MC LC

M U..........................................................................................................1
Chng 1. TNG QUAN...............................................................................3
1.1 Gii thiu v ha cht bo v thc vt.........................................................................3
1.1.1 nh ngha.............................................................................................................3
1.1.2. Phn loi [9].........................................................................................................3
1.1.3. Tc hi ca ha cht bo v thc vt [9]..............................................................4
1.1.4. Tnh hnh tn d ha cht bo v thc vt trong rau qu.....................................5
1.1.5. Tnh hnh ng c ha cht bo v thc vt........................................................6
1.2. Gii thiu v ha cht bo v thc vt nhm carbamat..............................................7
1.2.1. Gii thiu chung...................................................................................................7
1.2.2. Carbofuran [13]....................................................................................................8
1.2.3. Carbaryl [20]........................................................................................................9
1.2.4. Fenobucarb [21]...................................................................................................9
1.2.5. Propoxur [22].....................................................................................................10
1.2.6. Gii hn cho php .............................................................................................11
1.3. Cc phng php xc nh .......................................................................................11
1.3.1. Phng php cc ph.........................................................................................11
1.3.2. Phng php quang ph hp th phn t...........................................................12
1.3.3. Phng php phn tch dng chy (flow injection analysis FIA)...................13
1.3.4. Phng php in di mao qun..........................................................................15
1.3.5. Phng php sc k lng hiu nng cao............................................................16
1.3.6. Phng php sc k kh.....................................................................................17
1.3.7. Phng php sc k lng khi ph....................................................................18

Chng 2. I TNG V PHNG PHP NGHIN CU..............20

2.1. i tng, mc tiu v ni dung nghin cu ...........................................................20
2.1.1. i tng v mc tiu nghin cu.....................................................................20
2.1.2. Ni dung nghin cu..........................................................................................20
2.1.2.1 Xy dng phng php................................................................................20
2.1.2.2. ng dng phng php...............................................................................21
2.2. Phng php nghin cu...........................................................................................21
2.2.1. Phng php tch chit mu..............................................................................21
2.2.2. Phng php sc k lng khi ph....................................................................21
2.2.2.1. Nguyn tc chung v phng php HPLC..................................................21
2.2.2.2. Pha tnh trong HPLC...................................................................................22
2.2.2.3. Pha ng trong HPLC.................................................................................23
2.2.2.4. Detector trong HPLC..................................................................................24
2.2.2.5 Detector khi ph (Mass Spectrometry)......................................................24
2.3. Phng tin nghin cu.............................................................................................29
2.3.1. Thit b, dng c.................................................................................................29
2.3.1.1. Thit b........................................................................................................29
2.3.1.2. Dng c.......................................................................................................29
2.3.3. Dung mi, ha cht............................................................................................30

Chng 3. KT QU V THO LUN....................................................32

3.1. Ti u cc iu kin xc nh carbamat bng LC/MS/MS.......................................32

3.1.1. Chn cc iu kin chy ca detector khi ph.................................................32

3.1.1.1. Kho st iu kin bn ph i vi ion m.................................................32
3.1.1.2. Kho st iu kin bn ph ion con ............................................................34
3.1.2. Chn pha tnh.....................................................................................................36
3.1.3. Chn pha ng...................................................................................................36
3.2. nh gi phng php phn tch..............................................................................39
3.2.1. Kho st lp ng chun..................................................................................39
3.2.2. Gii hn pht hin LOD [10].............................................................................43
3.2.3. Gii hn nh lng LOQ [10]..........................................................................44
3.2.4. chnh xc ca php o..................................................................................45
3.3. Kho st iu kin x l mu.....................................................................................46
3.3.1. Kho st dung mi chit.....................................................................................47
3.3.2. Kho st dung mi ra gii................................................................................49
3.3.3. Kho st th tch dung mi ra gii...................................................................51
3.3.4. lp li v thu hi ca phng php.........................................................52
3.4. Phn tch mu thc t................................................................................................54

Chng 4. KT LUN.................................................................................60
TI LIU THAM KHO............................................................................61
PH LC.......................................................................................................66

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).

Mc tiu thc hin ti lun vn l:

1. Xy dng phng php xc nh d lng ha cht bo v thc vt

carbamat trong rau qu, bao gm:

Kho st cc iu kin tch chit mu v phn tch

Thm nh phng php xy dng

2. p dng phng php xc nh d lng thuc bo v thc vt

carbamate kho st mt s mu rau qu trn a bn H Ni.

Chng 1. TNG QUAN

1.1 Gii thiu v ha cht bo v thc vt
1.1.1 nh ngha
Ha cht bo v thc vt l nhng hp cht c ngun gc t nhin hoc tng
hp ha hc c dng phng v tr sinh vt gy hi cy trng v nng sn. Ha
cht bo v thc vt gm nhiu nhm khc nhau, gi theo tn nhm sinh vt gy
hi, nh thuc tr su dng tr su hi, thuc tr bnh dng tr bnh cy
1.1.2. Phn loi [9]
Cc loi ha cht bo v thc vt gm nhiu loi, ch yu gm 4 nhm
chnh:
- Nhm Clo hu c (organnochlorine) l cc dn xut clo ca mt s hp
cht hu c nh diphenyletan, cyclodien, benzen, hexan. Nhm ny bao gm nhng
hp cht hu c rt bn vng trong mi trng t nhin v thi gian bn phn hu
di (v d nh DDT c thi gian bn phn hu l 20 nm, chng t b o thi v
tch lu vo c th sinh vt qua chui thc n). i din ca nhm ny l Aldrin,
Dieldrin, DDT, Heptachlo, Lindan, Methoxychlor
- Nhm ln hu c (organophosphorus) u l cc este, l cc dn xut hu
c ca acid photphoric. Nhm ny c thi gian bn phn hu ngn hn so vi nhm
Clo hu c v c s dng rng ri hn. Nhm ny tc ng vo thn kinh ca
cn trng bng cch ngn cn s to thnh men Cholinestaza lm cho thn kinh
hot ng km, lm yu c, gy chong vng v cht. Nhm ny bao gm mt s
hp cht nh parathion, malathion, diclovos, clopyrifos
- Nhm Carbamat l cc dn xut hu c ca acid cacbamic, gm nhng ho
cht t bn vng hn trong mi trng t nhin, song cng c c tnh cao i vi
ngi v ng vt. Khi s dng, chng tc ng trc tip vo men Cholinestraza
ca h thn kinh v c c ch gy c ging nh nhm ln hu c. i din cho
nhm ny nh: carbofuran, carbaryl, carbosulfan, isoprocarb, methomyl

- Nhm Pyrethroid l nhng thuc tr su c ngun gc t nhin, l hn hp

ca cc este khc nhau vi cu trc phc tp c tch ra t hoa ca nhng ging
cc no . i din ca nhm ny gm cypermethrin, permethrin, fenvalarate,
deltamethrin,
Ngoi ra, cn c mt s nhm khc nh: cc cht tr su v c (nhm asen),
nhm thuc tr su sinh hc c ngun gc t vi khun, nm, virus (thuc tr nm,
tr vi khun), nhm cc hp cht v c (hp cht ca ng, thy ngn, ).
1.1.3. Tc hi ca ha cht bo v thc vt [9]
Hu ht ha cht bo v thc vt u c vi con ngi v ng vt mu
nng cc mc khc nhau. Theo c tnh ha cht bo v thc vt c chia
lm hai loi: cht c cp tnh v cht c mn tnh.

Cht c cp tnh: Mc gy c ph thuc vo lng thuc xm

nhp vo c th. di liu gy cht, chng khng kh nng gy t

vong, dn dn b phn gii v bi tit ra ngoi. Loi ny bao gm cc hp
cht Pyrethroid, nhng hp cht Pht pho hu c, Carbamat, thuc c
ngun gc sinh vt.

Cht c mn tnh: C kh nng tch lu lu di trong c th v chng

rt bn, kh b phn gii v bi tit ra ngoi. Thuc loi ny gm nhiu hp

cht cha Clo hu c, cha Thch tn (Asen), Ch, Thu ngn; y l
nhng loi rt nguy him cho sc kho.
Ha cht bo v thc vt c th thm nhp vo c th con ngi v ng vt
qua nhiu con ng khc nhau; thng thng qua 03 ng chnh: h hp, tiu
ho v tip xc trc tip. Khi tip xc vi ha cht bo v thc vt, con ngi c
th b nhim c cp tnh hoc mn tnh, ty thuc vo phm vi nh hng ca
thuc.
Nhim c cp tnh: L nhim c tc thi khi mt lng ln ho cht
bo v thc vt thm nhp vo c th. Nhng triu chng nhim c tng t l vi

vic tip xc v trong mt s trng hp nng c th dn ti t vong. Biu hin

bnh l ca nhim c cp tnh: mt mi, nga da, au u, lm ging, bun nn,
hoa mt chng mt, kh hng, mt ng, tng tit nc bt, yu c, chy nc mt,
sy thai, nu nng c th gy t vong.
Nhim c mn tnh: L nhim c gy ra do tch lu dn dn trong c th.
Thng thng, khng c triu chng no xut hin ngay trong mi ln nhim. Sau
mt thi gian di, mt lng cht c ln tch t trong c th s gy ra cc triu
chng lm sng. Biu hin bnh l ca nhim c mn tnh: kch thch cc t bo
ung th pht trin, gy qui thai, d dng, suy gim tr nh v kh nng tp trung,
suy nhc nghim trng, nh hng n h thn kinh, gy tn hi cho gan, thn v
no.
1.1.4. Tnh hnh tn d ha cht bo v thc vt trong rau qu
Theo bo co ca Cc Bo v thc vt, c 23% s h nng dn vi phm quy
nh v s dng thuc bo v thc vt, dn n tn d ha cht bo v thc vt trn
nng sn. Mt s loi thuc tr su c hi b cm s dng nhng hin vn c
nhiu ngi tm cch a v nng thn. S mu rau, qu ti c d lng ha cht
bo v thc vt chim t 30-60%, trong s mu rau, qu c d lng ha cht
bo v thc vt vt qu gii hn cho php chim t 4-16%, mt s ha cht bo v
thc vt b cm s dng nh Methamidophos vn cn d lng trong rau. [7]
Trong nm 2006, Chi cc bo v thc vt TP H Ch Minh kim tra 790
mu ca 52 n v kinh doanh rau an ton trn a bn thnh ph, pht hin 26 mu
c d lng thuc tr su, chim t l 3,29%. Nm rm Tr Vinh, cn ty, ci tha,
x lch xong, b ngt, bng ci xanh (sp l), rau dn, cn... l nhng loi rau n l
c t l d lng thuc tr su cao (3,94%). c bit l tnh trng vt nhim thuc
tr su i vi cc loi rau c qu, tri cy nhp khu t Trung Quc. Kt qu kim
tra ca Chi cc bo v thc vt TP.HCM cho thy, c 5 trong tng s 26 mu hng
Trung Quc c kim tra c kt qu lng thuc tr su tn d cao, chim t l
n 19,23%. [3]

u nm 2009, Cc Bo v thc vt ly 25 mu rau v nm mu qu ti

cc tnh pha Bc (TP H Ni v tnh Vnh Phc) kim nh. Kt qu c 11 mu
rau c d lng thuc bo v thc vt mc khc nhau. cc tnh pha Nam,
trn 35 mu rau v 5 mu qu ly TP H Ch Minh, Bnh Dng, Tin Giang, kt
qu trn 50% mu c d lng thuc bo v thc vt mc khc nhau. [11]
Ti TP H Ch Minh, trong su thng u nm 2009, qua kim nghim hn
2.200 mu rau, qu ti ba ch u mi (Bnh in, Hc Mn, Th c), pht hin
50 mu dng tnh (t l 2,4%), cao hn so vi cng k nm 2008 l 1,3%. Cn ti
Bnh Dng, phn tch gn 310 mu rau ly cc ch, vng sn xut, bp n tp
th trong tm thng u nm 2009 c gn 80 mu c d lng thuc bo v thc
vt. [11]
Trn th gii, ti n , Cuc iu tra c B Nng nghip n tin
hnh trong mt nm t thng 11 nm 2007 n thng 10 nm 2008 trn ton t
nc n . Kt qu l 18% rau v 12% hoa qu ni a v nhp khu ca n
u c d lng thuc tr su, k c nhng loi thuc tr su b cm, trong 4%
lng rau v 2% lng hoa qu c d lng thuc tr su cao hn mc cho php.
Khong 18% (664 mu) trong tng s 3.648 mu rau nh mp ty, c chua, bp
ci v sp l u c d lng thuc tr su. Cc loi rau nh bp ci, sp l v c
chua c d lng thuc tr su ln nht. Cc loi thuc tr su tm thy trong cc
loi qu ch yu l chlorpyriphos, monocrotophos, profenophos v cypermethrin.[1]
1.1.5. Tnh hnh ng c ha cht bo v thc vt
Theo thng k ca T chc Lao ng Quc t ILO, trn th gii, hng nm
c trn 40.000 ngi cht v ng c rau trn tng s 2 triu ngi ng c. Ti
Vit Nam, con s ngi b ng c cng khng nh. T nm 1993 - 1998, hng
chc ngn ngi b nhim c do n phi rau qu cn d lng thuc tr su. Nng
nht ng bng sng Cu Long, nm 1995 c 13.000 ngi nhim c, trong
c 354 ngi cht. [8]

Nm 1990, mt thng k qu ca T chc y t th gii (WHO) cho thy c

khong 25 triu lao ng trong ngnh nng nghip b nhim c ha cht bo v
thc vt mi nm. Cho n nay, chng ta vn cha c nhng con s c tnh trn
phm vi ton cu, nhng hin c n 1,3 t lao ng trong ngnh nng nghip v c
th hng triu ca nhim c ha cht bo v thc vt vn ang xy ra hng nm. [2]
Nm 2000, B y t Braxin c tnh trong mt nm nc ny c 300.000 ca
nhim c v 5.000 ca t vong do ha cht bo v thc vt. Trong mt nghin cu
Innxia, 21% trong s cc ca lin quan n ha cht bo v thc vt c nhng
du hiu hay triu chng v tm thn, h hp v tiu ho. Trong mt cuc kho st
ca Lin hp quc, 88% nng dn Campuchia s dng ha cht bo v thc vt
tng c triu chng nhim c. [2]
1.2. Gii thiu v ha cht bo v thc vt nhm carbamat
1.2.1. Gii thiu chung
Thuc tr su carbamat l cc dn xut ca acid cacbamic c tnh c tr
su. Cc thuc carbamat thng khng c tnh c vn nng nh thuc ln hu c.
Nhiu hp cht trong nhm tuy c hiu lc cao vi su hi nhng khng c tc
dng tr nhn hoc ch c tc dng tr mt s thuc nhm ny m khng tr c
nhm su khc. Mt s thuc trong nhm cn c c tc dng tr tuyn trng.
V c ch tc ng ca thuc tr su carbamat tng t nh cc thuc tr
su ln hu c. Cc thuc carbamat km hm men cholinesteraza bng cch
cacbaryl ha cc v tr hot ng ca ton men. Qu trnh cacbaryl ha cng l qu
trnh thun nghch. Nhng s lin kt gia cc thuc carbamat vi cholinesteraza
thng khng bn, nn c trng hp su hi phc hi c. Cc thuc ln hu c
ch kt hp vi cc gc hot ng ca men, nn cc thuc ln hu c c thy
phn cng mnh, cng d gy c cho cn trng ; ngc li cc thuc carbamat ch
c ch c men cholinesteraza khi ton b phn t ca chng gn c ln b mt
ca men. Cc cht carbamat cng bn, cng c ch men cholinesteraza mnh. C
ln hu c v carbamat u km hm v tr men tc ng, dn n h thn kinh

khng kim sot c, lm mt kh nng phi hp gia cc c quan, gii phng qu

mc hormon, sinh vt mt nc v cht.
Cc thuc carbamat an ton vi cy, t c i vi c hn cc thuc ln hu
c; khng tn lu qu lu trn nng sn v mi trng sng. c ca thuc i
vi ng vt mu nng rt khc nhau, ty thuc vo loi thuc.
Cc cht ch yu thuc nhm bao gm: carbaryl, methiocarb, pirimicarb,
oxamyl, carbendazim, propoxur, aminocarb, aldicarb
1.2.2. Carbofuran [13]
Carbofuran l mt trong nhng thuc tr su nhm carbamat c nht, c tn
l 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate, tn thng mi l
Furadan, Curater.

Cng thc phn t: C12H15NO3.

M = 221,25g/mol.
tnc = 151C.
d = 1,18g/cm3.
Carbofuran l mt trong nhng thuc tr su c c tnh cao i vi con
ngi. N c th xm nhp vo c th qua h hp, qua ming v qua da. Triu
chng khi b ng c carbofuran: bun nn, au bng, tiu chy, gim tm nhn
liu cao c th gy t vong. Ch cn ung 1ml carbofuran cng c th dn ti t
vong.
Theo WHO, mc hp th hng ngy cho php (ADI) ca carbofuran l
0,01mg/kg trng lng c th. Liu gy cht trung bnh i vi chut qua ming l
LD50 = 5mg/kg.

1.2.3. Carbaryl [20]

Carbaryl c tn l 1-naphthyl methylcarbamate, tn thng mi l Sevin, l
mt loi thuc tr su nhm carbamat. Carbayl l tinh th mu trng, tan km trong
nc nhng tan nhiu trong dung mi phn cc nh imethyl sulfoxide v imethyl
formaldehyde.

Cng thc phn t C12H11NO2.

M = 201,2g/mol.
ts = 145C.
d = 1,232g/cm3.
Carbaryl l mt cht c ch men cholinesteraza v c c vi con ngi. N
c xp vo loi cht gy ung th i vi con ngi. Carbaryl l mt cht rn, c
mu trng hoc xm ty thuc vo tinh khit ca n, tinh th khng mi.
Carbaryl l mt thuc tr su c c tnh trung bnh. Khi tip xc vi carbaryl c
th gy ra ng c cp v mn tnh vi cc triu chng nh: bun nn, chut rt d
dy, tiu chy. Cc triu chng khc liu lng cao bao gm m hi, lm m
ca tm nhn, v co git, nh hng n phi, thn v gan.
Mc hp th hng ngy ti a cho php ADI ca carbaryl l 0,1mg/kg trng
lng c th. i vi chut, liu gy cht trung bnh qua ming LD50 = 250
850mg/kg, liu gy cht trung bnh qua h hp LC50 = 0,005 0,023mg/kg.
1.2.4. Fenobucarb [21]
Fenobucarb c tn l 2-(1-Methylpropyl)phenol methylcarbamate, l mt
loi thuc tr su nhm carbamat.

Cng thc phn t: C12H 17NO2

M = 207,3g/mol
ts = 32C
d = 1,035g/cm3
Fenobucarb tan km trong nc, tan tt trong cc dung mi Acetone,
Benzene, Toluene, xylene. Fenobucarb c s dng lm thuc tr su trn la v
bng, rt c hi i vi con ngi, n nh hng n h thn kinh, b phn sinh
sn, gy ung th v ng c cp tnh. Liu gy cht trung bnh qua ming i vi
chut l 410mg/kg.
1.2.5. Propoxur [22]
Propoxur c tn theo IUPAC l 2-isopropoxyphenyl methylcarbamate, l
mt dn xut ca carbamat v c s dng lm thuc tr su.

Cng thc phn t: C11H15NO3

M = 209,2g/mol
ts = 91C

Propoxur c c tnh cao i vi rui, mui, gin v b cht. N l cht c

c tnh cao vi con ngi, n c th xm nhp vo c th qua h hp, qua ng
ming v qua da. Triu chng ng c propoxur: bun nn, au bng, ra m hi,
tng huyt p, mt m, mt mi, kh th. Propoxur nhim c mn tnh i vi con
ngi gy ung th, nh hng n c quan sinh sn v h thn kinh trung ng.

10

i vi chut, liu gy cht trung bnh qua ming l 90 128mg/kg, qua da

l 800 1000mg/kg. Theo WHO, mc hp th hng ngy ti a cho php ADI ca
propoxur l 0,02mg/kg trng lng c th
1.2.6. Gii hn cho php
D lng l phn cn li ca hot cht, cc sn phm chuyn ha v cc
thnh phn khc c trong thuc, tn ti trn cy trng, nng sn, t, nc sau mt
thi gian di tc ng ca h sng v iu kin ngoi cnh. D lng ca thuc
c tnh bng mg thuc c trong 1kg nng sn, t hay nc.
Mc d lng ti a cho php (MRL) l gii hn d lng ca mt loi
thuc, c php tn ti v mt php l hoc xem nh c th chp nhn c
trong hay trn nng sn, thc n gia sc m khng gy hi cho ngi s dng v vt
nui khi n cc nng sn .
Bng 1. Mc d lng ti a cho php s dng thuc tr su carbamat mt
s quc gia. [6]

Quc gia
Nht Bn
Vit Nam

i tng

Carbofuran Carbayl Propoxur Fenobucarb

(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

1.3. Cc phng php xc nh

1.3.1. Phng php cc ph

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

ca carbofuran t 5.10-7 5.10-5M vi lch chun tng i tng ng l 1,62 v

1,86%.
1.3.2. Phng php quang ph hp th phn t
Cc tc gi Urmila Tamrakar, Vinay K. Gupta v Ajai K. Pillai [32] xc
nh ng thi 3 loi thuc tr su nhm carbamat bng phng php quang ph
hp th phn t. Phng php da trn s to mu ca carbamat vi thuc th paminoacetanlide. Khong nng tun theo nh lut Lambert - Beer ca carbaryl,
propoxur v carbosulfan tng ng l 0,04 0,36g/ml, 0,032 0,32g/ml v 0,08
0,64g/ml. Phng php c p dng phn tch thuc tr su nhm
carbamat trn cc mu rau, t, thc n, nc vi hiu sut thu hi khong 95%.
Tc gi L. Alvarez-Rodriguez [26] xc nh thuc tr su carbamat nh
carbaryl, bendiocarb, carbofuran, methiocarb, promecarb v propoxur bng phng
php quang ph hp th phn t ti bc sng 510nm. Cc thuc tr su c thy
phn trong mi trng kim nh to thnh 1-naphtol hoc phenolate, sau n s

12

to mu vi diazo trimethylanilin c cha mixen natri dodecyl sunfat. Gii hn pht

hin ca phng php trong khong 0,2 2mg/ml.
Phng php xc nh carbosulfan bng phng php quang ph hp th
phn t c cc tc gi Y.Koteswara Rao, K. Lokanath Swaroop,
P.Chiranjeevi, B. Rangamannar [35] cp. Carbosulfan c thy phn trong
mi trng kim to thnh hp cht phenolic v to cp vi 2, 4-dimethoxy aniline
trong mi trng c cha cht oxi ha K2Cr2O7 to thnh mt hp cht mang
mu cyanogen. Cht cyanogen ny c chit vo chloroform ti pH=3,5 v o ph
ti bc sng 430nm. Khong nng tun theo nh lut Lambert - Beer ca
carbosulfan l 0,1 1,0ppm. thu hi ca phng php trn cc mu nc ung,
go v la m u trn 93%.
Tc gi O. Bhargavi v cng s [31] pht trin mt k thut quang ph
hp th phn t n gin v nhy xc nh carbofuran trong cc mu nc v mu
ht. Carbofuran c thy phn trong mi trng kim v tng tc vi mui diazo
4, 4-azo-bis-3, 3, 5, 5-tetrabromo aniline to thnh cht mu v xc nh ti
bc sng 470nm. Khong tun theo nh lut Lambert - Beer ca carbofuran l 0,1
16,0g/ml .
Cc phng php quang ph hp th phn t ch phn tch c mt loi
carbamat no hoc phn tch ng thi mt s carbamat. Hn na, phng php
c nhy km. Do , hin nay phng php ny rt t c ng dng phn
tch carbamat.
1.3.3. Phng php phn tch dng chy (flow injection analysis FIA)
Phn tch dng chy l mt k thut phn tch ng, trong mu phn tch
dng lng c bm vo dng cht mang chuyn ng lin tc. Sau trong vng
phn ng cht phn tch s phn ng vi thuc th c trong dng cht mang, hay
c bm trc tip vo u vng phn ng, to ra mt sn phm c th pht hin
c theo mt tnh cht ha l no nh mt loi detector ph hp. Cc tnh cht
ha l thng l: s hp th quang phn t UV-VIS v nguyn t, tnh cht pht

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 KMnO 4. 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

CH3COONH4 5mM (pH=6,5) cha 1mM SDS v 0,01%

trietylamine (TEA). Ti cc iu kin ti u, 10 carbamat c tch nhanh trong

vng 20 pht. Cc mu rau c lm sch qua SPE. Phng php c gii hn pht
hin t 0,05 1,6mg/kg v hiu sut thu hi t 51,3 109,2% vi lch chun
RSD < 11,4%. Phng php c p dng xc nh 10 loi carbamat trong
mt s loi rau.
Xc nh d lng fenoxycarb trong la m bng phng php in di mao
qun kh v phng php sc k lng hiu nng cao. Cc mu bt m c chit
vi aceton ri c lm sch bng cch chit lng-lng vi diclometan. Phng
php HPLC s dng detector UV ti bc sng = 199nm, ct C18 v pha ng
l MeOH : H2O = 6 : 4 (theo th tch). Phng php in di s dng mao qun
ng knh 50m x 48,5cm x 48cm chiu di hiu dng, th gia hai u l 30kV,
dung dch m CH3COONH4 20mM (pH=9) trong 95% MeOH. C hai phng
php u c gii han pht hin thp 0,008mg/kg i vi HPLC v 0,024mg/kg i
vi in di mao qun kh v hiu sut thu hi cao trn 85%. Hai phng php
c ng dng xc nh fenoxycarb trong cc mu la m.[28]
Phng php sc k mao qun in ng hc mixen xc nh ng thi
aldicarb, carbofuran v mt s dng chuyn ha ca n trong nc b mt. Cc mu
c c lm sch qua ct chit pha rn c cha 500mg than hot tnh. Cc cht

15

c tch bng h thng sc k mao qun in ng hc mixen s dng ct mao

qun c ng knh 75m, chiu di hiu dng ca ct 50cm. Cc cht c tch
trong mi trng m natri borat/acid clohidric (20mM, pH=8) v s dng natri
dodecyl sunfat 140mM lm cht hot ng b mt to ra cc mixen. Cc iu
kin chy my: in th tch 23kV, thi gian bm mu 12s, nhit ct tch 25C
v detector UV ti bc sng 210nm. Phng php c gii hn pht hin t 2
7,4g/l, thu hi cao t 77 97% vi lch chun tng i 2 7%.[15]
K thut in di mao qun l mt k thut mi c pht trin khong hn 10
nm tr li y. y l mt k thut c thi gian phn tch nhanh, tn t dung mi v
ha cht. Vic xc nh cc ha cht bo v thc vt bng thit b ny vn ang
c nghin cu v cha c nhiu loi thuc tr su c xc nh bng phng
php ny.
1.3.5. Phng php sc k lng hiu nng cao
Tc gi Elvira Grou v cng s [16] xc nh thuc bo v thc vt
carbamat trong t v nc bng phng php sc k lng hiu nng cao s dng
detector UV bc sng 254nm. Cc mu nc c chit lng lng vi
diclometan, cc mu t c lm sch bng ct florisil. Dch chit c em c
quay n cn, ha cn bng 1ml metanol v em o. Gii hn pht hin ca phng
php i vi mu nc t 0,005 0,01g/g, i vi mu t t 0,05 0,1g/g.
Tc gi Feng Tang v cng s [17] xc nh d lng thuc tr su nhm
carbamat trong sau bng phng php sc k lp mng hiu nng cao HPTLC ti 2
bc sng = 243nm v = 207nm. Phng php c hiu sut thu hi t 70,13
103,7% ti nng 1 5mg/kg
Phng php sc k lng hiu nng cao s dng detetor hunh quang xc
nh ng thi cc cht carbamat nh aldicarb, propoxur, carbofuran, carbaryl v
methiocarb trong mt. Mu c chit bng methanol v cho qua ct florisil lm
sch. S dng dung mi diclometan:hexan = 1:1 ra gii cc cht carbamat ra khi
ct. Dch ra gii em c quay 40C n cn v ha cn bng 1ml acetonitril. Cc

16

cht carbamat c tch v xc nh ng thi bng h thng sc k lng vi

detector hunh quang ghp ni vi tin ct. Phng php c gii hn pht hin thp
t 4 5ng/g v thu hi tng i cao t 72,02 92,02% ng vi nng t 50
200ng/g.[18]
Phng php sc k lng hiu nng cao l mt phng php thng dng
xc nh cc hp cht hu c. Phng php ny c ng dng xc nh
ng thi cc cht carbamat. Tuy nhin, phng php c nhy km khi s dng
detector UV, cn khi s dng detector hunh quang, phng php c nhy tt
hn nhng ch c th nhn bit cht phn tch thng qua thi gian lu. i vi
nhng nn mu phc tp, cc cht phn tch rt d b nh hng bi nn mu, nu
ch da vo thi gian lu s rt kh c th khng nh cht cn phn tch.
1.3.6. Phng php sc k kh
Xc nh ethylcarbamat trong ung bng phng php sc k kh vi
detector bt in t v sc k kh khi ph. Cc mu c pha long bng ethanol
10% ri c chit bng diclometan. Dch chit c em c n gn cn v em
o. Phng php ny c nh gi 5 phng th nghim vi 4 phng s dng
detector ECD v 1 phng s dng detector MS. Gii hn pht hin ca phng
php thp, khong 5g/kg i vi detector ECD v 0,5g/kg i vi detector MS.
[14]
Xc nh thuc tr su carbamat v nhm nito hu c trong thc phm bng
phng php sc k kh khi ph. Phng php xc nh ng thi 29 loi thuc
tr su trong mt s thc phm nh to, khoai ty, go, chui Mu c chit
bng aceton v c lm sch bng 3 loi ct chit pha rn khc nhau: ct
diatomaceous, ct diatomit kt hp vi ct C18, ct florisil. Hiu sut chit cc mu
thc phm bng 3 loi ct u trn 80%. Sau , mu c xc nh bng phng
php sc k kh khi ph. Chng trnh chy khi ph c chia lm 7 ca s thi
gian lu v mi ca s c t 10 15 mnh ion con. Gii hn pht hin ca phng
php thp t 0,01 0,1g/ml. [27]

17

Xc nh a d lng thuc tr su trong nc to bng phng php sc k

kh khi ph. Mu nc to c chit bng phng php khuch tn trn nn pha
rn diatomaceous (to ct) v ra gii bng dung mi hexan:diclometan = 1:1 tc
5ml/pht. Phng php c thu hi 70 110% v h s bin thin t 1,62
18,3% vi khong nng 0,01 0,2mg/kg. [33]
Phng php sc k kh c ng dng rng ri xc nh cc ha cht
bo v thc vt nh cc cht clo hu c, ln hu c, pyrethroid v carbamat. Tuy
nhin phng php ch phn tch c nhng cht d bay hi, cn cc cht kh bay
hi th phi to dn xut nn tn thi gian v ha cht. Hn na, phn tch c
ng thi cc cht th cn thi gian phn tch di. Do vy, phng php t c ng
dng phn tch carbamat.
1.3.7. Phng php sc k lng khi ph
Gianni Sagratini v cng s [19] xc nh d lng thuc tr su
carbamat v phenylure trong mt s loi qu bng phng php vi chit pha rn v
sc k lng khi ph. iu kin chit mu ti u nhit 20C, thi gian hp ph
mu l 90 pht v th tch mu 1ml. Cc si silica c ph 3 loi cht hp ph:
cacbowax 50m, polydimetylsiloxan/divinylbenzen (PDMS/DVB) 60m v
polyacrylat 85m. Gii hn nh lng ca phng php t 0,005 0,05g/ml, ty
thuc tng cht. Phng php c ng dng xc nh thuc tr su trong
cc mu qu.
Xc nh ng thi ha cht bo v thc vt nhm carbamat v ln hu c
trong rau qu bng phng php sc k lng khi ph. Mu c chit bng
acetonitril, sau c tch bng cch chit pha rn khuch tn (dispersive SPE)
vi cht hp ph l primary secondary amine (amin bc mt hai). Hiu sut thu hi
cao, t 70 110% vi RSD < 8%. Gii hn pht hin thp 0,5 10ng/ml, ty
thuc tng cht. Phng php c ng dng xc nh thuc tr su trong rau
qu. Trong 25 mu rau qu c ly t cc ch, gn 70% mu cha mt hoc vi

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

Chng 2. I TNG V PHNG PHP NGHIN CU

2.1. i tng, mc tiu v ni dung nghin cu
2.1.1. i tng v mc tiu nghin cu
Hin nay, nhiu ngi nng dn lm dng thuc bo v thc vt lm cho
d lng thuc bo v thc vt trong nhiu mu rau vt gii hn cho php hng
chc ln; nht l cc loi rau n l nh ci ngt, mng ti, ci b xanh, ci bp, ci
tho, rau mung, da leoD lng ha cht bo v thc vt trong cc loi rau qu
qu cao gy nh hng nghim trng n mi trng v sc khe con ngi, l
nguyn nhn chnh gy ra cc v ng c thc phm. Do , i tng nghin cu
l mt s loi rau nh rau ci, rau thm, rau rn, bp ci, v mt s loi qu nh
cam, l, to, qut Mc tiu ca ti l nghin cu phng php xc nh ng
thi cc cht carbamat trong rau qu bng phng php sc k lng khi-ph khi
ph LC/MS/MS.
2.1.2. Ni dung nghin cu
t c mc tiu ra, cn nghin cu mt cch c h thng cc vn
sau:
2.1.2.1 Xy dng phng php
Kho st phng php bao gm:
iu kin tch chit mu
iu kin chy my
Thm nh phng php:
Gii hn pht hin LOD, gii hn nh lng LOQ
Khong tuyn tnh
chm ( lp li)
ng ( chch, thu hi)

20

2.1.2.2. ng dng phng php

p dng phng php mi xy dng xc nh tn d thuc bo v thc
vt h carbamat trong mt s loi rau v qu trn a bn H Ni.
2.2. Phng php nghin cu
2.2.1. Phng php tch chit mu
i tng mu phn tch trong lun vn ny l cc loi rau c, c nn mu
phc tp. Do cn c phng php tch chit mu thch hp gim nh hng
ca nn mu, trnh lm bn detector, tng kh nng pht hin.
Trong bn lun vn ny, chng ti s dng phng php chit lng lng
tch chit v lm giu mu. Thng thng, phng php ny s dng hai pha
lng khng trn ln. Tuy nhin, chng ti s dng mt loi ht nhi l kieselguhr
nh cht mang trong sc k phn b lng lng.
Kieselguhr hay cn gi l diatomaecous earth (t diatomit) hay Celite, c
mu trng ng, c khong pH lm vic rng t 1 13. N c s dng chit
lng lng cc mu thc phm m khng cn dng n phu chit. Mu sau khi
chit bng dung mi phn cc dng lng c a qua ct nhi ht kieselguhr
v c gi li trn ct. Sau cht phn tch c ra gii bng dung mi
khng phn cc.
S dng ct nhi ht kieselguhr c u im hn so vi chit lng lng
thng thng nh thi gian chit nhanh hn, khng cn phi mt thi gian tch
lp, lng dung mi s dng ra gii t hn nhiu, c thu hi v lp li cao.
2.2.2. Phng php sc k lng khi ph
2.2.2.1. Nguyn tc chung v phng php HPLC
Sc k lng l qu trnh tch xy ra trn ct tch vi pha tnh l cht rn v
pha ng l cht lng (sc k lng - rn). Mu phn tch c chuyn ln ct tch
di dng dung dch. Khi tin hnh chy sc k, cc cht phn tch c phn b
lin tc gia pha ng v pha tnh. Trong hn hp cc cht phn tch, do cu trc

21

phn t v tnh cht l ho ca cc cht khc nhau, nn kh nng tng tc ca

chng vi pha tnh v pha ng khc nhau. Do vy, chng di chuyn vi tc
khc nhau v tch ra khi nhau. S cu to thit b HPLC c ch ra hnh 2.1.

Hnh 2.1. S cu to h thng HPLC

Sc k lng hiu nng cao bao gm nhiu phng php c tnh c th ring,
l sc k lng pha lin kt, sc k phn b lng lng v sc k trao i lng
rn, sc k hp ph lng rn
2.2.2.2. Pha tnh trong HPLC
Trong HPLC, pha tnh chnh l cht nhi ct lm nhim v tch hn hp cht
phn tch. l nhng cht rn, xp v kch thc ht rt nh, t 3 7mm. Tu
theo bn cht ca pha tnh, trong phng php sc k lng pha lin kt thng chia
lm 2 loi: sc k pha thng (NP-HPLC) v sc k pha ngc (RP-HPLC)

Sc k pha thng: pha tnh c b mt l cc cht phn cc ( l cc

silica trn hoc cc silica c gn cc nhm ankyl c t cacbon mang
cc nhm chc phn cc: -NH2, -CN...), pha ng l cc dung mi hu

22

c khng phn cc nh: n-hexan, toluene....H ny c th tch a dng

cc cht khng phn cc hay t phn cc.

Sc k pha ngc: pha tnh thng l cc silica c ankyl ho,

khng phn cc, loi thng dng nht l C18H37, cn pha ng phn
cc: nc, methanol, axetonitril....Trong rt nhiu trng hp th thnh
phn chnh ca pha ng li l nc nn rt kinh t. H ny c s
dng tch cc cht c phn cc rt a dng: t rt phn cc, t
phn cc ti khng phn cc .

2.2.2.3. Pha ng trong HPLC

Pha ng trong HPLC ng gp mt phn rt quan trng trong vic tch cc
cht phn tch trong qu trnh sc k nht nh. Mi loi sc k u c pha ng ra
gii ring cho n c c hiu qu tch tt nhng nhn chung phi p ng c
cc iu kin sau:
Pha ng phi tr vi pha tnh.
Pha ng phi ha tan tt mu phn tch, phi bn vng v khng b
phn hy trong qu trnh chy sc k.
Pha ng phi c tinh khit cao.
Pha ng phi nhanh t c cc cn bng trong qu trnh sc k, nh
cn bng hp ph, phn b, trao i ion tu theo bn cht ca tng loi
sc k.

Phi ph hp vi loi detector dng pht hin cc cht phn tch.

Pha ng phi khng qu t.

C th chia pha ng lm hai loi:
Pha ng c phn cc cao: c thnh phn ch yu l nc, tuy

nhin phn tch cc cht hu c, cn thm cc dung mi khc

gim phn cc nh MeOH, ACN. Pha ng loi ny c dng
trong sc k pha lin kt ngc.

23

 Pha ng c phn cc thp: bao gm cc dung mi t phn cc nh

xyclopentan,

n-pentan,

n-heptan,

n-hexan,

2-chloropropan,

cacbondisulfua (CS2), chlorobutan, CCl4, toluene....Tuy nhin pha

ng mt thnh phn i khi khng p ng c kh nng ra gii,
ngi ta thng phi hp 2 hay 3 dung mi c c dung mi c
phn cc t thp n cao ph hp vi php phn tch. S thay i
thnh phn pha ng theo thi gian gi l ra gii gradient nng .
2.2.2.4. Detector trong HPLC
Detector l b phn quan trng quyt nh nhy ca phng php. Tu
thuc bn cht l ho ca cht phn tch m la chn detector cho ph hp.
Detector quang ph hp th phn t UV-VIS: p dng cho cc cht
c kh nng hp th nh sng trong vng t ngoi (UV) hoc vng
kh kin (VIS).
Detector hunh quang RF: s dng pht hin cc cht c kh nng

pht hunh quang. i vi nhng cht khng c kh nng nh vy,

cn phi dn xut ho cht phn tch, gn n vi cht c kh nng
pht hunh quang hoc cht phn tch phn ng vi thuc th to
thnh sn phm c kh nng pht hunh quang.
Detector dn: ph hp vi cc cht c hot tnh in ho: cc ion

kim loi chuyn tip....

Hin nay, cc detector hin i ngy cng c ci tin nh diot-aray, mass
spectrometry, n gip ngi phn tch xc nh chnh xc cht phn tch. Ngoi ra
do k thut tin hc pht trin, ngi phn tch c th thc hin php tch theo
chng trnh nh sn, c th thc hin cc php tch t ng nhiu mu phn tch.
2.2.2.5 Detector khi ph (Mass Spectrometry)
Khi ph l thit b phn tch da trn c s xc nh khi lng phn t ca
cc hp cht ha hc bng vic phn tch cc ion phn t theo t s gia khi lng

24

v in tch (m/z) ca chng. Cc ion c th to ra bng cch thm hay bt in tch

ca chng nh loi b electron, proton ha,... Cc ion to thnh ny c tch theo
t s m/z v pht hin, t c th cho thng tin v khi lng hoc cu trc phn
t ca hp cht.
Cu to ca mt thit b khi ph bao gm 3 phn chnh: ngun ion, thit b
phn tch v detector. Trc ht, cc mu c ion ha trong ngun ion, sau a
vo b phn phn tch khi tch cc ion theo t s m/z. Cc tn hiu thu c s
chuyn vo my tnh x l v lu tr.
2.2.2.5.1. Ngun ion
Cht phn tch sau khi ra khi ct tch s c dn ti ngun ion chuyn
thnh dng hi v c ion ha nguyn t. Mt s k thut ion ha c s dng
trong sc k lng khi ph nh: ion ha phun in t (electrospray ionization
ESI), ion ha ha hc p sut kh quyn (atmospheric-pressure chemical
ionization APCI), ion ha bn ph nguyn t nhanh (fast-atom bombardment
FAB). Di y l hai phng php ion ha c s dng trn thit b Finnigan
LCQDUO:
a) Ion ha phun in t ESI
K thut ny chuyn ha cc ion t dung dch lng thnh cc ion dng kh.
Dung dch mu c dn vo vng c trng in t mnh c duy tr hiu in
th cao 4kV. Ti y, dung dch mu b chuyn thnh cc git nh tch in v c
ht tnh in ti li vo ca thit b phn tch khi ph. Cc git nh trc khi vo
thit b phn tch khi ph s c kt hp vi dng kh kh lm bay hi dung
mi. C 2 ch bn ph: bn ph vi ch ion dng v ion m.

25

Hnh 2.2. K thut ESI bn ph vi ch ion dng

y l k thut ion ha mm, c nhy cao. K thut ny ng dng phn
tch cc cht khng phn cc nh: protein, peptit, cacbonhydrat, nucleotit,
polyetilen glycocol,... v cc cht phn cc c khi lng phn t nh.
b) Ion ha ha hc p sut kh quyn APCI
y cng l mt k thut ion ha mm. APCI c s dng phn tch cc
cht c khi lng phn t trung bnh. K thut ny c th bn ph 2 ch : ion
m v ion dng.

Hnh 2.3. K thut APCI bn ph vi ch ion dng

26

Cht phn tch v dung mi dng lng c chuyn thnh cc git nh ri

ha hi nhit cao khong 500C. Mt in th cao t 3 5kV to ra cc
electrron v ion ha cht phn tch. i vi k thut APCI bn ph vi ch ion
dng, s ion ha mu c thc hin qua 3 giai on:
Giai on th nht:
e + N 2 N 2+. + 2e

Giai on th hai:
N 2+. + H 2O N 2 +H 2O +.
H 2O +. + H 2O H 3O + + HO .

Giai on th ba:
H 3O + + M ( M + H ) + + H 2 O

APCI l mt k thut ion ha mnh, n khng b nh hng khi thay i m

chy v nng m. N c s dng ion ha cc cht c khi lng phn t
nh (c khi lng phn t < 2000u).
2.2.2.5.2. B phn phn tch khi lng
a) B phn tch t cc (Quadrupole Analyser)
T cc c cu to bi 4 thanh in cc song song to thnh mt khong
trng cc ion bay qua. Mt trng in t c to ra bng s kt hp gia dng
mt chiu (DC) v in th tn s radio (RF). Cc t cc c ng vai tr nh mt
b lc khi. Khi mt trng in t c p vo, cc ion chuyn ng trong n s
dao ng ph thuc vo t s gia m/z v trng RF. Ch nhng ion c t s m/z
ph hp mi c th i qua c b lc ny.
b) B phn tch by ion t cc (Quadrupole Ion-Trap Mass Analyser)
Loi thit b ny bao gm mt in cc vng (ring electrode) vi nhiu in
cc bao xung quanh, in cc u ct (end-cap electrode) trn v di. Tri vi

27

li thit b t cc trn, cc ion sau khi i vo by ion theo mt ng cong n

nh c by li cho n khi mt in p RF c t trn in cc vng. Cc ion
khc nhau m/z sau tr nn khng n nh v s c hng i v pha detector. Do
in p RF khc nhau trong h thng ny m thu c mt ph khi lng y .
Cc ion tn ti trong by c th c chn ring v phn tch theo s khc
nhau v m/z, ng thi c th chn ring v thc hin qu trnh bn ph thu c
cc mnh ion con, t thc hin phn tch theo m/z ca ion con (khi ph 2 ln).
V nguyn tc cc ion c th tn ti trong by thi gian lu c th thc hin n
MS n ln, tuy nhin trong thc t thng ch c kh nng thc hin n khi ph 3
ln.
c) B phn tch thi gian bay (Time of Flight Analyser)
Phn tch thi gian bay da trn c s gia tc cc ion ti detector vi cng
mt nng lng. Do cc ion c cng nng lng nhng li khc nhau v khi lng
nn thi gian i ti detector s khc nhau. Cc ion nh hn s i ti detector nhanh
hn do c vn tc ln hn cn cc ion ln hn s i chm hn, do vy, thit b ny
c gi l thit b phn tch thi gian bay do t s m/z c xc nh bi thi gian
bay ca cc ion. Thi gian bay ca mt ion ti detector ph thuc vo khi lng,
in tch v nng lng ng hc ca cc ion. phn gii ca b phn tch thi
gian bay thp nhng n c u im l khi lng ion c th phn tch khng b hn
ch.
2.2.2.5.3. B phn pht hin
Sau khi i ra khi thit b phn tch khi lng, cc ion c a ti phn
cui ca thit b khi ph l b phn pht hin ion. B phn pht hin cho php
khi ph to ra mt tn hiu ca cc ion tng ng t cc electron th cp c
khuch i hoc to ra mt dng do in tch di chuyn. C hai loi b phn pht
hin ph bin: b phn pht hin nhn electron v b phn pht hin nhn quang.
B phn pht hin nhn electron l mt trong nhng detector ph bin nht,
c nhy cao. Cc ion p vo b mt dinot lm bt ra cc electron. Cc electron

28

th cp sau c dn ti cc dinot tip theo v s to ra electron th cp nhiu

hn na, to thnh dng cc electron.
B phn pht hin nhn quang cng ging nh thit b nhn electron, cc ion
ban u p vo mt dinot to ra dng cc electron. Khc vi detector nhn
electron, cc electron sau s va p vo mt mn chn phtpho v gii phng ra
cc photon. Cc photon ny c pht hin bi mt b nhn quang hot ng nh
thit b nhn electron. u im ca phng php ny l cc ng nhn quang c
t trong chn khng nn loi b c cc kh nng nhim bn.
2.3. Phng tin nghin cu
2.3.1. Thit b, dng c
2.3.1.1. Thit b
H thng sc k lng khi ph khi ph LC/MS/MS ca Thermo bao

gm: b phn bm dung mi, b loi kh, b phn iu nhit v

detector MS.
Ct sc k C18 ca Water (150mm 4,6mm 5m).
My lc vortex.
My ng nht mu.

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

- Dung dch chun hn hp lm vic 200g/l: ly chnh xc 0,2ml dung dch

chun hn hp trung gian 10mg/l cho vo bnh nh mc 10ml v nh mc n
vch bng methanol.
* Chun b dung mi pha ng
- Knh A: dung dch acid focmic 0,1% trong nc: ly chnh xc 1ml acid
focmic vo bnh nh mc 1000ml v nh mc n vch bng nc ct.
- Knh B: methanol.

31

Chng 3. KT QU V THO LUN

3.1. Ti u cc iu kin xc nh carbamat bng LC/MS/MS
3.1.1. Chn cc iu kin chy ca detector khi ph
3.1.1.1. Kho st iu kin bn ph i vi ion m
Cc cht carbamat c khi lng phn t nh v km phn cc. Qua tham
kho mt s bi bo, chng ti kho st tin hnh xc nh carbamat bng k thut
ion ha phun in t ESI vi ch bn ion dng. ti u ha iu kin khi
ph, dng xyranh 500l bm tng chun carbamat 1000ppb vo detector kho
st. Chn ch kho st t ng i vi tng cht carbamat, ti u ha tng ion
m, ta c iu kin chy ngun ion ha ESI bng 3.1.
Bng 3.1. iu kin chy ngun ion ha ESI
Tc kh phun = 80 (arb)
Tc kh b tr = 10 (arb)
Th phun in t = 4kV
Nhit mao qun = 270 C
Trong k thut ion ha phun in t vi ch bn ion dng, cc ion m
thng dng (M+1). Tin hnh kho st bn ph cc ion m, kt qu nh sau:
Bng 3.2. Kt qu bn ph cc ion m
Carbamat

Khi lng phn t M

Ion m

Carbofuran

221,3

221,98

Propoxur

209,3

210

Carbaryl

201,2

201,84

Fenobucarb

207,3

208,00

32

kscarbaryl
#900
RT: 11.92
T: +cESIFull ms[ 110.00-210.00]
100

AV:

NL:

4.60E6
201.84

Phkhi ioncarbaryl

Relative Abundance

90
80
70
60
50
40
30

114.95

20
145.22

202.90

10

168.07
124.88

0
110

146.13

136.24

120

130

140

154.95

150

173.15

179.22

167.18
160
m/z

170

190.07

180

196.18

190

203.83
200

210

Hnh 3.1. Ph khi ion m ca carbaryl

kscarbofuran
#761
RT: 10.17
F: +cESIFull ms[ 150.00-230.00]
100

AV:

NL:

2.98E7
221.98

Phkhi ioncarbofuran

Relative Abundance

90
80
70
60
50
40
30
20
222.97

10
0
150

165.26
162.00

154.97

160

168.23

173.32

170

185.14
180

196.44

190.06
190
m/z

199.35
200

210.51

213.99

210

223.94

220.56
220

230

Hnh 3.2. Ph khi ion m ca carbofuran

ksfenobucarb
#665
RT:
T: +cESIFull ms[ 110.00-220.00]

10.86

AV:

NL:

3.42E6
208.00

100

Relative Abundance

90

Phkhi ionfenobucarb

80
70
60
50
40
30
20
10
0
110

209.07
114.24

118.98
120

144.39

130.39
130

140

152.12
150

158.23

168.22

160

170

185.22

175.26
180

196.42
190

205.01
200

210.00
210

220

m/z

Hnh 3.3. Ph khi ion m ca fenobucarb

33

kspropoxur
#473
RT: 9.18
T: +cESIFull ms[ 110.00-230.00]

AV:

NL:

3.26E7
209.90

100

Relative Abundance

90

Phkhi ionpropoxur

80
70
60
50
40
30
20

111.16
0
110

226.57

210.92

10
125.09
120

130.58
130

144.18
140

168.17

153.15
150

160

180.28

170
m/z

180

208.36

196.23

185.31
190

200

211.93
210

220

230

Hnh 3.4. Ph khi ion m ca propoxur

3.1.1.2. Kho st iu kin bn ph ion con
Detector c s dng trong nghin cu ny l khi ph hai ln, do
pht hin ng cht phn tch th vic chn c ion con l rt quan trng. Ion con
phi c tn hiu gp t nht 10 ln so vi ion m. thu c mnh ion con c tn
hiu cao th cn phi chn c mc nng lng bn ph thch hp. Dng xyranh
500l bm tng chun vo detector v my t ng ti u ha mc nng lng
bn ph ion m to cc ion con. Kt qu thu c bng 3.2.
Bng 3.3. Nng lng bn ph v cc ion con ca carbamat
Nng lng bn ph

Carbamat

Ion m

Carbofuran

222

48

165

Propoxur

210

45

168, 153

Carbaryl

202

45

145

Fenobucarb

208

37

152

Collision Energy (%)

34

Ion con

Carbofuran
#954
RT: 13.85
AV: 1
F: +c ESIFull ms2222.00@48.00[ 60.00-230.00]
100

NL:

4.38E5
164.90

Phkhi ionconcaCarbofuran

Relative Abundance

90
80
70
60
50
40
30
20
10
70.69

84.38

0
60

98.52

80

113.06

100

123.21

133.29

120

149.33

161.09

182.94

160

180

140

191.31

200.32

226.40

210.77

200

220

m/z

Hnh 3.5. Ph khi ion con ca Carbofuran sau khi bn ph

Fenobucarb
#857
RT: 14.57
AV: 1
F: +c ESI Full ms2208.00@37.00 [ 55.00-230.00]
100

NL:

1.39E5
151.84

Phkhi ionconcaFenobucarb

90

Relative Abundance

80
70
60
50
40
30
20
10
60.38

72.81

85.61
81.85

150.67

94.94

148.35
105.24

119.13

130.65

164.29

172.07

204.72

192.40

216.41

229.31

0
60

80

100

120

140
m/z

160

180

200

220

Hnh 3.6. Ph khi ion con ca Fenobucarb sau khi bn ph

Propoxur
#689
RT: 13.75
AV: 1 NL:
F: +cESI Full ms2210.00@
45.00[ 55.00-230.00]

4.85E4
167.84

100
Phkhi ionconcaPropoxur

Relative Abundance

90
80
70
60
152.78

50
40
30
20

69.75

123.42

84.37

74.65

10

99.91

110.84

150.89

196.64

154.66
164.70

177.28

192.63

204.25
219.16

228.11

0
60

80

100

120

140
m/z

160

180

200

220

Hnh 3.7. Ph khi ion con ca Propoxur sau khi bn ph

35

Carbaryl
#1002
RT: 14.24
AV: 1
F: +cESIFull ms2202.00@
45.00[ 55.00-230.00]

NL:

5.87E4
144.95

100

Phkhi ionconcaCarbaryl

Relative Abundance

90
80
70
60
50
40
30
20
57.90
10

102.44
66.05

76.00

92.05

189.65
118.97

140.14

151.43

166.56

176.10

198.68

218.86

200

220

0
60

80

100

120

140
m
/z

160

180

Hnh 3.8. Ph khi ion con ca Carbaryl sau khi bn ph

3.1.2. Chn pha tnh
Ct tch l tri tim ca h sc k, n ng gp mt phn quan trng trong
vic quyt nh qu trnh tch. Cc cht nhm carbamat l cc cht km phn cc,
do ct tch c s dng l ct pha o. Hn na, cht nhi pha o s dng h
dung mi phn cc c tnh kinh t cao, ph hp vi iu kin ca phng th
nghim. Trong nghin cu ny, chng ti chn ct pha o C18 tch cc cht
carbamat. bo v ct, chng ti s dng thm tin ct. Thng s ct tch v tin
ct:
Ct Symestry Shield C18 ca Water (150mm x 4,6mm x 5mm).
Tin ct Symestry C18 ca Water (20 mm x 3,9 mm x 5mm).

3.1.3. Chn pha ng

Trong phng php sc k lng khi ph, pha ng khng ch nh hng ti
qu trnh tch cc cht m n cn nh hng ti qu trnh ion ha v tn hiu ca
cht phn tch. Vi k thut ion ha phun in t bn ph ch ion dng, qu
trnh ion ha tng khi c thm cc cht nh acid acetic, acid focmic. Dng dung
dch chun hn hp carbamat 1000ppb kho st thnh phn pha ng khi c
thm cht trn, cc iu kin chy my c c nh nh sau:
-

Ct Symestry Shield Water C18 v tin ct.

36

Detector: khi ph.

Tc dng: 0,5 ml/pht.

Pha ng: knh B l methanol, knh A ln lt l acid focmic 0,1%,

acid acetic 0,1%, CH3COONH4 0,1% trong nc.
Bng 3.4. nh hng ca thnh phn pha ng

Din tch pic St

Carbamat
Acid focmic 0,1%

Acid acetic 0,1%

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.

o Knh B: dung mi methanol.

37

Chn dung dch chun hn hp 4 cht nhm carbamat 1000ppb kho st t

l dung mi, c nh cc iu kin:
-

Ct Symestry Shield Water C18 (150mm x 4,6mm x 5mm).

Ct bo v: Symestry Water C18 (20 mm x 3,9 mm x 5mm).

Detector: MS/MS.

Tc dng: 0,5 ml/pht.

Thi gian chy: 30 pht.

Kt qu kho st t l dung mi pha ng c ch ra bng di y.

Bng 3.5. nh hng ca t l dung mi pha ng ti thi gian lu.
T l pha ng

Thi gian lu (pht)

%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

Bng 3.6. Chng trnh chy gradient ra gii cc cht carbamat

Thi gian (pht)

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

Tm li, cc thng s ti u cho qu trnh chy sc k nh sau:

Ct Symestry C18 ca Water (150mm x 4,6mm x 5mm).
Tin ct Symestry C18 ca Water (20 mm x 3,9 mm x 5mm).
Thnh phn pha ng: Knh A l dung dch acid focmic 0,1%

trong nc, knh B l dung mi MeOH.

Chng trnh chy gradient bng 3.6.

Tc dng 0,5ml/pht.
Detector MS/MS vi cc thng s bng 3.1 v 3.3.

3.2. nh gi phng php phn tch

3.2.1. Kho st lp ng chun
Lp ng chun l mt trong nhng yu cu u tin ca phng php
phn tch. T ng chun ta c th bit c khong tuyn tnh ca cht phn tch,
t a nng mu thc nm trong khong tuyn tnh. Chng ti tin hnh
xy dng ng chun nh sau: pha mt dy dung dch chun c nng t 20ppb

39

n 1500ppb t dung dch chun gc 100ppm v chun trung gian 10ppm. Cc

dung dch chun c pha trong methanol. Sau em o cc iu kin nh
ti u trn, kt qu thu c bng 3.7.
Bng 3.7. S ph thuc din tch pic vo nng carbamat
Nng

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

4000000

5000000

3500000
3000000

4000000

Din tch

Din tch

y = 3990x - 5018.5
R2 = 0.9994

4500000

6000000

3000000
2000000
1000000

2500000
2000000
1500000
1000000
500000
0

0
0

500

1000

1500

2000

500

Nng (ppb)

1000

1500

Nng (ppb)

Hnh 3.9. S ph thuc ca din tch pic vo nng Fenobucarb v ng chun

ca Fenobucarb

n g ch u n C ar b ar yl
7000000

9000000
8000000

6000000

7000000

5000000
Din tch

Din tch

6000000
5000000
4000000

y = 6376 x - 11658
R2 = 0 .9 9 9 3

4000000
3000000

3000000

2000000

2000000

1000000

1000000

500

1000

1500

2000

200

400

600

800

1000

1200

N n g ( p p b )

Nng (ppb)

Hnh 3.10. S ph thuc ca din tch pic vo nng Carbaryl v ng chun

ca Carbaryl

41

10000000
9000000
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
0

8000000

y = 7038.3x + 89642

7000000

R = 0.9995

6000000
Din tch

Din tch

ng chun Propoxur

5000000
4000000
3000000
2000000
1000000
0

500

1000

1500

2000

200

400

600

800

1000 1200

Nng (ppb)

Nng (ppb)

Hnh 3.11. S ph thuc ca din tch pic vo nng Propoxur v ng chun

ca Propoxur

ng chun Ca rbofura n

100000000

70000000

80000000
60000000

Din tch

Din tch

y = 74735x + 1E+06
R2 = 0.9993

80000000

40000000

60000000
50000000
40000000
30000000
20000000
10000000

20000000
0

0
0

500

1000

1500

2000

Nng (ppb)

500

1000

1500

Nng (ppb)

Hnh 3.12. S ph thuc ca din tch pic vo nng Carbofuran v ng

chun ca Carbofuran

42

RT:

0.00- 18.04

Relative Abundance

NL: 2.60E6
TICF: + c ESI SRMms2
222.00@48.00 [
164.50-165.50] MSmix
500ppb

RT: 8.87
MA: 38708909

100
50
1.07

2.82

4.23

6.15

6.68

100

9.57
7.29
RT: 8.88
MA: 3668940

10.97

11.85

13.43

16.67

17.72
NL: 2.57E5
TICF: + c ESI SRMms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MSmix
500ppb

50
0.73

2.31

3.01

4.41

5.02

7.13

9.23

7.92

12.03

13.35

16.15

16.77
NL: 2.15E5
TICF: + c ESI SRMms2
202.00@45.00 [
144.50-145.50] MSmix
500ppb

RT: 9.86
MA: 3127832

100
50
0.83

1.88

3.02

4.25

5.04

7.40

7.93

9.15

100

10.82
RT: 10.93
AA: 1923068

12.75

13.97

16.25

16.95
NL: 1.36E5
TICF: + c ESI SRMms2
208.00@37.00 [
151.50-152.50] MS ICISmix
500ppb

50
0
0

8
Time(min)

10

12

14

16

18

Hnh 3.13. Sc chun hn hp carbamat 500ng/g

T cc th trn ta thy, t nng trn 1000ppb th mi quan h gia din
tch pic v nng cc cht carbamat khng cn tuyn tnh na. Nh vy, gii hn
tuyn tnh ca cacbofuran, propoxur, carbaryl v fenobucarb l 1000ppb.
3.2.2. Gii hn pht hin LOD [10]
Gii hn pht hin LOD c xem l nng thp nht ca cht phn tch
m h thng phn tch cn cho tn hiu phn tch khc c ngha vi tn hiu ca mu
trng hay tn hiu nn.
xc nh gii hn pht hin, chng ti dng chun hn hp 50ppb ri tin
hnh pha long cho ti khi thu c chiu cao cht phn tch gp 3 ln tn hiu
ng nn. Kt qu thu c nh sau: gii hn pht hin ca carbofuran l 5ng/ml;
gii hn pht hin ca carbaryl, propoxur v fenobucarb l 15ng/ml.

43

RT: 0.00 - 18.04

NL: 3.24E5
TIC F: + c ESI SRMms2
222.00@48.00 [
164.50-165.50] MS mix
15ppb

8.87

100

Relative Abundance

50
1.16

0
100

2.82

7.46

6.76

5.62

4.40

8.60

9.48

11.67

12.37

13.86

14.47

16.66

RT: 8.96
8.79

50
1.08

3.53

2.57

6.69

6.42

4.32

7.91

12.73

11.50

9.49

13.26
15.01

10.28

0
100

16.15

16.32

NL: 2.98E4
TIC F: + c ESI SRMms2
202.00@45.00 [
144.50-145.50] MS mix
15ppb

RT: 9.85

50
2.58

1.70

3.89

7.05

6.08

5.65

8.80

11.60

0
100

14.23

12.65

17.12

17.47
NL: 1.39E4
TIC F: + c ESI SRMms2
208.00@37.00 [
151.50-152.50] MS mix
15ppb

RT: 10.92
7.24

50
0.85

5.67

4.00

2.25

7.59

6.37

NL: 2.04E4
TIC F: + c ESI SRMms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MS mix
15ppb

13.47

12.33

RT: 8.82

15.22

15.57

0
0

8
10
Time (min)

12

14

16

18

Hnh 3.14. Sc chun hn hp carbamat 15ng/ml

RT: 0.00 - 18.04

5.54
50
Relative Abundance

NL: 3.62E4
TIC F: + c ESI SRMms2
222.00@48.00 [
164.50-165.50] MS mix
5ppb

RT: 8.87

100

1.33
0
100

2.12

4.31

6.50

7.20

10.10

5.28
5.46
6.51

0.82

2.57

50

2.75
3.54

0
100

5.47
4.51
1.71
1.27

50

2.49

0
100

12.99

12.12
11.42

17.28

15.27
16.85

13.96

17.90

14.84

6.00
6.88

9.85

7.84
9.59
8.45

4.88
5.85

2.25

50

10.37

4.25
4.09

0.50

8.97

6.78

5.20

11.94

2.78

6.81
7.42

13.36

10.38

12.40

13.62

8.30
8.74

15.90

17.48

14.70

10.05

13.29

11.10

17.15

17.59

NL: 1.15E4
TIC F: + c ESI SRMms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MS mix
5ppb
NL: 1.07E4
TIC F: + c ESI SRMms2
202.00@45.00 [
144.50-145.50] MS mix
5ppb

NL: 7.56E3
TIC F: + c ESI SRMms2
208.00@37.00 [
151.50-152.50] MS mix
5ppb

0
0

8
10
Time (min)

12

14

16

18

Hnh 3.15. Sc chun hn hp carbamat 5ng/ml

3.2.3. Gii hn nh lng LOQ [10]
Gii hn nh lng LOQ c xem l nng thp nht m h thng phn
tch nh lng c vi tn hiu phn tch khc c ngha nh lng vi tn hiu
ca mu trng hay tn hiu nn. Theo l thuyt thng k trong ha phn tch th LOQ
= 3,33 LOD. Do , gii hn nh lng ca carbofuran l 20ng/ml cn gii hn
nh lng ca carbaryl, fenobucarb v propoxur l 50ng/ml.

44

3.2.4. chnh xc ca php o

Theo ISO, chnh xc ca php o c nh gi qua ng v chm.
chm l mc gn nhau ca cc gi tr ring l ca cc php o lp li.
ng l mc gn nhau ca gi tr phn tch vi gi tr thc. ng c biu
din di dng sai s tuyt i hoc sai s tng i.
Sai s c tnh theo cng thc:
Si St
100%
St

%X =

% X tb =

%X
i=1

Trong : %X : Sai s phn trm tng i.

Si : gi tr din tch pic o c.
St : gi tr din tch pic tm c theo ng chun.
n : s ln o.
lp li ca php o c xc nh theo cc i lng S2 v CV.
S

( S S
=
i

tb

CV =

n 1

S
100
S tb

Trong : Stb : Din tch pic trung bnh.

n

: 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

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

pic St

%Xtb

Ln o

Carbofuran 38651499
500

Din tch

Din tch pic Si

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

Nhn xt: Phn trm sai s v h s bin thin CV ca php o ti 3 mc

nng 50ppb, 500ppb v 1000ppb c gi tr t 1,2 7,6% u nm trong gii hn
cho php ca AOAC.
3.3. Kho st iu kin x l mu
Cc cht carbamat u c phn cc km, tan nhiu trong dung mi t phn
cc. Do , chng ti tin hnh tch chit carbamat theo nguyn tc sau: cc cht
carbamat c tch ra khi nn mu bng dung mi methanol, sau c lm
sch qua ct kieselguhr v nh lng bng sc k lng khi ph.
Qui trnh d kin chit carbamat:

46

Mu /ng li tm 50ml
+ thm chun hn hp 4 carbamat
+ MeOH
ng nht

Lc vortex

Li tm 6000 v/ph, 5 pht

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

3.3.1. Kho st dung mi chit

tch chit cc cht carbamat khi nn mu, chng ti s dng dung mi
Methanol : H2O vi cc t l khc nhau. Ht chnh xc 0,5ml dung dch chun hn
hp carbamat 1000ppb cho vo cc bnh nh mc 50ml. Thm vo cc bnh 40ml
dung mi methanol : H2O vi cc t l khc nhau v nh mc bng dung dch NaCl
bo ha ri lc u. Ht chnh xc 20ml dung dch trn cho qua ct kieselguhr. Mu

47

c ra gii, em c quay n cn v ha cn bng 1ml methanol ri em o

LC/MS/MS. Kt qu thu c nh sau:
Bng 3.9. Kt qu kho st t l dung mi chit i vi cc cht carbamat
MeOH:H2O mlt (ng)

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 (%)

n
1:1

200

2:1

200

3:1

200

4:1

200

100

R (%)

80
Carbofuran

60

Propoxur

40

Fenobucarb

Carbaryl

20
MeOH:H 2O
0
1:1

2:1

3:1

4:1

48

Hnh 3.16. th biu din s ph thuc hiu sut chit carbamat vo t l

dung mi chit
Nhn xt: Ti t l dung mi MeOH:H2O = 2:1 v 3:1 th hiu sut chit l
tt nht. Do , chng ti chn t l MeOH:H 2O = 2:1 tit kim dung mi MeOH
cho cc ln kho st sau.
3.3.2. Kho st dung mi ra gii
i tng nghin cu l cc mu rau qu c nn mu phc tp. Do , cn
phi c qu trnh lm sch mu trc khi bm vo my. Trong lun vn ny, chng
ti s dng ct kieselguhr lm sch mu. Carbamat c chit theo quy trnh
nh trn v c ra gii bng cc dung mi khc nhau: hexan, diclometan v
etylacetat. Kt qu thu c bng di.
Bng 3.10. Kt qu kho st loi dung mi ra gii i vi cc cht carbamat
Dung mi

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 (%)

400

Khng ha tan c

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

fenobucarb th thu hi tt hn khi dng hexan. Do , chng ti s dng c 2

dung mi trn ra gii carbamat.
c c thu hi tt nht, chng ti tin hnh kho st t l dung mi
ra gii hexan : diclometan nh sau: carbamat c chit nh quy trnh trn v
ra gii bng dung mi hexan:diclometan cc t l khc nhau. Kt qu thu c
bng di.
Bng 3.11. Kt qu kho st t l dung mi ra gii i vi cc cht carbamat
Diclometan:hexan mlt (ng)

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

40

Fenobucarb

20
CH2Cl2 :hexan

0
1:2

1:1

2:1

3:1

Hnh 3.17. th biu din s ph thuc hiu sut chit carbamat vo t l

dung mi ra gii
Nhn xt: t th trn ta thy, thu hi cc cht carbamat l tt nht ti t
l diclometan:hexan =1:1. Do , chng ti chn t l dung mi ra gii
diclometan:hexan =1:1 cho cc ln kho st sau.
3.3.3. Kho st th tch dung mi ra gii
Cc cht carbamat c chit theo quy trnh nh trn v c ra gii
bng hn hp dung mi diclometan:hexan =1:1 ti cc th tch khc nhau. Kt qu
thu c bng 3.10.
Bng 3.12. Kt qu kho st th tch dung mi dung mi ra gii i vi cc
cht carbamat
V (ml)

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

50

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 (%)

200

60

200

R (%)

100
80

Carbofuran
Propoxur

60

Carbaryl

40

Fenobucarb

20
V (ml)
0
0

10

20

30

40

50

60

70

Hnh 3.18. th biu din s ph thuc hiu sut thu hi carbamat vo th

tch dung mi ra gii
Nhn xt: T th trn ta thy, thu hi carbamat tng i cao bt u
t th tch ra gii bng 50ml. Do , va c hiu sut thu hi cao va tn
dung mi, chng ti chn th tch ra gii l 50ml cho cc nghin cu tip theo.
3.3.4. lp li v thu hi ca phng php
Mt phng php phn tch tt phi c lp li v h s thu hi cao.
nh gi hai yu t trn, chng ti tin hnh kho st trn nn mu thc. S dng

52

mu trng, thm chun ti 3 mc nng 100ppb, 500ppb v 1000ppb. Mi mc

tin hnh lm lp li 4 ln. lp li v thu hi c xc nh nh sau:
lp li ca phng php c xc nh theo cc i lng S2 v CV.
S

( S S
=
i

tb

CV =

n 1

S
100
S tb

Trong : Stb : Din tch pic trung bnh.

n

: s ln o.

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

R=

(Cm +c Cm ) 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

Din tch pic Si

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

Nhn xt: thu hi ca phng php ti 3 mc nng 100ppb, 500ppb

v 1000ppb u trn 80% v nm trong gii hn cho php ca AOAC.
Theo AOAC, lp li ca phng php CV (%) ti nng 100 1000ppb
cho php t 11 15%. lp li ca cc carbamat ti nng 100ppb cao nht
trong 3 mc nng , tuy nhin vn nm trong gii hn cho php ca AOAC.
Nh vy, phng php c thu hi trn 80% v lp li cao, c th p
dng phng php phn tch d lng thuc tr su carbamat trong rau qu.
3.4. Phn tch mu thc t
Sau khi nghin cu cc iu kin tch chit carbamat, chng ti tin hnh
phn tch mt s mu thc. i tng mu l mt s loi rau qu sau: qu l, qu
cam, qu qut, rau dn, rau thm, rau ci xanh Cc mu rau v qu trc khi em

54

phn tch cn phi x l s b. Cc mu c nghin nh v ng nht, sau c

em cn v tin hnh phn tch nh qui trnh trn. Mi mu c lm lp li 3 ln
v ly gi tr trung bnh ca 3 ln.

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

Ha cn bng 1ml MeOH

LC/MS/MS
55

Bng 3.14. Kt qu phn tch cc mu qu

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

Qut

Carbaryl

Fenobucarb

Carbofuran

Propoxur
4

Nho xanh

Carbaryl

Fenobucarb

Carbofuran

Propoxur

57

250

205,58,4

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

Carbaryl

Fenobucarb

200

161,36,4

80,6

KPH

200

162,74,4

81,4

KPH

200

166,25,2

83,1

Bng 3.15. Kt qu phn tch cc mu rau

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

khi ph nh: pha ng, ct sc k, detector.

2. Nghin cu v nh gi c khong tuyn tnh, gii hn pht
hin v gii hn nh lng ca cc carbamat, lp li v thu
hi ca phng php.
3. Nghin cu v a ra iu kin tch chit cc cht carbamat
trong mt s loi rau qu.

60

4. a ra quy trnh phn tch xc nh ng thi d lng ha cht

bo v thc vt nhm carbamat trong mt s loi rau qu bng
phng php sc k lng khi ph.
5. Tin hnh phn tch trn 30 mu rau qu trn a bn H Ni v

pht hin 2 mu rau c cha d lng carbofuran.

T cc kt qu thu c chng ti nhn thy c th p dng phn tch d
lng thuc tr su carbamat trong cc loi rau qu vi tin cy cao. y l mt
phng php c nhiu u im trong phn tch cc cht nhm carbamat mc d chi
ph cho phn tch cn kh cao. Nu c th, ti mong tip tc nghin cu xc nh
ng thi cc cht khc thuc carbamat.

TI LIU THAM KHO

A. TING VIT
1. Cng thng tin in t B Nng Nghip v Pht Trin Nng Thn [2009],

D lng thuc tr su rau qu n tng cao.

2. Con ngi v thin nhin (2007), Ha cht bo v thc

vt v sc kho con ngi (K I).
3. Vit bo (2006), Rau an ton tha thuc tr su.

4. Phm Lun (1988), C s l thuyt K thut phn tch FIA, HTH H Ni

5. Phm Lun, Trn Chng Huyn, T Vng Nghi (1990), Mt s phng

php phn tch in ha hin i, HTH H Ni.

61

6. Q 46/2007/Q-BYT, Quy nh gii hn ti a nhim sinh hc v ho

hc trong thc phm.

7. Rau Hoa Qu Vit Nam (2006), V sinh an ton thc phm: Nhng con

s ng ngi.
8. S khoa hc v cng ngh tnh An Giang (2007), D lng thuc tr su

trong mt s loi rau xanh ngn ngy ti TP. Long Xuyn.

9. S Ti nguyn v Mi trng tnh Vnh Phc ( 2008 ), Thuc bo v thc

vt v nhng tc ng ca chng.
10.

T Th Tho (2006), Bi ging chuyn thng k trong ho phn

tch.
11.

Cng An Ninh Thun ( 2009), Hn hai triu ngi n rau bn.

B. TING ANH
12.

A. Guiberteau , T. Galeano Diz, F. Salinas, J.M. Ortiz (1995),

Indirect voltammetric determination of carbaryl and carbofuran using

partial least squares calibration, Analytyca Chimica Acta, 305, pp. 219
226.
13.

Carbofuran, http://en.wikipedia.org/wiki/Carbofuran

14.

Conacher HB, Page BD, Lau BP, Lawrence JF, Bailey R, Calway P,

Hanchay JP, Mori B (1987), Capillary column gas chromatographic

determination of ethyl carbamate in alcoholic beverages with confirmation
by gas chromatography/mass spectrometry, Journal-Assocoation of
Official Analytical Chemist.
15.

David Arrez-Romn, Antonio Segura-Carretero, Carmen Cruces-

Blanco, Alberto Fernndez-Gutirrez (2004), Determination of aldicarb,

carbofuran and some their main metabolites n groundwater by application
of micellar electrokinetic capillary chromatography with diode-array

62

detection and solid-phase extraction, Pest Management Science, 60, pp.

675-679.
16.

Elvira Grou, Valeria Rdulescu (1983), Direct determination of some

carbamat pesticides in water and soil by high-performance liquid

chromatography, Journal of Chromatography, 260, pp. 502-506.
17.

Feng Tang, Shimei Ge, Yongde Yue, Rimao Hua, Rong

Zhang

(2005),

High-performance

thin-layer

chromatographic determination of carbamate residues in

vegetables, Journal of Planar Chromatography, Volume 18,
Number 101, pp. 28-33.
18.

Feride Koc, Yusuf Yigit, Yavuz Kursad Das, Yasemin Gurel, Cevdet

Yarali (2008), Determanation of aldicarb, propoxur, carbofuran, carbaryl

and methiocarb residues in honey by HPLC with post-column
derivatization and fluorescence detection after elution from a florisil
column, Journal of Food and Drug Analysis, Vol. 16, No. 3, pp. 39-45.
19.

Gianni Sagratini, Jordi Manes, Dario Giardin, Pietro Damiani,

Yolanda Pic (2007), Analysis of carbamate and phenylure pesticide

residues in fruit juices by solid-phase microextraction and liquid
chromatography-mass spectrometry, Journal of Chromatography A,
1147, pp. 135-143.
20.

Jinno Laboratory (2001), Carbaryl, School of Materials Science,

Toyohashi University of Technology, Japan.

21.

Jinno Laboratory (2001), Fenobucarb, School of Materials Science,

Toyohashi University of Technology, Japan.

22.

Jinno Laboratory (2001), Propoxur, School of Materials Science,

Toyohashi University of Technology, Japan.

63

23.

Jos Fernando Huertas-Prez, Ana M. Garca Campana, Laura

Gmiz-Gracia, Antonio Gonzlez-Casado, Monsalud del Olmo Iruela

(2004), Sensitive determination of carbaryl in vegetal food and natural
waters

by

flow-injection

analysis

based

on

the

luminol

chemiluminescence reaction, Analytica Chimica Acta, 524, pp. 161-166.

24.

Jos Fernando Huertas-Prez, Laura Gmiz-Gracia, Ana M. Garca

Campana, Antonio Gonzlez-Casado, Jos L. Martnez Vidal (2005),

Chemiluminescence determination of carbofuran at trace levels on
lettuce and waters by flow-injection analysis, Talanta, 65, pp. 980-985.
25.

Karim D. Khalaf, A. Morales-Rubio, M. de la Duardia, Simple and

rapid flow-injection spectrophotometric determination of carbaryl after

liquid-liquid extraction, Analytica Chimica Acta, 208, pp. 231-238.
26.

L. Alvarez-Rodrguez, Ll. Monferrer-Pons, J. S. Esteve-Romero, M.

C.Garca-Alvarez-Coque, G. Ramis-Ramos (1997), Spectrophotometric

Determination of Carbamate Pesticides With Diazotized Trimethylaniline
in a Micellar Medium of Sodium Dodecyl Sulfate, Analyst, Vol 122,
pp.459-463.
27.

Masuru Kawasaki, Tsuyoshi Inoue, Katsuharu Fukuhara, Sadao

Uchiyama (1999), Study on GC/MS (SIM) for determination of

carbamate and organonitrogen pesticides in foods with simple clean-up by
SPE method, J. Japan, Vol 4, No. 5.
28.

Mian Liu, Hui Yang, Hongxia Liu, Po Han, Xie Wang, Shusheng

Zhang, Yangjie Wu (2007), Development of high-performance liquid

chromatography and non-aqueous capillary electrophoresis methods for
the determination of fenoxycarb residues in wheat samples, Journal of
the Science of Food and Agriculture, Volume 88, Issue 1, pp. 62-67.
29.

Min Liu, Yuki Hashi, Yuanyuan Song, Jin-Ming Lin (2005),

Simultaneous determination of carbamate and organophosphorus

64

pesticides in fruits and vegetables by liquid chromatography-mass

spectrometry, Journal of Chromatography A, 1097, pp. 183-187.
30.

M. Fernndez, Y. Pic, J. Manes (2000), Determination of carbamate

residues in fruits and vegetables by matrix solid-phase dispersion and

liquid chromatography-mass spectrometry, Journal of Chromatography
A, 871, pp. 43-56.
31.

O. Bhargavi, K. Kiran, K. Suvardhan, D. Rekha, K. Janardhanam, P.

Chiranjeevi (2006), A sensitive determination of carbofuran by

spectrophotometer

using

4,

4-azo-bis-3,35,5-tetrabromoaniline

in

various environmental samples, E-Journal of Chemistry, vol. 3, pp. 68

77.
32.

Urmila Tamrakar, Vinay K. Gupta, Ajai K. Pillai (2009),

Spectrophotometric analysis of carbamate pesticides after thermal

gradient separation, Journal of Planar Chromatography, Volume 22,
Number 2, pp. 77-82.
33.

Xiaozhong Hu, Yu Jianxin, Yan Zhigang, Ni Lansun, Lin Yanfei,

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.

Xiaoping Wu, Ling Wang, Zenghong Xie, Professor, Jieshan Lu,

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.

Rangamannar, Spectrophotometric determination of carbosulfan in

various environments using novel oxidative coupling, Proceedings of the

65

Third International Conference on Environment and Health, Chennai,

India (2003), pp. 400 403.

PH LC
1. Kho st thnh phn pha ng ch isocractic (HCOOH 0,1% : MeOH)

66

RT: 0.00 - 5.86

NL: 5.03E5
TIC F: + c ESI SRM ms2
222.00@45.00 [ 164.50-165.50]
MS mix 1000ppb-90%MeOH

3.83

100

Relative Abundance

50
0.14

0
100

0.80

1.07

1.99

1.79

2.78

2.32

4.23

3.11

4.62

5.15

5.48
NL: 4.91E4
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS mix
1000ppb-90%MeOH

3.78

50
0.35

1.28

0.62

1.54

1.93

3.65

3.12

2.46

4.17

0
100

4.57

5.03

5.55
NL: 4.44E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS mix 1000ppb-90%MeOH

4.12

50
0.76

0.50

1.09

1.48

4.45

2.27

2.08

3.26

2.87

3.79

0
100

5.63

4.78

5.24
NL: 9.23E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS mix 1000ppb-90%MeOH

4.34

50
0.85

0.52

0
0.0

0.5

1.18

1.0

1.37
1.5

2.23
2.0

2.63
2.5

3.28

4.67

3.48

3.0
Time (min)

3.5

4.0

4.5

5.00

5.59

5.0

5.5

Thnh phn pha ng 10 : 90

RT: 0.00 - 7.68

NL: 7.29E5
TIC F: + c ESI SRM ms2
222.00@45.00 [ 164.50-165.50]
MS mix 1000ppb-80%MeOH

4.36

100

Relative Abundance

50
0.28

0
100

1.00

1.72

2.19

2.38

4.75 4.89

3.63

5.41

6.14

7.06
NL: 7.29E4
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS mix
1000ppb-80%MeOH

4.30

50
0.68

1.14 1.54

2.00

3.32

2.72

4.63
4.90

3.78

0
100

5.49

6.34

7.27

7.00

NL: 1.07E5
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS mix 1000ppb-80%MeOH

4.91

5.10

50
0.96

0
100

1.29

1.68 1.94

2.60

3.06

5.24

4.51

3.52

7.08

5.57 6.29

NL: 9.78E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS mix 1000ppb-80%MeOH

5.52

50
0.52
0
0

0.85
1

1.70 1.97
2

2.76

3.28
3

3.88
4
Time (min)

4.27

4.93
5

6.38

6.90

7.37

Thnh phn pha ng 20 : 80

67

RT: 0.00 - 9.61

NL: 8.38E5
TIC F: + c ESI SRM ms2
222.00@45.00 [ 164.50-165.50]
MS mix 1000ppb-70%MeOH

5.29

100

Relative Abundance

50
2.32

0.94 1.27

0
100

3.05 3.51

4.69

5.94 6.60 7.39 7.85

8.97
NL: 6.95E4
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS mix
1000ppb-70%MeOH

5.23

50
2.60

0.95 1.08 1.35

7.27

4.57

3.26 3.78

8.33 8.72

6.22 6.61

0
100

NL: 8.92E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS mix 1000ppb-70%MeOH

6.43

50
0.37

0
100

1.16

1.88

3.00 3.66 4.06

6.89 7.22
8.20 8.93 9.32

6.10

4.78

NL: 9.49E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS mix 1000ppb-70%MeOH

8.29
8.49

50
1.25

0.33
0
0

2.04 2.50

3.68 4.08 4.21

3

6.58 7.04

5.40

5
Time (min)

9.02

7.90

Thnh phn pha ng 30 : 70

RT: 0.00 - 18.10

NL: 8.30E5
TIC F: + c ESI SRM ms2
222.00@45.00 [ 164.50-165.50]
MS mix 1000ppb-60%MeOH

7.19

100

Relative Abundance

50
1.53

0
100

2.85

4.23

7.85 9.24 10.68

6.08

13.65 14.37

16.35
NL: 8.47E4
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS mix
1000ppb-60%MeOH

7.27

50
1.28 1.81

0
100

7.47
8.00

6.81

3.32 3.98

13.07 14.32 14.51 16.55

10.56

NL: 7.75E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS mix 1000ppb-60%MeOH

9.78
9.65

50
2.94 3.73

0.96

0
100

5.77

7.15

9.46
9.06

10.51 11.23
13.14

15.38 16.83

15.40 15.53
15.73
15.21

50
1.71

0
0

3.55
4

7.50 8.42 9.08 11.91

5.33
6

8
10
Time (min)

12.44
12

15.86
16.19

14.81
14.61
14

NL: 8.34E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS mix 1000ppb-60%MeOH

16

18

Thnh phn pha ng 40 : 60

68

RT: 0.00 - 30.02

NL: 7.32E5
TIC F: + c ESI SRM ms2
222.00@45.00 [ 164.50-165.50]
MS mix 1000ppb-50%MeOH

11.48

100

Relative Abundance

50
1.34 2.92

0
100

5.95 7.39

10.62

12.13 13.85

19.18 21.02 23.39 26.03 28.07

NL: 7.69E4
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS mix
1000ppb-50%MeOH

11.49
11.36 11.62

50
11.82 13.13

6.81 8.72 10.83

1.61 3.52
0
100

18.60 20.64
17.82

50
1.69 3.07
2.50

0
100
50

7.17 7.44
4.01 6.65
6.12

2.24

15.51

6.36 7.75 10.38 12.88

11.06

18.21
18.48

17.49

13.56

27.03
NL: 7.79E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS mix 1000ppb-50%MeOH

19.79 22.63 25.85 27.56

NL: 8.10E3
TIC F: + c ESI SRM ms2

17.31

12.31

23.67

18.08

21.33
20.61

29.82 208.00@37.00 [ 151.50-152.50]

26.00

MS mix 1000ppb-50%MeOH

22.25

0
0

10

15
Time (min)

20

25

30

Thnh phn pha ng 50 : 50

2. Kho st thnh phn pha ng s dng cht ci bin nn
RT: 0.00 - 18.03

NL: 2.74E6
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS mix
1000ppb-acetic

RT: 8.83
MA: 62596017

100
50
0.24

Relative Abundance

2.23 3.00

5.15 6.22 6.83

100

9.60 10.98 12.28

RT: 8.84
MA: 7095289

14.58

16.73
NL: 2.89E5
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS mix 1000ppb-acetic

50
0.94 2.01

3.93 4.47

6.16

8.07

100

9.61 10.53 12.37 13.21

RT: 9.85
MA: 4205380

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

10.31 12.15

8.62

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

RT: 10.87
AA: 2191283

100
50
1.74

0
0

4.19 5.04 5.96

4

7.57 8.11

10.41

8
10
Time (min)

11.18
12

13.86 14.01
14

17.24
16

18

Dung dch acid acetic 0,1% trong nc

69

RT: 0.00 - 18.03

NL: 2.02E6
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS mix
1000ppb-NH4Ac

RT: 8.91
MA: 52548096

100
50
0.47 1.62 2.69

Relative Abundance

9.60 11.44 12.74 13.51 14.74

6.68 7.22
RT: 8.92
MA: 5289116

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
1.55 2.32 3.24

8.61

6.92

5.16

9.46 10.84

12.76

16.75 17.90

13.22

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

1.26 2.02 3.33 4.25

0
100

11.16 11.92 13.76

RT: 10.95
MA: 2239988

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

5.35 6.04

2.35 3.04
2

6.42 8.41

10.56

8
10
Time (min)

11.41 12.10 14.09

12

14

16.55
16

18

Dung dch amoni acetat 0,1% trong nc

RT: 0.00 - 18.03

NL: 3.92E6
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS mix
1000ppb-NH4OH

RT: 8.75
MA: 88164531

100
50
0.24

Relative Abundance

9.52 10.67 12.51 13.28 14.51 16.04

6.45 7.22
RT: 8.84
MA: 8026138

2.39 3.46 4.23

100

NL: 3.68E5
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS mix 1000ppb-NH4OH

50
2.78

0.79

10.91 12.14
RT: 9.77
MA: 8972544

6.39 7.23

4.78

100

12.60

15.52 16.74
NL: 4.78E5
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

Dung dch acid focmic 0,1% trong nc

70

3. Kho st t l dung mi chit

RT: 0.00 - 18.05
NL: 3.62E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS
MeOH-H2O-1-1

RT: 8.87
MA: 4416725

100

Relative Abundance

50
1.86

0.37

9.22
6.68 7.73
RT: 8.88
MA: 654621

3.87 4.49

100

9.92 11.85

14.04 14.82 15.96

50
1.96 2.48 4.06 4.67

0.73

9.14

6.25 7.30

100
7.31
50

3.28

1.53

6.35
4.16

15.45

17.64

NL: 1.48E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS
MeOH-H2O-1-1

RT: 9.77
MA: 238176
9.94
11.87

8.89

5.03

14.75

9.67 12.82 13.17

12.92

14.06

15.64

17.39
NL: 1.96E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS
MeOH-H2O-1-1

RT: 10.84
MA: 295354

100
50
0.59

0.85

7.33

3.74 4.71 5.58

8.12

15.13

11.36 12.68

8.91

NL: 4.65E4
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MS
MeOH-H2O-1-1

16.97

0
0

8
10
Time (min)

12

14

16

18

MeOH:H2O = 1:1

RT: 0.00 - 18.05

NL: 3.62E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS
MeOH-H2O-1-1

RT: 8.87
MA: 4416725

100

Relative Abundance

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

14.04 14.82 15.96

50
0.73

1.96 2.48 4.06 4.67 6.25 7.30

100
7.31
50

1.53

3.28

6.35
4.16

9.14

NL: 1.48E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS
MeOH-H2O-1-1

RT: 9.77
MA: 238176
9.94
11.87 12.92

8.89

5.03

14.75 15.45 17.64

9.67 12.82 13.17

14.06

15.64

17.39
NL: 1.96E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS
MeOH-H2O-1-1

RT: 10.84
MA: 295354

100
50
0.59 0.85

3.74 4.71 5.58

7.33

8.12 8.91

NL: 4.65E4
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] 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 = 2:1

71

RT: 0.00 - 18.04

NL: 1.07E6
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS
MeOH-H2O-3-1

RT: 8.86
MA: 16042383

100

Relative Abundance

50
1.50 2.47

3.78

5.01

100

9.65
6.50 7.37
RT: 8.87
MA: 1605778

12.54 13.16 14.38

16.84
NL: 8.83E4
TIC F: + c ESI SRM ms2
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

5.90 6.77 7.82

12.55 13.34 14.04 16.32 17.29

NL: 6.74E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS
MeOH-H2O-3-1

RT: 9.76
MA: 970162

100
50
3.89 4.59 6.26 6.70

1.61

10.29
10.64

8.18

13.35 14.32

15.90 17.12
NL: 8.37E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS
MeOH-H2O-3-1

RT: 10.84
MA: 877065

100
50
3.30 3.83 4.35 6.02

1.55

0
0

7.59 8.73 10.40

8
10
Time (min)

12.06 14.08 14.69

12

16.18

14

16

18

MeOH:H2O = 3:1

RT: 0.00 - 18.04

NL: 9.18E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS
MeOH-H2O-4-1

RT: 8.86
MA: 13760894

100
50

Relative Abundance

9.48 11.05 12.02 13.51

2.91 4.05 5.27 6.41 7.46
RT: 8.88
MA: 1094608

1.42

0
100
50

0.64

2.39

3.97 4.76

6.16

8.35

16.14 17.19

12.03 13.43 14.39

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

2.67 3.28

10.29 11.25

6.78 7.48 9.59

4.86

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

4.62 6.54 6.89

8.82 10.66

11.45 12.33
14.34

16.79

0
0

8
10
Time (min)

12

14

16

18

MeOH:H2O = 4:1

72

4. Kho st dung mi ra gii

RT: 0.00 - 18.04

NL: 1.78E6
TIC F: + c ESI SRM ms2
222.00@48.00 [ 164.50-165.50]
MS chiet bang diclometan

RT: 9.04
MA: 27949229

100

Relative Abundance

50
0.80 1.68

3.26

5.18

6.50

100

7.55
9.57 11.32
RT: 9.05
AA: 2633800

13.25 14.56

16.31
NL: 1.57E5
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS ICIS chiet
bang diclometan

50
0

NL: 1.37E5
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS ICIS chiet bang diclometan

RT: 10.03
AA: 1843101

100
50
0

NL: 8.79E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS ICIS chiet bang diclometan

RT: 11.10
AA: 980813

100
50
0.85

2.43

4.18
4

11.45 12.68

9.79

7.07 7.95

8
10
Time (min)

12

17.93

14.52

14

16

18

Ra gii carbamat bng dung mi diclometan

RT: 0.00 - 18.04

NL: 5.29E5
TIC F: + c ESI SRM ms2
222.00@48.00 [ 164.50-165.50]
MS chiet bang n-hexan

RT: 8.95
MA: 7225108

100

Relative Abundance

50
1.24 2.03

3.43 4.57 6.32 6.59

100

8.34
10.18 11.14
RT: 8.96
AA: 853691

13.33 14.21

16.75
NL: 7.26E4
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS ICIS chiet
bang n-hexan

50
0

NL: 6.91E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS ICIS chiet bang n-hexan

RT: 9.85
AA: 916035

100
50
0.65 1.70

4.15 4.50 5.64 6.70

10.29

8.36

12.39

14.32

16.68 17.56
NL: 8.83E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS chiet bang n-hexan

RT: 11.01
MA: 1380078

100
50
1.72

0
0

7.24 7.86

3.21 4.26 4.70

4

12.85

9.08

8
10
Time (min)

12

15.04 16.09 16.44

14

16

18

Ra gii carbamat bng dung mi n-hexan

73

5. Kho st t l dung mi ra gii

RT: 0.00 - 18.02
NL: 1.05E6
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS ICIS mix
200ppb

RT: 8.90
AA: 16288884

100

Relative Abundance

50
1.15

3.00 3.69

6.37

5.22

100

9.44
8.14
RT: 8.91
MA: 1788709

11.20 11.90 13.51

16.11 17.80
NL: 1.09E5
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MS mix
200ppb

50
2.47 3.24

1.01

10.68 10.91

8.53

6.69

5.08

13.52

15.97 16.74
NL: 7.57E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS mix
200ppb

RT: 9.92
MA: 1370381

100
50
0.33

1.87 2.86

6.93 8.16 9.54

4.78 5.47

12.84

10.77

14.37 15.45

17.59
NL: 5.20E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS ICIS mix
200ppb

RT: 10.94
AA: 762900

100
50
0
0

8
10
Time (min)

12

14

16

18

Sc chun carbamat 200ng/ml

RT: 0.00 - 18.02

NL: 9.76E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS
CH2Cl2-hexan-1-2

RT: 8.83
MA: 15323127

100

Relative Abundance

50
1.39 2.15 3.61

9.29 10.90
6.76 7.98
RT: 8.84
MA: 1743626

5.38

100

12.89 13.81 15.20

17.42
NL: 1.01E5
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS CH2Cl2-hexan-1-2

50
0.17

2.70 3.47 3.70

6.92 7.23

9.84

11.29 12.21 13.60

16.05 17.74
NL: 6.34E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS
CH2Cl2-hexan-1-2

RT: 9.77
MA: 990046

100
50
1.10

2.48

4.09

5.32 7.55

7.78

10.15

9.39

12.53

14.45 14.76
16.52
NL: 5.12E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS
CH2Cl2-hexan-1-2

RT: 10.87
MA: 581813

100
50
1.35 2.43

3.66

0
0

6.65
6

9.72

11.25

8
10
Time (min)

12

6.80 7.80

13.94 14.78
14

16

17.16
18

Ra gii carbamat bng dung mi diclometan/hexan (1:2)

74

RT: 0.00 - 18.03

NL: 1.01E6
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS
CH2Cl2-hexan-1-1

RT: 8.91
MA: 16221063

100
50
0.78 2.16 3.00

Relative Abundance

10.29
6.38 7.30 7.99
RT: 8.84
MA: 1619068

4.30

100

12.05 13.13 14.59 15.35 16.66

NL: 9.91E4
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS CH2Cl2-hexan-1-1

50
1.09 1.86 3.17

6.31

4.93

11.91 12.60 13.60

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

5.48

5.17

11.00 12.23
RT: 10.95
MA: 725971

6.86 7.86 8.93

100

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

5.19 6.88 7.11

3.50

11.56 12.10

8
10
Time (min)

12

16.85

14.86
14

16

18

Ra gii carbamat bng dung mi diclometan/hexan (1:1)

RT: 0.00 - 18.03

NL: 9.71E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS
CH2Cl2-hexan-2-1

RT: 8.91
MA: 15246098

100
50
0.16 2.08 2.77

Relative Abundance

0
100

9.45 10.90 11.90 13.66 14.74

4.46 5.46 6.53 7.30
RT: 8.92
MA: 1570343

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

2.01 3.09 5.39

5.77 6.77

8.61

10.68 11.30

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

RT: 9.85
AA: 1025568

100
50
0.72 1.87 3.02

4.79

6.47 8.85

9.54

12.15 12.77 13.76 14.91

17.22
NL: 3.19E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS
CH2Cl2-hexan-2-1

RT: 10.95
MA: 445020

100
50

1.05 2.66 2.89

4.35 5.65 6.80 7.65

8.95 9.34

11.79

13.86

15.63

17.77

0
0

8
10
Time (min)

12

14

16

18

Ra gii carbamat bng dung mi diclometan/hexan (2:1)

75

RT: 0.00 - 18.02

NL: 1.03E6
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS
CH2Cl2-hexan-3-1

RT: 8.98
MA: 15646460

100

Relative Abundance

50
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

14.81 16.50 17.57

NL: 9.69E4
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS CH2Cl2-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
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS
CH2Cl2-hexan-3-1

RT: 9.92
MA: 1042118

100
50
0.64

2.33

6.85 8.08 9.31

4.55 5.09

14.52 15.44

10.76 11.69

17.82
NL: 3.89E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS
CH2Cl2-hexan-3-1

RT: 11.02
MA: 533507

100

10.86

50

1.04

3.34

8.33

3.50 4.04 6.03 6.64

9.94

11.86

16.92

14.85

13.39

0
0

8
10
Time (min)

12

14

16

18

Ra gii carbamat bng dung mi diclometan/hexan (3:1)

6. Kho st th tch dung mi ra gii

RT: 0.00 - 18.03

NL: 6.20E5
TIC F: + c ESI SRM ms2
222.00@48.00 [ 164.50-165.50]
MS the tich rua giai 20ml

RT: 8.98
MA: 9661932

100
50

Relative Abundance

2.77 3.61 5.69 6.22

0.93

0
100

8.68

9.52
RT: 8.92
MA: 810528

50
0.40 2.55 2.86

4.47

6.62 7.61

11.75 13.13 14.20 15.12

9.15
9.46 9.92 11.60 13.37
13.75

17.42
NL: 5.93E4
TIC F: + c ESI SRM ms2
210.00@45.00 [ 152.50-153.50,
167.50-168.50] MS the tich rua
giai 20ml

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

RT: 9.93
AA: 483706

100
50
0.34 1.95

5.78 6.40 7.09

3.41

12.00 12.46

8.93

15.37

16.45
NL: 1.51E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS ICIS the tich rua giai 20ml

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

Th tch dung mi ra gii 20ml

76

RT: 0.00 - 18.02

NL: 8.61E5
TIC F: + c ESI SRM ms2
222.00@48.00 [ 164.50-165.50]
MS the tich rua giai 40ml

RT: 8.98
MA: 14658407

100
50
1.00 1.84

Relative Abundance

6.45 7.14

3.76 4.61

9.75
RT: 8.99
MA: 1414805

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

8.61

5.84 6.69

4.08

9.99 10.83 12.14 13.29

16.36
NL: 6.43E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS the tich rua giai 40ml

RT: 9.85
MA: 935027

100
50
0.33 1.41

4.94

3.63

9.00

6.55 7.31

10.61

13.37

15.91 16.06
NL: 6.02E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS the tich rua giai 40ml

RT: 10.94
MA: 722695

100

11.10

50
0.81

4.50 5.65 6.72

2.73

0
0

8.10

10.63

8
10
Time (min)

11.56
12

14.47 15.93 17.31

14

16

18

Th tch dung mi ra gii 40ml

RT: 0.00 - 18.05

NL: 1.12E6
TIC F: + c ESI SRM ms2
222.00@48.00 [ 164.50-165.50]
MS the tich rua giai 50ml

RT: 8.96
MA: 15748852

100
50
0.28

Relative Abundance

2.38 3.61

9.66 10.53 12.55 13.69

6.77 7.64
RT: 8.97
MA: 1662739

4.93

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

4.41 4.94 5.46 7.30 8.70

100

9.40 11.77 12.38 12.91 14.75

RT: 9.94
AA: 1147846

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

10.90 12.04
RT: 11.01
AA: 720851

6.52

100
50
1.64

4.27

0
0

4.62

6.55 7.42 8.21

6

10.58

8
10
Time (min)

14.06 15.29 16.60

NL: 5.54E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS ICIS the tich rua giai 50ml

11.98 13.29
12

14

17.85

13.91
16

18

Th tch dung mi ra gii 50ml

77

RT: 0.00 - 18.02

NL: 1.07E6
TIC F: + c ESI SRM ms2
222.00@48.00 [ 164.50-165.50]
MS the tich rua giai 60ml

RT: 8.90
MA: 15587186

100
50
0.39

Relative Abundance

2.69

9.29 10.44
8.37
RT: 8.84
MA: 1719752

6.37

4.53

100

12.89 14.12

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

0.40 1.93 4.00

7.23

5.54

10.22 11.68 12.37

15.05 15.74
NL: 7.02E4
TIC F: + c ESI SRM ms2
202.00@45.00 [ 144.50-145.50]
MS the tich rua giai 60ml

RT: 9.92
MA: 1159284

100
50
3.40

0.26 1.18

8.23 9.62

6.09 6.39

11.46 12.84

14.37 16.60 17.21

NL: 3.90E4
TIC F: + c ESI SRM ms2
208.00@37.00 [ 151.50-152.50]
MS the tich rua giai 60ml

RT: 10.94
MA: 627767

100
50

4.65

2.58 2.73

8.79

6.65 7.34

9.25

11.71 13.17

13.63 15.31 16.47

0
0

8
10
Time (min)

12

14

16

18

Th tch dung mi ra gii 60ml

7. Sc phn tch mt s mu thc
RT: 0.00 - 18.00
100

8.39

1.51

3.40 4.49
5.41

0.68

Relative Abundance

50

7.65

9.27

11.06

17.11 202.00@45.00 [

15.49

144.50-145.50] MS cam

5.89

0
100

NL: 5.67E3
TIC F: + c ESI SRM ms2

13.65 13.82
15.79
12.68

NL: 1.19E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS cam

12.26
3.06

50

0.43

5.21
4.24

1.04

0
100

5.29

6.83

0.89

2.25

3.78 5.10

0
100
50

0.05 1.54

6.91 7.75

12.39 14.45

10.81

6.50

3.12

50

15.06 16.29

3.24 4.60

6.37

6.72

10.00 10.96
9.34
11.71

10.03
7.36 8.19
10.17
9.33
6.71
10.78
5.00 6.31

12.89

17.56

14.56

17.45
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

NL: 8.72E3
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MS cam

17.70

0
0

8
10
Time (min)

12

14

16

Mu cam khng thm chun

78

RT: 0.00 - 18.00

9.49

100

Relative Abundance

2.96
2.40 3.40 4.72 5.33

0.60

50

8.62

0
100
0.79
50

12.95

10.98

17.95 202.00@45.00 [

14.57 15.84

144.50-145.50] MS rau cai

7.70

5.03
2.80
4.64
5.91
3.37

2.06

NL: 9.58E3
TIC F: + c ESI SRM ms2

12.12

9.75

8.45

10.77

9.46

7.40

13.75 14.06
11.82

17.78 NL: 8.17E3

15.90

16.25

TIC F: + c ESI SRM ms2

208.00@37.00 [
151.50-152.50] MS rau cai

6.48

0
100

17.67 NL: 1.40E4

4.49
0.19

50

6.85

1.16 2.52

6.02

4.05

8.08

7.12

8.39 9.39

0
100

9.56
1.28
0.45

50

3.91

2.94

5.40

6.40
6.23

6.80

7.94

11.32

11.89

13.02

11.05

14.99

12.93

8.37

TIC F: + c ESI SRM ms2

210.00@45.00 [
152.50-153.50,
167.50-168.50] MS rau cai

14.47 15.26
16.58

13.19

16.43

NL: 1.26E4
TIC F: + c ESI SRM ms2
222.00@48.00 [
17.40 164.50-165.50] MS rau cai

0
0

8
10
Time (min)

12

14

16

Mu rau ci xanh khng thm chun

RT: 0.00 - 17.99

100

Relative Abundance

50

0.64

0
100

1.47 2.48
3.62
4.58

3.76

1.61

3.06

4.28

NL: 1.13E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS rau
thom

14.04

9.09 10.10
6.81 7.86
5.24
10.67
5.54

12.73
14.35
16.23

6.52
6.43
5.73

8.53

9.41 9.63
10.24

12.78

50

13.92

16.81
16.55

14.05

0
100
0.10

50

2.90

3.25

5.22
4.92
4.26

7.77
6.98

11.53

8.47 9.04

12.76

9.87

13.07
14.73

0
100

0.97

50

6.44 7.67
5.91
6.66
5.43
2.45 3.02 3.72
3.90

9.20

10.65

10.86
11.87

NL: 8.76E3
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS rau
thom

NL: 1.55E4
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50,
17.93 167.50-168.50] MS rau
16.13
thom

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

Mu rau thm khng thm chun

79

RT: 0.00 - 17.99

8.00

100
4.76

Relative Abundance

4.15

0.60 1.48
2.57

50

6.73
5.07

0
100

9.05 9.71

6.99

11.07 12.69

13.65

7.58

13.84
9.02

2.41
2.63

10.77

4.90

0.74 2.28

16.24

13.23
12.00

NL: 8.06E3
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS rau den

14.45 16.07
16.95

0
100

NL: 1.54E4
TIC F: + c ESI SRM ms2

16.58

50

1.46 2.21

6.41 7.03

5.10

3.65

0
100

9.31

6.49
6.36

50
1.37 1.89 3.69

5.13

6.10
5.31

10.40
11.36

13.73
12.98 14.91

17.10 210.00@45.00 [

152.50-153.50,
167.50-168.50] MS rau den

16.27

NL: 1.66E4
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS rau den

8.68
9.73

7.32

11.00 12.36

NL: 9.37E3
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS rau den

14.00

6.39

50

15.84

13.63
14.38 15.30

17.40

0
0

8
10
Time (min)

12

14

16

Mu rau rn khng thm chun

RT: 0.00 - 17.99

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
50
0.88 1.89 2.68

Relative Abundance

4.52

6.27

8.46

9.29 9.82 11.83 12.97

15.21

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

9.00

50
4.97 5.97 7.03

1.33 1.90 2.73

8.47

9.65 10.49

13.25 14.21 15.22

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
50
0.51

2.39

3.88

6.25 6.42

8.96 9.67

10.37

11.11 13.56

15.18

17.51
NL: 6.43E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS rau den-tc
500ng

RT: 11.78
MA: 1102168
11.91

100
50
1.66 2.23 3.89 5.12 6.04

0
0

7.92

9.24

8
10
Time (min)

11.56

12.04
12.26 13.44
12

15.55 15.98

14

16

Mu rau rn thm chun 500ng/ml

80

RT: 0.00 - 17.99

NL: 1.38E6
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS rau
thom-tc 500ng

RT: 8.76
MA: 30634148

100
50
0.27 1.58 2.85 3.95

Relative Abundance

8.37

6.22 7.36

9.20 9.73 11.52 13.10

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

RT: 8.77
MA: 2753331

100

8.95

50
0.50

8.47
6.58 6.89

1.85 2.77 4.09

9.08

9.78

12.59

14.60 15.39

17.80
NL: 9.02E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS rau
thom-tc 500ng

RT: 10.01
MA: 1520063

100

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

11.99

50
0.26 1.88

0
0

11.51
5.29 6.12 7.18 8.10 9.15 9.76

3.32
4

8
10
Time (min)

12.43 14.10
12

15.76

14

17.82

16

Mu rau thm thm chun 500ng/ml

RT: 0.00 - 17.99

NL: 1.47E6
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS rau cai-tc
500ng

RT: 8.77
MA: 31082281

100
50
0.58

Relative Abundance

9.20 9.73
5.53 6.71 8.07
RT: 8.78
MA: 3153493

2.46 3.60

100

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

8.69
8.60

50
0.11

0.76

3.52

6.89

5.36

8.52

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
0.86 1.61

3.97 4.58

7.65

8.35

9.62

10.15

11.59

16.23

13.83

NL: 7.32E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS rau cai-tc
500ng

RT: 11.65
MA: 1082094

100

11.82

50
1.31 2.19

0
0

3.98 4.07 6.17 7.27

4

9.24
8
10
Time (min)

11.25

11.95 12.87
12

15.98 17.17

14

16

Mu rau ci xanh thm chun 500ng/ml

81

RT: 0.00 - 18.02

NL: 8.97E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS cam-tc
250ng

RT: 8.98
MA: 14023139

100
50
1.39

Relative Abundance

2.84

5.61 6.60

4.22

100

10.06
8.44
RT: 8.92
MA: 1460845

50
2.62

2.16

8.69

6.46

3.93 5.08

9.53

12.05 13.05 14.43 15.73

17.42
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

11.37 12.90 13.98

NL: 6.20E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS cam-tc
250ng

RT: 9.85
MA: 811777

100
50
0.56

8.31

5.17 5.70

2.25 3.10

12.53

10.31

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

13.01

8.87 10.64

14.55 14.93

17.77

0
0

8
10
Time (min)

12

14

16

18

Mu cam thm chun 250ng/ml

RT: 0.00 - 18.02

NL: 9.95E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS bap cai-tc
250ng

RT: 8.90
MA: 14786230

100
50

Relative Abundance

9.44
6.29 6.91 8.37
RT: 8.91
MA: 1598760

1.23 2.31 3.30 4.61

0
100

12.05

13.89

16.34 17.42
NL: 1.29E5
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50, 167.50-168.50]
MS bap cai-tc 250ng

50
1.55 2.32 3.16 4.85

6.38 7.46

9.68 10.99 11.29

14.74 15.74 17.81

NL: 5.42E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS bap cai-tc
250ng

RT: 9.85
MA: 786793

100
50
0.26

2.48

3.94

9.46
5.40 6.47 8.08 8.77

10.08
10.61

11.61 13.53 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

RT: 10.94
MA: 615061

100
50
2.81

0.43

0
0

4.27 5.49
4

7.03 7.87 9.64

6

10.64

8
10
Time (min)

11.25
12

14.78 15.16 15.85

14

16

18

Mu bp ci thm chun 250ng/ml

82

RT: 0.00 - 18.00

100

6.05
0.83

Relative Abundance

50

2.41
1.75

6.79
8.54
7.67

8.98

10.87
10.56 11.79

13.58 14.15

4.65 5.39

0
100

10.26
0.85

3.52 3.65

1.24

5.49 6.67

50
0
100
50
0
100

4.72

6.08

14.78

11.50
12.38

10.07 10.81
9.54

7.18

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

11.84
13.11 14.25

8.43
9.66 10.27

5.06 5.41

5.16

2.05
0.60
2.14
1.66 2.66

50

6.28

7.25
3.88

0.37

11.31

8.99 9.56

8.30

2.52
1.47 2.08 2.78

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

13.87 15.22 16.67

NL: 1.22E4
TIC F: + c ESI SRM ms2
202.00@45.00 [
144.50-145.50] MS rau cai
ngot

NL: 8.25E3
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS rau cai
14.27 16.55 17.86 ngot

14.01
12.48

8.23

12.56

0
0

8
10
Time (min)

12

14

16

Mu rau ngt khng thm chun

RT: 0.00 - 17.98

50
Relative Abundance

NL: 3.63E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS can tay

RT: 9.03
MA: 7157181

100

2.81 3.68

1.18

0
100

RT: 3.78
AA: 142037

8.81
8.72
7.32 8.41
9.33 11.22 12.31 13.41 14.63
5.35
RT: 8.86
AA: 197083 RT: 10.44
RT: 7.63
RT: 15.26
AA: 144010
AA: 62987
AA: 160150

17.52

50
0
RT: 1.51
AA: 32696

100

RT: 3.66
AA: 20863

RT: 6.51
AA: 22677

RT: 9.66
AA: 32743

RT: 11.54
AA: 43206

RT: 17.81 NL: 7.58E3

AA: 30437 TIC F: + c ESI SRM ms2

RT: 13.30
AA: 62916

202.00@45.00 [
144.50-145.50] MS ICIS can
tay

50
0
RT: 7.09
AA: 85774

100
RT: 1.57
AA: 30051

50

RT: 4.50
AA: 33664

RT: 11.07
AA: 93405

RT: 12.87
AA: 60167

NL: 1.47E4
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MS ICIS can
tay

RT: 16.02
AA: 56238

NL: 1.05E4
TIC F: + c ESI SRM ms2
208.00@37.00 [
151.50-152.50] MS ICIS can
tay

0
0

8
10
Time (min)

12

14

16

Mu rau cn ty khng thm chun

83

RT: 0.00 - 18.00

8.77

50
5.70 6.31

1.32 2.15 3.47

0
Relative Abundance

NL: 1.12E5
TIC F: + c ESI SRM ms2
222.00@48.00 [
164.50-165.50] MS mung toi

RT: 8.94
MA: 2006583

100

100

0.94 2.47
1.20

50

7.37 8.68

5.58

2.82
3.57

9.34

11.83

13.32 13.67

16.61 17.70

7.33
16.36
13.51
8.95 9.04
13.29
7.68
11.06
14.04 14.96
9.65
17.58

5.10

0
100
1.34

50

2.04 2.79

4.06

6.51
5.33

8.75
8.66

9.05 10.28

11.24 12.03
12.47

14.66

15.76

NL: 9.45E3
TIC F: + c ESI SRM ms2
202.00@45.00 [
17.86 144.50-145.50] 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

6.13 6.30 7.14 8.19

9.55

11.30
11.69

14.54
13.62

NL: 1.28E4
TIC F: + c ESI SRM ms2
210.00@45.00 [
152.50-153.50,
167.50-168.50] MS mung toi

14.76

17.91

0
0

8
10
Time (min)

12

14

16

Mu rau mng ti khng thm chun

84