NHNG THCH THC TRONG PHN

TCH KIM NGHIM THC PHM

HIN NAY, MI QUAN TM LN

CA CC PHNG KIM NGHIM

Nguyn Hng Tho, Nguyn Phng Phi, V Trng Duy, Nguyn S Hong Lin,

V Phng Tho, inh th H Long, Phm th nh, Chu Phm Ngc Sn

Hi Ha hc TP H Ch Minh

Cng ty Dch v KHCN Sc K Hi ng

PHN TRNH BY

I. NHNG S KIN V AN TON THC PHM

II. CC HA CHT C HI

III. NHNG THCH THC TRONG PHN TCH

KIM NGHIM M BO AN TON THC PHM

I. NHNG S KIN1.Cung cp thc phm (TP) hin nay mang tnh ton cu i hi phi

tng cng gim st m bo an ton thc phm (ATTP)

2. Thc phm hin rt nhiu v phc tp, ph gia thc phm rt a dng,

an xen vi ha cht c kh nng gy c c tnh hay do thiu hiu bit c

cho thm vo to c mt c trng nhm t li nhun bt chnh

3. Mc nguy him c th rt ln i vi nhng thc phm sn xut ti cc

nc c h tng cha tht pht trin v c cu gim st cha tht hiu qu

Cc mi nguy him: vi sinh, vt l, ha hc, hng nhi

4 Mt chuyn ngnh gi l Foodomics chuyn nghin cu thc phm(dinh dng, thc phm bin i gen, protein hc, c cht hc lin quan)

TNH TON CU CA S LY NHIM MELAMINE

H THNG THNG BO V CNH BO CA CHU U V CHT LNG

THC PHM CHO NGI V THC N CHN NUI

Nm S l hng khng t

yu cu

Th

hng

Nm S l hng khng t

yu cu

Th hng

2002 67 7 2007 45 18

2003 19 35 2008 56 15

2004 59 13 2009 100 11

2005 124 7 2010 71 13

2006 68 13 2011 109 9

Trong nhng nm gn y, hng ho Vit Nam xut khu nhn chung c cht

lng tt hn nh cc bin php qun l cht ch, h thng phng kim nghim

ngy cng c tng cng v hot ng c hiu qu

*Trong nc, v sinh an ton thc phm (VSATTP) vn cn b e da v hin

ang l mt vn bc xc\ca x hi.

*Qun l VSATTP vn cn phn no lng lo, cha tht m bo TP an ton.

Vic nhim vi khun c hi vn cn chim t l kh cao.

*Vi tc th ha v cng nghip ha, tng dn s kh nhanh hin nay,

nu qun l khng cht, nhim cho t c cht mi trng nh hng khng

nh n VSATTP

*Vic gi nhn hiu, vic s dng nhng ha cht nhi ph gia TP c th nguy

hi cho sc khe ngi tiu dng, v mc ch li nhun phi php, to nhiu vi

phm v ATTP:

-melamine trong sa v sn phm t sa, ng cho vo mt ong

-DEHP dng lm cht to c, phm mu cng nghip b cm dng trong TP,

-nc tng nhim 3-chloro-1,2-propandiol (3-MCPD)

- phm mu cng nghip rhodamine B nhum ht da, 2,4-diaminoazobenzene

dng nhum g vt cho c mu vng ti, orange II nhum tht quay v tht x xu

cho c mu cam ti bt mt .

-khng sinh, cht dit nm mc trong nui trng thy sn,

-ha cht tng trng b cm: clenbuterol v salbutamol, ractopamine , to tht siu

nc trong chn nui gia sc gia cm

-trifluralin trong thy sn v ethoxyquin trong tm do b nhim t thc n.

VSATTP ca thc n ng ph: vn rt ng lo

CAC S KIEN VE NGO OC THC PHAMSO VU NGO OC

THC PHAMSO NGI B NGO OC THC PHAM

SO NGI CHET

1997-2000 1391 25 509 217

2001 245 3 901 63

2002

2005

2006

2007

2008

2009

2010

2011

2012 (n 12/2012)

208

144

165

248

205

152

175

148

164

4 894

4 300

7135

7329

7828

5200

5664

4700

5400

71

53

57

55

61

35

51

27

33

CHI PH/NM Trung bnh 200 triu USD theo WHO (10/2007)

Nhng kh khn trong gim st, kim nghim ATTP

*Trong tnh hnh sn xut hin nay, kh d on ht tt c nhng

cht nguy hi c th c trong thc phm v thc n chn nui v do

rt him khi kim sot chng trn vn.

Vic nhp khu phi php qua bin gii nhng ha cht, sn phmkhng r ngun gc, vic qun l cn lng lo cc ph gia thc phm

trong nc cng lm trm trng thm s mt VSATTP.

* Ph gia TP vn by bn chung vi ho cht dng cho mc ch

khc, qun l Nh nc cha quy nh rch ri, to iu kin cho

ngi sn xut, v li nhun bt chnh, lm dng trong ch bin

TP.

* Lu cng mt ha cht nhng s dng cho thc phm

th kht khe hn nhiu so vi nhiu mc tiu cng

nghip khc.

*Cc quy nh v tiu chun VSATTP nhiu nc trn th gii ngy

cng kht khe, thng xuyn c duyt li, cc n v kim nghim

phi lin tc ci tin cc phng php kim nghim ph hp hn v nu

khng th c xut khu cng b e da.

Cc phng th nghim cung cp dch v kim nghim thc phm phii mt vi nhng gii hn lin tc c h thp v mc nhim ha

cht c th gy nguy him.

*Nhng hot ng kim nghim cng lc cng tng cng c th to nh

hng xu n sc khe con ngi v mi trng vi vic s dng

nhng lng ln ha cht v dung mi c hi c thi b thiu kim

sot sau .

*Vic ci tin cc phng php kim nghim lm

gim thiu ti a nguy hi cho sc khe v mi

trng sng l rt cn thit.

*Nhiu phng tin kim nghim hin c trong nc ch yu

kim sot c cc i tng nhm n ch cha cho php

nhn din thm cc cht l khc khng nm trong tm nhm.

Ngun nhn lc c trnh chuyn mn cao, kinh nghim cn

mng.

*khng c nhng phng tin kim nghim ph hp qun l tt cht

lng thc phm th xut khu sang EU, Bc M, Nht s b e da.

*Ngay c trong nc, ngi tiu dng ngy nay cng ngy cng thc r

cht lng thc phm khng phi ch l ngon ming, bt mt m cn phi

an ton, khng gy hi n sc khe.

Bo co ny xin c gii hn vo nhng phc tp trong kim

nghim ha cht hu c c hi trong thc phm bng cc

phng php sc k nhm gp phn vo m bo VSATTP

trong tnh hnh thc t hin nay ca Vit Nam

Agilent GC-MS/MS

II.CC LOI HA CHT HU C C HI

C TH PHT HIN TRONG THC PHM

1. Ha cht c gc t nhin:* Cyanogenic glycosides trong mng, khoai m

* Tetrodotoxin trong c nc v trong mt s

hi sn khc

* c cht sinh hc bin trong cc loi nhuyn

th hai mnh v (ASP, DSP,PSP)

* Mycotoxins (aflatoxin, ochratoxin)

* Histamine v cc biogenic amines khc

2. Cc loi thuc bo v thc vt

b cm hoc dng qu gii hn

cho php:* organochlorides,

* organophosphates,

* carbamates, pyrethroids,

triazines, trifluralin

3. Cc loi thuc th y, dc liu b cm hoc dng qu gii hn cho

php ( tetracyclines, sulfonamides, aminoglycosides, chloramphenicol, malachite green, crystal violet, nitrofurans, fluoroquinolones, nitroimidazoles, beta-agonists

nh clenbuterol, salbutamol, ractopamine)

4. Ph gia b cm hoc dng qu gii hn cho php (cht bo qun, phm mu)

5. Ha cht c sinh ra trong qu trnh ch bin thc phm(acrylamide, 3-chloro-1,2-propandiol, 1,3-dichloro-2-propanol)

KHNG SINH ACRYLAMIDE 3-MCPD

6. Ha cht c gc mi trng ( kim loi nng, alkylphenols, PAH,PCB, dioxins..)

7. Ha cht c thi ra t bao b (styrene, dialkyl phthalates, bisphenol A)

8. Ha cht nhi (Adulterants) nhm to mt c trng cho thc

phm (melamine gi tng m, ng saccharose gi glucose,fructose tng ngt mt ong, sa pha long vi nc, phm mu

Sudan trong bt t, bt cary, DEHP to c)

DEHP MELAMINEBIS PHENOL A

OC CHAT DE SINH RA T CACH CHIEN, XAO NNG LAM THC AN CUA TA.

HAM LNG ACRYLAMIDE AC BIET CAO TRONG KHOAI TAY CHIEN.

IARC SAP ACRYLAMIDE VAO LOAI CO KHA NANG GAY UNG TH CHO NGI (Class 2A, LD50 chuot 107/mg/kg the trong).

Acrylamide

Loi thc phm N

Hm lng

[g/kg]

Trung

bnh

[g/kg]

Hm lng

Thng gpSo mau

nhiem

min. max.

Khoai chin lt

mng192 140 3640 819 1000 76

Khoai cng chin 98 < 10 2779 151 570 11

Bnh biscuit, bnh

nng38 < 10 1090 190 660 4

C ph bt 30 115 1685 343 370 14

Bnh m nng ming nh

32 15 1714 133 610 8

Ng cc n sng 32 < 10 846 65 260 4

HAM LNG ACRYLAMIDE

Asparagine Acrylamide

Nhit, ng(glucose, fructose)

Cht beo trans (Trans fat) trong thc phm chin vi

du thc vt

*T phn ng hydrogen ha cc cht bo c nhiu ni kp trn

dy triglycerid

*T s dng phn ha cht bo dng cis thnh trans trong qu

trnh chin nng lin tc thng qua s hnh thnh gc t do

Acid elaidic (trans) Acid oleic (cis)

Canada: nh hn 0,2 mg/ phn n

M : nh hn 0,5 mg/ phn n

Trng hp ny c th ghi:

TRANS FAT = 0

nhit

Nguy c thc phm b nhim cht c thi ra t bao bi

Mt s loi bao b cho thc phm cha nhng ph gia c th

thi ra v i vo thc phm v gy nhim thc phm:

-Cht ha do DEHP (thng gi l DOP) trong cc bao b

PVC d dng thi vo thc phm, nht l cc thc phm nhiu

bo.

-Nhiu cun loi nha trong dng bc thc phm a vo l

nng hay l vi sng thc cht l nha PVC vi cht ha do

DOP, d dng thi DOP vo thc phm nhit cao.

-Formaldehyde t chn a bng nha melamine formaldehyde

c th thi vo thc phm khi s dng nhit cao.

CO

O CH2 CH

CH2

(CH2)3 CH3

CH3

C O CH2 CH

CH2 CH3

(CH2)3 CH3

O

C

O

O

C O

O

(CH2)3

(CH2)3

CH3

CH3

DEHP : trong cac loai bao b, tham trainha, ao i ma bang PVC

DBP : my pham

DEHP DBP

Environment Health Perspect, 108,895-900 (2000)

QUI NH NAY CUNG C VIET NAM AP DUNG (QUYET NH 3339/2001/Q-BYT NGAY 30/7/2001).

TUY NHIEN, TRONG DANH SACH CAC HOA CHAT CO THE THOI RA TH

OI VI ESTE PHTALAT, VIET NAM CH LIET KE DIETHYL PHTALAT.

QUI NH CHAU AU 90/128/EEC:-SO LNG TOI A CHAT THNG T BAO B I VAO 1KG THC PHAM LA 60 MG HOAC 10MG/DM2 DIEN TCH BAO B-VI CHAT OC CO QUI NH RIENG

Pht hin c cht phthalate trong nc gii kht

50 loi nc gii kht cha c dc gy hi c pht

hin Trung Quc. i Loan va pht hin mt cng ty sn

xut cht to c dng trong thc phm v ung c s

dng ha cht DEHP rt c hi cho sc khe

(26/5/2011).

C

C

O

O

OCH2CH(CH2)3CH3

OCH2CH(CH2)3CH3

CH2CH3

CH2CH3

Di(2-ethylhexyl) phthalate (DEHP)

Bisphenol A, ha cht c c th

thi ra t cc binh sa

Vit Nam c quy nh mc BPA cho php l 2,5 mg/kg (Quyt

nh 46/2007/Q-BYT).

Kt qu cc mu kim nghim BPA thi nhim t bnh sa tr

em do Vin Kim nghim An ton v sinh thc phm Quc gia

tin hnh u thp so vi quy nh hin hnh (ti cng ty Sc

K Hi ng:0,7 ppm trn mt s chai sn xut ti

Nht).

Theo cc nghin cu ti M, BPA c

th gy tn thng no, nh hng

ti kh nng sinh sn, thay i chc

nng h min dch, v lu di c

nguy c gy ung th.

Gan ay, mot so mau cong nghiep a c tm thay trong thc pham va a c chau Au xep vaoloai doi tng kiem tra:

Orange II Rhodamine B Para Red

Phm mu cng nghip

N N

H2N

NH2

2,4-diaminoazobenzene

Tht heo quay, x xu g, vt ti sng ht da gia v, mt s loi ht

III.NHNG THCH THC C TRNG

TRONG PHN TCH KIM NGHIM

M BO AN TON THC PHM

III.1. CHUN BI MU: chit ra c cht phn tch t nhng nn

mu thng rt phc tp: tht , c, sa, mt ong, thc n a dng

III.2. PHNG PHP O:

* pht hin va o c chnh xc nhng lng cht tht nh, nht

l i vi nhng cht c b cm hn, khng c c trong thc

phm, phng php khng to m tnh gi hay dng tnh gi

* c th pht hin v nh lng c nhiu cht c trong mt

ln x l mu

* phng php phi n nh, p dng c cho nhiu nn mu

tng t, nhanh, t tn ha cht, dung mi nht l ha cht dung

mi c hi, bo m an ton cho sc khe, khng gy hi mi

trng

III.3. PHT HIN C NHNG CHT KHC (NON-

TARGETS, UNKNOWNS) NGOI CC CHT NHM N

(TARGETS)

PHT HIN V INH LNG

THERMO TSQ

8000 GC-MSMS

*c cht trong thc phm ch yu dng vi lng rt kh pht

hin v phn tch, c bit trong nn mu phc tp

* Phng php phn tch lun ci tin:

-p ng tiu chun ngy cng kht khe

-nhanh, ng, lp li tt, khng lm nhim mi trng, khng

gy hi n sc khe

Chit cht phn tch Lm m c v tinh ch nh lng

(Extraction) loi tp (Clean- up) GC-MS; GC-MS/MS

LC-MS, LC-MS/MS

Mc ich: Xc nhn ng cht phn tch, tng nhy caphng php, bo v thit b phn tch

III.1. CHUN BI MU

KH KHN TRONG CHUN BI MU:Nn mu phc tp* Cht phn tch dng vt

* S cht phn tch c th nhiu v kh khc bn cht

* Cht phn tch c th to phn ng vi nn mu

*Tp ng chit vi cht phn tch (co-extractants) gy kh trong

clean-up

*Thi gian dnh cho chun b mu c th chim n trn 70% ton

thi gian hon tt phn tch

Khu ny c th gy hi cho sc khe ngi v cho mi

trng sng nu s dng nhiu ha cht c hi

Cn p dng nhng nguyn tc ca ha hc xanh trong chun

b mu

Trong khu ny, xu hng chung hin nay l phi t cnhng mc tiu sau y:

- chit c cng lc nhiu cht,

- hiu sut chit phi t gn 100%,

- gii hn pht hin phi thp,

- t tp cht i km theo gim ti a nh hng ca nn mu v

tng chn lc,

- lp li tt, n nh ca phng php chit t tt,

- p dng c cho nhiu nn mu khc nhau,

- s dng cng t mu cng tt nhm gim hiu ng nn, nhng

phi m bo c tnh i din ca mu phn tch,

- s dng t ha cht trong tch chit, an ton cho ngi

thao tc, t gy nhim mi trng,

-nhanh, d thao tc, gi thnh thp.

-Trong mt s trng hp, phng php nh lng trc tip

trn my, nu c, rt c khuyn khch.

Nhng vn cn ch trng khu ny:

* bn cht ca nn mu, bn cht ca cht phn tch

*mc hp ph ca cht phn tch trn nn mu, thm ch c

th phn ng vi mu

* bn cht ca tp:

hm lng tp i km khng nhng gy kh khn trong tch

chit cht phn tch, to m tnh gi hay dng tnh gi m

cn c th to tr ngi trong khu nh lng.

H QU

* Sc km cht lng

* Kh khn trong nhn danh cht phn tch

* Gim nhy khin khng phn tch c lng nh cht

* Gim kh nng to ion t cht phn tch, nht l u to

ion ESI, dn n nh lng sai nu khng c bin php ph

hp

* lm bn h my phn tch, gy nght ct.

Cc k thut tch chit v clean-up thng dng:

k thut chit lng siu ti hn (Supercritical Fluid Extraction SFE),

k thut chit nhanh vi dung mi (Accelerated Solvent Extraction ASE),

k thut sc k gel (Gel Permeation Chromatography GPC),

k thut chun b mu trc tuyn,

k thut clean-up bng ly trch trn pha rn c ci tin (Solid Phase Extraction

SPE) nh:

- ct Mixed Mode SPE,

- ct c hiu MIPSPE,

- ct i lc min dch (Immunoaffinity column),

- b kit QuEChERS p dng cho phn tch thuc bo v thc vt, dc

m rng ra thm cho mt s i tng khc nh, khng sinh, thuc th y,

k thut phn tch trc tip trn my (HS-GC, SPME- HS-GCvi u d khi

ph nu c

Chit nhanh ASE Phn tch pha hi Headspace H Combi-Pal

Vi ly trch trn pha rn Hot ha Np mu Ra loi tp Ra gii

Ly trch trn pha rn SPE

HEADSPACE GC, HEADSPACE- GC/MS

Gn nh khng chun b mu

V mu

ml

Vncl

VMeOH std l

Cstdppm

Vtng ml

Cchunthm ppm

Cng

mi sc k

Ct ng chun(ppm)

0.5 80 0 30400 0.58 0.00 1254132

795.91

0.5 70 10 30400 0.58 524.16 2230763

0.5 60 20 30400 0.58 946.71 2809327

0.5 40 40 30400 0.58 2096.55 4707576

y = 1629.6403x + 1297053.7546

R2 = 0.9986

0

1000000

2000000

3000000

4000000

5000000

-1000 0 1000 2000 3000

C (ppm)

Area

Phng php thm chun

nh lng Metanol trong mu ngi say ru

PHN TCH PHA HI T I HI CHUN BI MU

Phn tch tp cht trong du bo bng k thut

HS-SPME-GC-MS

Du thc phm olein c gi n cng ty Sc K

Hi ng tm cht l to mi v khc thng so

vi mu nhp trc y

Mu C, i chng

Mu B

C13 C14 C15 C16 C17 C18

C13 C14 C15 C16 C17

Dy hydrocarbon chun

Mu B

Mu D

Mu E

C12 C13 C14 C15 C16 C17

C12 C13 C14 C15 C16 C17

B KIT EZ:Faast CA PHENOMENEX

Nguyn tcPhng php EZ:faast nguyn thy c p dng cho phn tch aminoacid.

Aminoacid trong mi trng acid c cho qua v gi li trong mt u lc

cha nha trao i cation, sau c n vo mt vial thy tinh v c

chuyn ha nhanh bng n-propyl chloroformate trong chloroform. Sn

phm chuyn ha c chit khi mi trng phn ng bng isooctan . Mt

lng dung dch c em thi kh di N2 v nh mc li bng pha ng

, lc v tim vo my LC-MS/MS.

SO3- H

+ + R CH

COOH

NH3+

SO3- H3N

+CH

COOH

R

CH

COOH

RSO3- H3N

+NaOH

SO3- Na

++ R CH

NH2

COO-

RCH COO-

NH2+ Cl C

O

O CH2CH2CH3

Cl C

O

O CH2CH2CH3

R CH COOCH2CH2CH3

NHCOOCH2CH2CH3

u lc SCX

Ra vi nc kh ion

Ra gii

Chuyn ha

Isooctane

Sn phm chuyn haGC/MS; LC/MS, LC/MSMS

PHN TCH AMIN BIOGEN (Biogenic amines)

Sinh ra t s decarboxyl ha aminoacid di tc dng enzim

BAConc. of A

(mg/L)

Intensities of Ions for Quantitation

A/512 A/128 A/64 A/16 A/8 A/2

Phenethylamine 23.776 11137 43830 98330 356097 721678 2843597

Tryptamine 24.057 161497 665310 1239572 4729615 9534987 35716484

Putresceine 24.746 220446 883123 1633455 6632519 13265038 52943154

Cadaverine 47.134 569946 2263573 4533683 18881438 38013484 140317910

Histamine 10.094 91637 365599 770881 2681246 5406498 20467821

Tyramine 18 334 346657 1373636 2910502 12072790 24975146 98137104

Spermidine 12.375 20349 81682 184494 644621 1304684 5097514

Serotonine 15.741 94037 372146 683018 2948357 5913565 21551005

Spermine 28.906 22219 90016 194243 786734 1590137 6005443

-2-phenethylamine: y = 568351 x + 3563 R2 = 0.9999-Tryptamine: y = 7 133 502 x +170484 R2 = 0.9997-Putresceine: y = 10 586 246 x + 15625 R2 = 1.000-Cadaverine: y = 28 060 272 x + 648712 R2 = 0.9995-Histamine y = 4 086 002 x + 93564 R2 = 0.9998-Tyramine: y = 19 652 779 x + 40998 R2 = 1.000 .-Spermidine y = 1 018 489 x + 10374 R2 = 0.9999-Serotonine y = 4 308 694 x + 120835 R2 = 0,9993-Spermine: y = 1 201 369 x +17 763 R2 = 0.9998

ng chun cho amin biogen

Sc khi ca mu nc mm M4

Phenethylamine

Putresceine

Tryptamine

CadaverineSpermine

Serotonin

Spermidine

Tyramine

Histamine

Kt qu phn tch amin biogen trong mt s mu

2. Ly tm 2 3 pht

4.Ly tm 2 3 pht

3.Ly lp trn cho

vo C18, PSA,

MgSO4 clean-up

5. Cho vo LC-MSMS

5. Cho vo GC-MSK THUT QuEChERS

1.Mu + dung mi+ m

+ IS + Mg SO4 , lc 1 pht

K thut QuEChERS

*Lm n gin ha khu chun b mu so vi truyn thng

*Rt it tn thi gian

*Ph hp vi ha phn tch xanh

-khng i hi thy tinh th nghim phc tp

-it tn dung mi, ha cht

-t cht thi

-t gy nhim mi trng

PHM VI P DNG

*Thc phm:

d lng ha cht s dng trong nui trng c kh nng gy hi

cho ngi thng qua dy chuyn thc phm

*thuc tr su, dit c, dit nm mc, cht bo qun

*khng sinh

*cht tng trng

*ph gia s dng qu mc cho php

Mi trng :*Cht thi c hi t nh my

* Kim loi nng

*PCB, PAH, dioxins

*Mycotoxins

PHNG PHP INHLNG

TRIFLURALIN

TRN NN C

NH LUNG TRIFLURALIN TRN NN C BASA BNG GCMS

Chun b mu theo phng php QuEChERS

Giai on 1: Chit

1,25 ml ni chuntrifluralin d14 10

ppb

Mu xay nhuyncn 5 gram

Vortex13.75 ml AcOH 1%

/ACN

Lc u6 g MgSO4 v 1,5

g NaOAc

Chitlp trn

Ly tm 4000 vng/pht, 5 pht

1 g MgSO4 + 300 mg C18

Lc u, ly tm 4000 vng/pht, 5 pht

Rt 12 ml lp trn, thikh bng kh N2

nh mc 1 ml bnghexane, lc tim vo

my GCMS

Hiu sut thu hi trn 91%

(0,25-1,25 g/kg trong c)

LOD : 0,02 g/kg trong c

Gii hn ti a cho php:

1 g/kg c

nh hng nn: khng c

Giai on 2: Clean-up

MT S KT QU PHN TCH THC NGHIM

Bng 10. Mt s kt qu phn tch thc nghim

IV. MT S KT QU PHN TCH THC NGHIM

Loi muC basa

filletCh c Hi sn

S lng mu 99 11 22

S mu nhim

trifluralin29 11 10

Hm lng

trifluralin

0,3 n 44,7

g/kg

1,9 n 158,5

g/kg

0,3 n 59,1

g/kg

Tng s mu phn tch t thng 04-2010 n thng 10-2010 l 132 mu. Smu nhim trifluralin 50 mu

THEO MT TI LIU, CC PHNG PHP CHUN

BI MU C S DNG NHIU LABO TRN TH

GiI GM:

1. SPE 50 %

2. QuEChERS 37,5 %

3. CHIT LNG LNG HAY CHIT RN LNG 31,2%

4. LC QUA A 62,5%

5. KHC 18,2%

III.2. CI TIN THIT BI PHN TCH

III.2.1. Thit b sc k1.K thut sc k lng siu nhanh (UPLC) gim ng k thi gian

phn tch tng nhy v phn gii.

2.Nhng loi ct sc k lng c bit nh ct Poroshell, ct a c

ch Mixed Mode, ct Hilic gp phn nng cao kh nng phn tch

ca thit b.

3.Sc k kh nhanh vi ct ngn, ng knh nh v pha tnh

mng rt ngn bt thi gian phn tch.

4.K thut backflush gip bo v ct phn tch t b d

m bo tt hn kt qu phn tch,

5.K thut GCxGC vi phn mm deconvolution tch mi

nhn din chnh xc cc cu t c thi gian lu rt gn nhau trong

hn hp a cu t phc tp .

Mi thon:* phn gii tng

* nhy tng, LOD h thp

*o a d lng c hiu qu

nhy tng

phn gii tng

CT LI RN POROSHELL, KINETEX, ACCUCORE

NEXERA ACCELAFLEXAR FX 15

AGILENT 1290

HPLC UPLC

III.2.2. Ci tin u d khi ph1.Li th:

*xc nhn tt ha cht bng thi gian lu v ph (GC-MS) hoc nh

nhng mnh ion c trng (GC-MSMS, LC-MS, LC-MSMS)

nh lng tt nh nng cao nhy bng cch kh nhiu nn thchhp.

2.GC-MS, LC-MS: s dng nhiu trong nc phn tch vt hu c

trong thc phm

3. LC-MSMS v gn y GC-MSMS: s dng phn tch d lng trong

nhng nn mu phc tp

4.Cc u d khi ph lin tc c ci tin bn khu:

*hiu sut to ion b phn to ion,

*hiu sut chuyn ion ca b phn chuyn ion t b to ion n b phn

tch khi,

*cch kh cc tp trung ha trong qu trnh to ion hay phn mnh ion,

*cch pht hin ion detecto

Mc tiu cui cng:tng nhy v phn gii, cho php phn tch nhng hm lng cht rt nh trong nn thc phm rt phctp

L vo rng-ion vo nhiu

L ra hp hn-tptrung ion vo Q3

LC-MSMS ca Thermo Fisher vi k thut H-SRM cho

php ci t Q1=0,1 Da, loi c cc ion c phn t khi rt

gn ion phn tch , do tng phn gii v chn lc

Thc phm

Mi trng

Khoa hc ca s sng

Ch SIM (mt t cc) Ch MRM ( ba t cc)

Isoprothiolane trong gng (1ppb)

Metabolit (suberic acid) trong nc tiu chut

Hexa BDE trong bn

Thit b hin i GC-MSMS ba t cc QqQ v UPLC-MSMS ba

t cc QqQ:

-s dng nhiu hin nay trong nc do c nhy v phn gii tng, thch

hp cho phn tch vt hu c.

-gii hn ca u d khi ph 3 t cc khng th nhn danh c

ha cht hon ton khng bit.

-khc phc: ngoi cht phn tch nhm n, phn no c th nhn din c

thm nhng cht khc bit nu c c s d liu (non-target known

analytes) ci sn trong my (tin ion + 2 mnh ion con + khong thi gian lu

+ t l ion) thng qua phn mm thch hp. S cht nhn din c c th

n vi trm cht.

.

III.3. Phn tch a d lng hp cht nhm n

v nhng hp cht khng nhm n (Target,

Non-target, Unknown analytes)

Target:-cht cn phn tch thng qua GC-MS, LC-MS tt nht l qua

GC-MS/MS hay LC-MS/MS

-i hi c chun v ni chun so snh thm thi gian lu

Non-Target:-i hi c d liu, ion phn t, ion phn mnh, 2 mnh

ion con, thi gian lu, t l ion

-gii hn bi s d liu trong c s d liu database

Cht khng bit (unknown) : cht mi khng c trong cs d liu

Yu cu khch hng: nh lng carbaryl trong nho

Column : GL InertSustain C18 ( 150 mm x 2.1 mm., 3 m)Mobile phase A : 0.1 % formic acid in WaterMobile phase B : 0.1 % formic acid in MethanolGradient program : Time (min)

Flow rate : 0.2 mL / minInjection volume : 5LColumn temperature : 40

MS : SHIMADZU LCMS-8030Nebulizing gas flow : 1.5 L / minDrying gas pressure : 10 L / minDL temperature : 250BH temperature : 400Interface : ESICID Gas : 230 kPa

iu kin vn hnh my

1.00 B Conc. 402.00 B Conc. 604.00 B Conc. 605.00 B Conc. 807.00 B Conc. 10010.00 B Conc. 10010.50 B Conc. 2014.00 Stop

Compounds m/z CE (V) Compounds m/z CE (V)

Methomyl 163.00>87.90 10 Carbofurane-3OH 238.50>181.30 10

Methomyl 163.00>106.00 12 Pirimicarb 239.00>72.00 35

Acephate 184.10>124.60 20 Pirimicarb 239.00>182.00 35

Acephate 184.10>143.00 10 Imidacloprid 256.00>175.00 15

Carbendazim 191.90>132.00 31 Imidacloprid 256.00>209.10 19

Carbendazim 191.90>160.05 19 Thiamethoxam 291.90>181.00 15

Isoprocarb 194.20>77.00 35 Thiamethoxam 291.90>211.20 25

Isoprocarb 194.20>95.10 16 Tebuconazole 308.10>57.10 30

Carbaryl 202.00>127.00 28 Tebuconazole 308.10>70.00 50

Carbaryl 202.00>145.10 15 Tebuconazole 308.10>125.10 40

Fenobucarb 208.10>77.10 30 Flusilazole 316.00>165.10 30

Fenobucarb 208.10>95.10 16 Flusilazole 316.00>247.15 20

Propoxur 210.20>152.90 10 Propiconazole 342.00>69.10 20

Propoxur 210.20>168.00 10 Propiconazole 342.00>158.95 20

Aldicarb 213.00>70.00 25 Thiodicarb 355.00>88.10 20

Aldicarb 213.00>89.00 25 Thiodicarb 355.00>108.10 20

2,4 D 218.85>125.00 30 Difenoconazole 406.00>187.00 30

2,4 D 218.85>161.00 15 Difenoconazole 406.00>250.95 30

Carbofurane 222.10>123.10 22 Chlorantraniliprole 484.00>285.80 15

Carbofurane 222.10>165.20 12 Chlorantraniliprole 484.00>453.05 15

Aldicarb-sulfone 223.10>123.00 24 Indoxacarb 528.00>150.00 30

Aldicarb-sulfone 223.10>166.20 12 Indoxacarb 528.00>218.00 30

Methiocarb 226.10>121.20 12 Emamectine benzoate 886.50>81.90 50

Methiocarb 226.10>168.60 20 Emamectine benzoate 886.50>158.25 45

Oxamyl 237.10>72.10 30 Abamectine 896.00>448.80 45

Oxamyl 237.10>108.90 30 Abamectine 896.00>751.10 50

Chromatogram of Grape sample detected some kinds of pesticide

CARBARYL NOT DETECTED

TEBUCONAZOLEDETECTED

DIFENOCONAZOLEDETECTED

EMAECTIN BENZOATEDETECTED

CARBENDAZIMDETECTED

Compounds m/z Re. Time Area Result (g/kg) Compounds m/z Re. Time Area Result (g/kg)

Methomyl --- 0 0 NDCarbofurane-3OH --- 0 0 ND

Methomyl --- 0 0 NDPirimicarb --- 0 0 ND

Acephate --- 0 0 NDPirimicarb --- 0 0 ND

Acephate --- 0 0 NDImidacloprid 256.00>175.00 5.232 5738 ND

Carbendazim 191.90>132.00 4.56 253980 5.22Imidacloprid 256.00>209.10 5.254 6193 ND

Carbendazim 191.90>160.05 4.563 1378045 5.22Thiamethoxam 291.90>181.00 4.762 661776 ND

Isoprocarb --- 0 0 NDThiamethoxam --- 0 0 ND

Isoprocarb --- 0 0 NDTebuconazole 308.10>57.10 9.177 539979 15.21

Carbaryl --- 0 0 NDTebuconazole 308.10>70.00 9.203 2195189 15.21

Carbaryl 202.00>145.10 7.925 11669 NDTebuconazole 308.10>125.10 9.203 389237 15.21

Fenobucarb 208.10>77.10 8.59 62695 NDFlusilazole 316.00>165.10 8.997 14170 ND

Fenobucarb 208.10>95.10 8.59 516093 NDFlusilazole 316.00>247.15 9.022 18907 ND

Propoxur --- 0 0 NDPropiconazole 342.00>69.10 9.31 254589 4.97

Propoxur 210.20>168.00 7.523 7555 NDPropiconazole 342.00>158.95 9.31 161899 4.97

Aldicarb 213.00>70.00 6.766 16463 NDThiodicarb --- 0 0 ND

Aldicarb 213.00>89.00 6.808 5283 NDThiodicarb 355.00>108.10 8.024 24423 ND

2,4 D --- 0 0 NDDifenoconazole 406.00>187.00 9.471 4567308 83.58

2,4 D --- 0 0 NDDifenoconazole 406.00>250.95 9.48 138018832 83.58

Carbofurane --- 0 0 NDChlorantraniliprole --- 0 0 ND

Carbofurane --- 0 0 NDChlorantraniliprole --- 0 0 ND

Aldicarb-sulfone --- 0 0 NDIndoxacarb --- 0 0 ND

Aldicarb-sulfone --- 0 0 NDIndoxacarb --- 0 0 ND

Methiocarb --- 0 0 ND

Emamectine

benzoate 886.50>81.90 8.809 326320 6.44

Methiocarb --- 0 0 ND

Emamectine

benzoate 886.50>158.25 8.809 2235497 6.44

Oxamyl --- 0 0 NDAbamectine 896.00>448.80 10.193 379 ND

Oxamyl --- 0 0 NDAbamectine --- 0 0 ND

TM C V KHNG BI GII HN CC CHT

KHC TRONG MU K C UNKNOWNS NGOI

CHT CN PHN TCH: GC-QTOF V LC-QTOF, VI

PHN GiI CAO (10000 40000), ORBITRAP VI

PHN GII CAO HN (10 000- TRN 50 000)

*Full scan MS: tm cc cht c cng mi sc k trn

ngng ci t

*Vi mi cht , phn mnh tip cho Full MSMS

*C cc phn t khi chnh xc (sai s c ppm) ca

precursor ion , cc ion ng v, cc mnh ion con

*C cng thc nguyn tng ng vi cc ion

T , QUA MERCK INDEX HAY TH ViN C

CUNG CP HOC QUA CHEMSPIDER, XC NHN

CHT.

SC D FULL MS CA DICH CHIT T NHO

SPIROXAMINE

MS

MS/MS

CO

ON

H

C O + N

+

CH3CHO

C

O

O

N

H H

C O + N

O

H

m/z = 100,11262

m/z = 144,13883

ION PHN T V CC NG V

V. KT LUNMt h thng qun l c hiu qu, bt chng cho, d dng qui trch

nhim, hng mnh v xy dng chui thc phm an ton t trang tri

n bn n, cng thm mt h thng labo kim nghim c t chc rt

khoa hc vi trang b hin i chuyn dng v i ng giu kinh nghim,

nng n nhit tnh, c qun l theo mt h thng cht lng c quc

t cng nhn, c m rng thc s theo hng x hi ha, huy ng

c tng lc l cha kha gp phn m bo VSATTP trong nc trong

thc t nui trng v sn xut hin nay.

V MT NGY MAI AN TON, HNH PHC

THNH THT CM N