
8.82 10.66
16.79
0
0
8
10
Time (min)
12
14
16
18
MeOH:H2O = 4:1
72
RT: 0.00-18.04
NL: 1.78E6
RT:9.04
MA:27949229
100
TICF: +c ESISRMms2
222.00@48.00 [ 164.50-165.50]
MSchiet bang diclometan
50
0.80 1.68
RelativeAbundance
9.57 11.32
5.18 6.50 7.55
RT:9.05
AA: 2633800
3.26
100
13.25 14.56
16.31
NL: 1.57E5
TICF: +c ESISRMms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS ICISchiet
bang diclometan
50
0
RT:10.03
AA:1843101
100
NL: 1.37E5
TICF: +c ESISRMms2
202.00@45.00 [ 144.50-145.50]
MS ICISchiet bang diclometan
50
0
NL: 8.79E4
RT:11.10
AA:980813
100
TICF: +c ESISRMms2
208.00@37.00 [ 151.50-152.50]
MS ICISchiet bang diclometan
50
0.85
2.43
9.79
7.07 7.95
4.18
8
10
Time(min)
12
17.93
14
16
18
NL: 5.29E5
RT: 8.95
MA:7225108
100
TIC F: + c ESISRMms2
222.00@48.00 [ 164.50-165.50]
MS chiet bang n-hexan
50
10.18 11.14
1.24 2.03 3.43 4.57 6.32 6.59 8.34
RT:8.96
AA: 853691
RelativeAbundance
0
100
16.75
13.33 14.21
NL: 7.26E4
TIC F: + c ESISRMms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS ICIS chiet
bang n-hexan
50
0
RT: 9.85
AA: 916035
100
NL: 6.91E4
TIC F: + c ESISRMms2
202.00@45.00 [ 144.50-145.50]
MS ICIS chiet bang n-hexan
50
0.65 1.70
10.29
8.36
12.39
14.32
16.68 17.56
NL: 8.83E4
RT: 11.01
MA: 1380078
100
TIC F: + c ESISRMms2
208.00@37.00 [ 151.50-152.50]
MS chiet bang n-hexan
50
1.72
0
0
12.85
8
10
Time (min)
12
16
18
73
NL: 1.05E6
RT: 8.90
AA: 16288884
100
TICF: + c ESISRMms2
222.00@48.00 [
164.50-165.50] MS ICISmix
200ppb
50
1.15
RelativeAbundance
3.00 3.69
9.448.14
5.22
MA:1788709
100
TICF: + c ESISRMms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MSmix
200ppb
50
2.47 3.24
1.01
5.08
6.69
8.53
100
10.68 10.91
RT: 9.92
MA:1370381
13.52
15.97 16.74
NL: 7.57E4
TICF: + c ESISRMms2
202.00@45.00 [
144.50-145.50] MSmix
200ppb
50
0.33 1.87 2.86
4.78 5.47
12.84
10.77
14.37 15.45
17.59
NL: 5.20E4
RT:10.94
AA:762900
100
TICF: + c ESISRMms2
208.00@37.00 [
151.50-152.50] MS ICISmix
200ppb
50
0
0
8
10
Time (min)
12
14
16
18
RT: 8.83
MA: 15323127
100
50
1.39 2.15 3.61
RelativeAbundance
5.38
6.76 7.98
9.29 10.90
RT: 8.84
MA: 1743626
100
17.42
NL: 1.01E5
TIC F: + c ESI SRMms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS CH2Cl2-hexan-1-2
50
0.17
6.92 7.23
9.84
16.05 17.74
NL: 6.34E4
RT: 9.77
MA: 990046
100
50
1.10
0
2.48
4.09
5.32 7.55
7.78
10.15
9.39
12.53
RT: 10.87
MA: 581813
100
50
1.35 2.43
0
0
3.66
4
6.65
6
9.72
11.25
8
10
Time (min)
12
6.80 7.80
13.94 14.78
14
17.16
16
18
74
NL: 1.01E6
RT: 8.91
MA: 16221063
100
50
0.78 2.16 3.00
RelativeAbundance
10.29
6.38 7.30 7.99
RT: 8.84
MA: 1619068
4.30
100
50
1.09 1.86 3.17
4.93
6.31
10.15
8.00
16.36
NL: 9.48E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS
CH2Cl2-hexan-1-1
RT: 9.85
MA: 1273289
100
50
2.26
2.49
5.17
100
11.00 12.23
RT: 10.95
MA: 725971
14.22 15.22
17.60
NL: 5.54E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS
CH2Cl2-hexan-1-1
50
1.74 1.97
0
0
8.88 10.72
3.50
8
10
Time (min)
11.56 12.10
12
16.85
14.86
14
16
18
NL: 9.71E5
RT: 8.91
MA: 15246098
100
50
RelativeAbundance
17.35
NL: 1.11E5
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS CH2Cl2-hexan-2-1
50
0.10
5.77 6.77
8.61
100
10.68 11.30
RT: 9.85
AA: 1025568
13.06
15.44
17.59
NL: 6.71E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS ICIS
CH2Cl2-hexan-2-1
50
0.72 1.87 3.02
4.79
6.47 8.85
9.54
17.22
RT: 10.95
MA: 445020
100
50
8.95 9.34
11.79
NL: 3.19E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS
CH2Cl2-hexan-2-1
13.86
15.63
17.77
0
0
8
10
Time (min)
12
14
16
18
75
NL: 1.03E6
TICF: +c ESISRMms2
222.00@48.00 [
164.50-165.50] MS
CH2Cl2-hexan-3-1
RT:8.98
MA: 15646460
100
50
RelativeAbundance
9.52 10.90
3.22 4.37 5.91 6.52 7.67
RT: 8.91
MA:1413457
0.54 1.69
0
100
13.43
7
TICF: +c ESISRMms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MSCH2Cl2-hexan-3-1
50
1.62 2.47 3.39
5.46 7.68
8.61
10.29 11.37
13.29
15.28 16.74
NL: 7.33E4
RT: 9.92
MA: 1042118
100
TICF: +c ESISRMms2
202.00@45.00 [
144.50-145.50] MS
CH2Cl2-hexan-3-1
50
0.64
2.33
4.55 5.09
14.52 15.44
10.76 11.69
17.82
NL: 3.89E4
RT: 11.02
MA: 533507
100
TICF: +c ESISRMms2
208.00@37.00 [
151.50-152.50] MS
CH2Cl2-hexan-3-1
10.86
50
1.04
3.34
8.33
9.94
NL: 9.69E4
11.86
13.39
16.92
14.85
0
0
8
10
Time (min)
12
14
16
18
RT: 8.98
MA: 9661932
100
50
0.93
RelativeAbundance
100
8.68
9.52
RT: 8.92
MA: 810528
50
0.40 2.55 2.86
4.47
6.62 7.61
0
100
50
0.34 1.95
3.41
NL: 5.93E4
9.15
9.46 9.92 11.60 13.37
13.75
RT: 9.93
AA: 483706
17.42
15.37
16.28
NL: 3.00E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS ICIS the tich rua giai 20ml
16.45
NL: 1.51E4
RT: 10.95
AA: 250995
100
50
0.44
2.05
4.73
3.43
6.11 6.50
8.95
10.56
11.79 13.40
15.09 16.32
0
0
8
10
Time (min)
12
14
16
18
76
NL: 8.61E5
RT: 8.98
MA: 14658407
100
50
1.00 1.84
RelativeAbundance
9.75
RT: 8.99
MA: 1414805
6.45 7.14
3.76 4.61
100
11.36 12.28
14.27
15.88 16.57
NL: 1.13E5
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS the tich rua
giai 40ml
50
1.55 2.55
4.08
8.61
5.84 6.69
16.36
RT: 9.85
MA: 935027
100
NL: 6.43E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS the tich rua giai 40ml
50
0.33 1.41
3.63
4.94
6.55 7.31
9.00
15.91 16.06
100
10.61
RT: 10.94
MA: 722695
13.37
NL: 6.02E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS the tich rua giai 40ml
11.10
50
0.81
2.73
8.10
10.63
8
10
Time (min)
11.56
12
14
16
18
NL: 1.12E6
RT: 8.96
MA: 15748852
100
50
RelativeAbundance
0 0.28
2.38 3.61
4.93
6.77 7.64
9.66 10.53 12.55 13.69
RT: 8.97
MA: 1662739
100
16.31 17.45
NL: 1.22E5
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS the tich rua
giai 50ml
50
0.91 1.87
100
16.76
NL: 6.87E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS ICIS the tich rua giai 50ml
50
2.76 3.81 4.86 5.74
0.30
6.52
10.90 12.04
RT: 11.01
AA: 720851
100
50
1.64
4.27 4.62
0
0
10.58
8
10
Time (min)
11.98 13.29
12
17.85
13.91
14
16
18
77
NL: 1.07E6
RT: 8.90
MA: 15587186
100
50
0.39
RelativeAbundance
9.29 10.446.37
12.89
14.124.53
RT: 8.84
MA: 1719752
2.69
100
8.37
16.34
NL: 1.09E5
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS the tich rua
giai 60ml
50
4.23
7.23
5.54
15.05 15.74
RT: 9.92
MA: 1159284
100
NL: 7.02E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS the tich rua giai 60ml
50
3.40
0.26 1.18
8.23 9.62
6.09 6.39
11.46 12.84
RT: 10.94
MA: 627767
100
50
4.65
2.58 2.73
8.79 9.25
6.65 7.34
NL: 3.90E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS the tich rua giai 60ml
11.71 13.17
13.63 15.31 16.47
0
0
8
10
Time (min)
12
14
16
18
1.51
100
3.40
0.68
4.49
12.68
0
100
NL: 1.19E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS cam
12.26
3.06
5.29
0.43
1.04
0.89
2.25
10.81
17.56
6.50
3.12
50
6.91 7.75
4.24
0
100
15.06 16.29
12.39 14.45
6.83
5.21
50
12.89
3.78 5.10
0
100
6.37
6.72
14.56
10.00 10.96
9.34
11.71
10.03
7.36 8.19
10.17
9.33
6.71
5.00 6.31 10.78
50 0.05 1.54
NL: 5.67E3
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS cam
5.89
50
RelativeAbundance
13.65 13.82
15.79
15.49
17.11
11.06
7.65
5.41
15.87
NL: 1.10E4
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS cam
12.75
13.01 14.33 15.47
3.24 4.60
17.70
0
0
8
10
Time (min)
12
14
16
78
100
RelativeAbundance
2.96
2.40 3.40 4.72 5.33
0.60
50
0
100
2.06
0.79
50
5.03
2.80
4.64
5.91
3.37
NL: 9.58E3
TIC F: + c ESISRMms2
12.12
9.75
8.62
12.95
10.98
14.57 15.84
17.95 202.00@45.00 [
7.70
8.45
10.77
9.46
7.40
15.90
13.75 14.06
11.82
16.25
TIC F: + c ESISRMms2
208.00@37.00 [
151.50-152.50] MSrau cai
6.48
0
100
1.16 2.52
6.02
50
0
100
9.56
11.05 13.02
1.28 8.37
3.91
0.45
2.94
50
5.40
12.93
14.99
13.19
16.43
NL: 1.26E4
TIC F: + c ESISRMms2
222.00@48.00 [
17.40 164.50-165.50] MSrau cai
0
0
10
Time (min)
12
14
16
1.47
2.48 3.62
4.58
0.64
50
NL: 1.13E4
14.04
100
5.24
6.81 7.86
5.54
9.09 10.10
10.67
12.73
14.35
RelativeAbundance
16.23
0
100
3.76
1.61
3.06
6.52
8.53 9.41
9.63
10.24
4.28 6.43
5.73
12.78
50
13.92
16.81
16.55
NL: 8.76E3
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS rau
thom
14.05
0
100
11.53
0.10
50
0
100
0.97
50
9.87
6.98
7.67
5.91 6.44
5.43
2.45 3.02 3.72
6.66
3.90
12.76 13.07
10.65
9.20
10.86
11.87
13.40 13.93
14.54 15.46
17.43
NL: 1.01E4
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS rau
thom
0
0
8
10
Time (min)
12
14
16
79
NL: 9.37E3
8.00
100
0.60 1.48
2.57
TIC F: + c ESISRMms2
9.05 9.71
4.76 15.84
5.07
6.99
5
11.07 12.69
6.73
50
RelativeAbundance
16.24 202.00@45.00 [
13.65
4.1
14.00
0
100
7.58
13.23
6.39
14.45 16.07
16.95
9.02
2.41
50
10.77
4.90
12.00
0
100
11.36
6.41 7.03
50
1.46 2.21
9.31
TIC F: + c ESISRMms2
10.40
9.73
7.32
6.10
6.49
0
100
17.10 210.00@45.00 [
13.73
12.98 14.91
5.10
3.65
NL: 8.06E3
TIC F: + c ESISRMms2
208.00@37.00 [
151.50-152.50] MSrau den
13.84
152.50-153.50,
167.50-168.50] MSrau den
13.63
14.38 15.30
8.68
NL: 1.66E4
TIC F: + c ESISRMms2
222.00@48.00 [
164.50-165.50] MSrau den
6.36
11.00
50
12.36
17.40
5.31
0
0
8
10
Time (min)
12
14
16
6.27
50
RelativeAbundance
NL: 1.48E6
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS rau den-tc
500ng
RT: 8.85
MA: 30438356
100
8.46
15.21
4.52
17.44
NL: 1.72E5
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS rau den-tc 500ng
RT: 8.87
MA: 3096701
100
50
9.00
4.97 5.97 7.03
8.47
9.65 10.49
17.58
NL: 9.44E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS rau den-tc
500ng
RT: 10.06
MA: 1570040
10.15
100
2.39
50
0.51
3.88
6.25 6.42
8.96 9.67
10.37
11.11 13.56
15.18
17.51
NL: 6.43E4
RT: 11.78
MA: 1102168
11.91
100
50
11.56
1.66 2.23 3.89
0
0
5.12 6.04
6
7.92
9.24
8
10
Time (min)
12.04
12.26 13.44
12
14
15.55 15.98
16
80
NL: 1.38E6
RT: 8.76
MA: 30634148
100
50
RelativeAbundance
0
100
15.33 16.39
NL: 1.56E5
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS rau thom-tc 500ng
8.95
50
0.50
6.58 6.89
8.47
9.08 9.78
12.59
14.60 15.39
17.80
RT: 10.01
MA: 1520063
100
NL: 9.02E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS rau
thom-tc 500ng
10.14
50
1.38
3.22
6.73
5.37
8.87
9.75
10.54 12.03
12.60 15.01 15.93
NL: 7.28E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS rau
thom-tc 500ng
RT: 11.78
MA: 1162608
100
11.51
50
0.26 1.88
0
0
11.99
12.43 14.10
15.76
3.32
4
8
10
Time (min)
12
14
17.82
16
NL: 1.47E6
RT: 8.77
MA: 31082281
100
50
0.58
RelativeAbundance
9.20 9.73
5.53 6.71 8.07
RT: 8.78
MA: 3153493
8.69
2.46 3.60
100
8.60
50
0.11
0.76
3.52
6.89
5.36
8.52
11.04 13.32
15.73 17.00
NL: 1.61E5
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS rau cai-tc 500ng
8.95
9.30 10.40 12.15
14.65
16.84
NL: 1.13E5
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS rau cai-tc
500ng
RT: 10.02
MA: 1660425
100
50
9.62
0.86 1.61
7.65
3.97 4.58
10.15
8.35
11.59
16.23
13.83
RT: 11.65
MA: 1082094
100
NL: 7.32E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS rau cai-tc
500ng
11.82
50
1.31 2.19
0
0
9.24
8
10
Time (min)
11.25
11.95 12.87
12
15.98 17.17
14
16
81
NL: 8.97E5
RT: 8.98
MA: 14023139
100
50
1.39
RelativeAbundance
2.84
4.22
5.61 6.60
100
10.06
8.44
RT: 8.92
MA: 1460845
50
8.69
2.62
2.16
6.46
3.93 5.08
NL: 6.20E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS cam-tc
250ng
50
0.56
8.31
5.17 5.70
2.25 3.10
10.31
12.53
16.91
14.37
NL: 4.03E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS cam-tc
250ng
RT: 11.02
MA: 585526
100
50
0.97
2.96
4.35
6.95 7.41
0
0
14.55 14.93
13.01
8.87 10.64
8
10
Time (min)
NL: 9.86E4
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MS cam-tc
250ng
17.12 17.28
9.53
11.37 12.90 13.98
RT: 9.85
MA: 811777
100
17.42
12
14
17.77
16
18
NL: 9.95E5
RT: 8.90
MA: 14786230
100
50
RelativeAbundance
0
100
12.05
13.89
16.34 17.42
50
1.55 2.32 3.16 4.85
6.38 7.46
RT: 9.85
MA: 786793
100
50
0.26
2.48
3.94
9.46
5.40 6.47 8.08 8.77
100
10.08
10.61
11.61 13.53
RT: 10.94
MA: 615061
14.99
17.13
NL: 5.65E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS bap cai-tc
250ng
50
2.81
0.43
0
0
4.27 5.49
4
10.64
8
10
Time (min)
NL: 1.29E5
11.25
12
16
18
82
6.79
100
6.05
0.83
50
10.87
10.56 11.79
13.58 14.15
4.65 5.39
0
100
10.26
0.85
1.24
NL: 1.53E4
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS rau cai
17.61 ngot
12.31
7.67
2.41
1.75
RelativeAbundance
8.98
8.54
11.31
11.84
8.99 9.56
13.11 14.25
50
14.78
0
100
NL: 1.46E4
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50,
17.67 167.50-168.50] MS rau cai
ngot
8.30
2.52
1.47 2.08 2.78
50
0.37
0
100
0.60
11.50
3.88
5.41
9.66 10.27
12.38
10.07 10.81
5.16
4.72
6.08 7.18 8.23 9.54
2.05 2.14
1.66
5.06
7.25 8.43
NL: 8.25E3
TIC F: + c ESI SRM ms2
208.00@37.00 [
14.01
12.48
12.56 15
2.66
50
NL: 1.22E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS rau cai
ngot
1.50-152.
50] MS r
au cai
8
10
Time (min)
12
14
16
TICF: +c ESISRMms2
222.00@48.00 [
164.50-165.50] MScan tay
8.81
50
RelativeAbundance
NL: 3.63E5
RT:9.03
MA:7157181
100
1.18
2.81 3.68
8.72
AA:197083
RT:7.63
5.35 7.32 8.41 9.33 11.22 AA: 144010
12.31 13.41 14.63
RT: 8.86
RT: 3.78
100
AA:142037
AA:160150
RT:10.44
17.52
AA:62987
RT:17.81
50
0
RT: 1.51
100
RT: 3.66
RT:6.51
AA:22677
RT:9.66
AA:32743
AA:32696 AA:20863
50
RT:13.30
RT:11.54
AA:43206 AA:62916
NL: 7.58E3
202.00@45.00 [
144.50-145.50] MS ICIScan
tay
RT:11.07
RT: 7.09
AA:85774
RT:1.57
AA: 30051
50
RT:4.50
AA:33664
RT:12.87
AA: 93405 AA:60167
167.50-168.50] MS ICIScan
tay
0
100
NL: 1.47E4
TICF: +c ESISRMms2
210.00@45.00 [
152.50-153.50,
RT:15.26
RT: 16.02
AA: 56238
NL: 1.05E4
TICF: +c ESISRMms2
208.00@37.00 [
151.50-152.50] MS ICIScan
tay
0
0
8
10
Time (min)
12
14
16
83
8.77
50
5.70 6.31
0
RelativeAbundance
NL: 1.12E5
RT: 8.94
MA: 2006583
100
7.37 8.68
9.34
11.83
13.32 13.67
16.61 17.70
NL: 1.28E4
100
0.94 2.47
1.20
50
5.58
2.82
3.57
7.33
16.36
8.95 9.04
13.29 13.51
7.68
11.06
14.04 14.96
9.65
17.58
5.10
0
100
2.04 2.79
4.06
5.33
1.34
50
6.51
NL: 9.45E3
TIC F: + c ESI SRM ms2
14.66
15.76
[
17.86 202.00@45.00
144.50-145.50] MS mung toi
NL: 1.41E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS mung toi
10.86
100
1.22
50
2.67
4.68
9.55
11.30
11.69
14.54
13.62
17.91
14.76
0
0
8
10
Time (min)
12
14
16
84