2006 E. coli 7000 (AP ) 2008 3000 (CNN) 2008 (Farm Press) 200 (Time) 2
GC/MS LC/MS LC/Q-TOF GC/Q-TOF GC LC PCR/RFLP MS MassCode PCR SPE Poroshell 20 ZORBAX Rapid Resolution High Definition LC/MS MS ( ) : GC 4 FAME GC/MS/MS 6 GC/MS LC CE 2 LC/MS LC/MS/MS 4 (AA ICP-OES ICP-MS) 8 (NMRFTIR UV-Vis) 22 26 MassCode PCR 28 QuEChERS SPE (PAHs) www.agilent.com/chem/jp 3
40 GC GC : : 5 EPC : : GC : ( ) Agilent LTM (Low Thermal Mass) GC / 7693A Agilent 7890A GC LTM GC 4
Norm. 4 3 C8:0 C8: C8:2 2 C6:0 0 C6: 9 C8:3 8 7 C20:0 C20: 6 C8: trans 5 0 2 4 6 8 0 2 4 6 8 20 cis-trans HP-88 GC Hz 700 600 500 USP (Tf) Tw = 5 % n (Tr) W5.0 W5.0 = 5 % 2 T f =.0. -m- (SS) 2. α-bhc 3. γ-bhc 4. β-bhc 5. δ-bhc 6. 7. 8. 9. γ- 0. I. α- 2. 4,4 -DDE 3. 4. 5. II 6. 4,4 -DDD 7. 8. 9. 4,4 -DDT 20. 2. 22. (SS) SS - 400 300 200 2 3 45 6 7 89 0 2 3 4 5 6 7 20 8 9.0 T f =.02 T f =.02 22 00 5 7.5 0 2.5 5 7.5 20 22.5 25 min Agilent J&W HP-ms GC / www.agilent.com/chem/jp 5
GC/MS/MS GC/MS GC/MS/MS Agilent GC/MS (GC/MS/MS) Agilent 7200 Q-TOF : GC/MS : 500 MRM Agilent 7000B GC/MS Agilent 240 GC/MS MS/MS Agilent 7200 Q-TOF GC MS/MS 6
vs. [ ] vs. [ ] GC/MS/MS SIM 360 MRM ( ) TIC ( MRM ).5 4.3 MRM www.agilent.com/chem/jp 7
GC/MSD Agilent 5975 GC/MSD : / MS : : (DRS) DRS 3 :. MSD ChemStation 4 2. AMDIS 32 Agilent 5975C GC/MSD (LOD) (LOQ) 3. NIST AMDIS 6 3000 DRS 2 3 GC/MS 8
5000000 4000000 TIC: Gr Pepper_TID_2uL.D\data.ms 3000000 2000000 000000 > 4.0 6.00 8.00 0.00 2.00 4.00 6.00 8.00 20.00 22.00 24.00 26.00 28.00 59. 5000 0 m/z > 5000 0 m/z > 229 00 ppb GC/MS ( ) 5000 0 m/z > 79. 97. 26. 54. 96.2 238.2 28.3 77.0 220.3 26. 32.3 354.8 428.9 0 20 40 60 80 00 20 40 60 80 200 220 240 260 280 300 320 340 360 380 400 420.0.0 55.0 97.0 77.0 30.0 266.0 4.0 76.0 204.0 234.0 429.0 97.0 77.0 78.0 25.0 48.0 207.0 246.0 2467 (7.840 ): Gr Pepper_TID_2uL.D\data.ms (-2480) (-) 266.0 30.0 [_MS_PT]*AMDIS 0 20 40 60 80 00 20 40 60 80 200 220 240 260 280 300 320 340 360 380 400 420 [_MS_PT]*AMDIS 0 20 40 60 80 00 20 40 60 80 200 220 240 260 280 300 320 340 360 380 400 420 229 48 GC/MS 7.840 ( ) ( ) ( ) GC/MS : C:\MSDCHEM\DATA\08_03_07 FDA_S_CL\PEACH_S_CL [37.0] 703 (5.65 ) AMDIS TIC () 00 75 50 25 0 00 75 50 57 7 85 5 25 44 55 89 208 29 236 5.65 50 00 50 200 250 300 350 400 450 500 [y] 5 44 (5.65 ) / AMDIS ( ) () 25 89 0 m/z: 50 00 50 200 250 300 350 400 450 500 00 44 : 75 50 5 25 57 39 89 72 27 20 0 m/z: 50 00 50 200 250 300 350 400 450 500 9
GC GERSTEL MPS2 SPME (SBSE ) 0 g SBSE 60 min GERSTEL MPS2 Agilent 5975C GC/MS Fiehn Oliver Fiehn GC/MS 067 PubChem CAS (RTL) GC/MS GC/MS (m/z 50-600) : (0:) : DB-5 ms 30 m,0.25 mm,0.25 µm + Duragard 0 m : 60 ºC ( min)-0 ºC/min-325 ºC (0 min) ( ) 0
GC/MS Agilent Mass Profiler Professional (MPP) MS MPP Agilent Mass Profiler Professional (MPP) ( ) ( ) ( ) ( ) MPP ( ) MPP IDbrowser MPP : Volcano Plot 2 ( 2 ) GC/MSD (TIC) AMDIS Volcano Plot
HPLC Agilent LC Agilent LC LC LC/MS Agilent 290 Infinity LC : UHPLC Agilent 290 Infinity LC UHPLC HPLC Agilent 260 Infinity LC : UHPLC 60 MPa (600 bar) 80Hz 0 HPLC HPLC UHPLC Agilent 220 Infinity LC : HPLC 60 MPa (600 bar) 80 Hz Agilent 220 Infinity LC HPLC UHPLC HPLC UHPLC Agilent 220 Infinity LC Agilent 260 Infinity LC Agilent 290 Infinity LC 290 Infinity LC TOF QTOF : 0 mg/ml 30 µg : 0.29 ml/min 42 0 % 40 % MTBE vs. ACN 55 60 20 nm UV ZORBAX RRHD StableBond C8 2. mm 400 mm (50 mm x 2 00 mm x ).8 µm 20 ºC 730 bar 2
(CE) Agilent 700 CE () (GABA ) Agilent 700 CE 43 38! LC/MS CE/MS Agilent LC/MS CE/MS (290 UHPLC/6540 Q-TOF) www.agilent.com/chem/jp 3
LC/MS LC MS TOF-MS LC/MS Jet Stream LC/MS LC/MS/ MS 5 : MassHunter Optimizer Agilent 600 LC/MS : QC Agilent 600 LC/MS Agilent 6400 LC/MS 6400 LC/MS/MS MRM 4000 Jet Stream 6490 MRM 0 Agilent 6200 Accurate-Mass TOF : Agilent 6200 Accurate-Mass (TOF) LC/ MS UHPLC MS MS/MS ppm 20,000 Agilent 6500 Accurate-Mass Q-TOF : ppm Agilent 6500 Accurate-Mass Q-TOF 40,000 5 6550 Q-TOF Dual ifunnel Technology MS Mass Profiler Professional LC/MS 4
UHPLC/MS 0 *5.975 0 7 7 6 328. > 282. 6 = 45.9 5 5 328. > 254. 0 2 6 5 5.6 5.7 5.8 5.9 6 6. 6.2 6.3 ( ) 5.36 0 2 6 5 5.6 5.7 5.8 5.9 6 6. 6.2 6.3 ( ) 4 3 20. >. 4 3 = 48. 2 2 20. > 93.0 0 5 5. 5.2 5.3 5.4 5.5 5.6 5.7 ( ) 0 5 5. 5.2 5.3 5.4 5.5 5.6 5.7 ( ) www.agilent.com/chem/jp 5
G2 EIC B B2 G & 2 x ( ppb) vs. ( ) G2 EIC & B B2 G (2.5 ppb) vs. ( ) Aspergillus flavus Aspergillus parasiticus Agilent LC/MS/MS 2 LC/MS/MS ppb B B2 G G2 2.5 ppb LOD 40 ng/g ( 530 fg ) 6
未知化合物のスクリーニングと確認に おける Q-TOF の威力 このアプリケーションでは イチゴ抽 出液に農薬の混合物を添加し Agilent 200 シリーズ Infinity LC と 6500 シリー ズ Q-TOF を用いて分析しています 分子式による化合物検出 エクスト ラクターとデータベース検索を組み合 わせた手法で検出された 200 種類を 超える農薬の標準物質の EIC この高 感 度の構成は 複 数 残留農 薬 分析の 厳しい要件を満たしています 06.3 06.2.3..2. 0.9 0.8 0.9 0.7 0.8 0.6 0.7 0.5 0.6 0.4 0.5 0.3 0.4 0.2 0.3 0. 0.2 0 0. Cpd 323: トリブホス: +ESI ECC Scan Frag=50.0V SeqR_6-r003.d Cpd 323: トリブホス: +ESI ECC Scan Frag=50.0V SeqR_6-r003.d 5.22 Cpd 323: トリブホス 5.22 Cpd 323: トリブホス 0 2 3 4 5 6 2 3 4 5 6 7 8 9 0 カウント vs.vs. 取り込み時間 (分) ( 分 ) カウント 取り込み時間 7 8 9 0 2 3 4 5 6 2 3 4 5 6 カウント vs. 取り込み時間 (分) 農薬 200 種類の抽出化合物のクロマトグラム (MFE で検出した化合物 ) 0 4 2.3 2.24 0 2.3 2. 2.22 m/z 294.366 アバンダンス 294.366 m/z 294.366 295.396 294.366 296.337 295.396 2..9.82.9.7 296.337 2636 アバンダンス% 00 電荷 Sat 幅 0.0095 0.00 0.0095 0.0 0.00 0.0 アバンダンス アバンダンス% 電荷 Sat 660 30.5 359 2636 660 359 6.6 00 30.5 6.6 レスポンス 3044 幅 レスポンス 2922 3044 29608 2922 29608.8.6.7.5.6.4.5.3.4.2 Cl.3..2. 0.9 H3C CH3 H3C CH3 H3C 0.8 0.9 0.7 H3C 0.8 0.6 0.7 0.5 0 N N OH H3C CH3 H3C N NN 296.337 H3C N N OH N NN OH 296.337 N Cl CH3 N 295.396 295.396 0.4 0.2 0.3 0. 0.20 0. H3C OH 0.6 0.4 0.5 0.3 Cl Cl 294 294.25 294.5 294.75 295 295.25 295.5 294 294.25 294.5 294.75 295 295.25 295.5 295.75 296 296.25 カウント vs. 質量電荷比 (m/z) 295.75 296 296.25 296.5 296.75 297 297.25 297.5 297.75 296.5 296.75 297 297.25 297.5 297.75 カウント 質量電荷比(m/z) (m/z) カウント vs.vs. 質量電荷比 Agilent 290 Infinity LC と Agilent 6540 Q-TOF を用いた 3 分間分析のデータから得られた質 量スペクトル例 毎秒 0 スペクトルで優れた質量分解能が得られています アジレントの食品分析ソリューションの詳細については www.agilent.com/chem/jp をご覧ください 7
(AA MP-AES ICP-OES ICP-MS) ICP-MS ( ) LC-ICP- MS GC-ICP-MS (AA) (MP-AES) (ICP-OES) (ICP-MS) 9 He / Agilent 7700 ICP-MS 3 (ORS 3 ) He 7700 He Agilent 700 ICP-OES 720/730 MultiCal Agilent 240FS/280FS AA GTA 20 ( ppb ppt) Agilent 400 MP-AES ppb 8
AA NIST 8435 AA % AA Ca % 0.922 +/- 0.049 0.94 0.8 0.96 Mg/Kg 84 +/- 76 820 0.7 82 K %.363 +/- 0.047.364.0.35 Na % 0.356 +/- 0.040 0.366 0.8 0.372 n = 0 AA NIST 8435 AA 30 % ICP-OES As 88.980 Ca 370.602 Cd 24.439 Cr 267.76 mg/kg mg/kg % % mg/kg mg/kg mg/kg B 4 4 0.0233 0.0242 0.64 NA 0 Magruder 4B 2.05.75 2.7 2.48 2.3 NA 25.2 32.6 Magruder 6B 5.75 5.66 4.93 5.94.5 NA 50.88 5.08 Cu 327.395 Fe 26.382 K 2 O 404.72 Mg 279.078 % % % % % % K 2 O % % B 0.0407 0.0398 0.02 0.04 NA NA 2.6 2.2 Magruder 4B 0.046 0.0307 0.350 0.400.02 0.54.62.64 Magruder 6B.00 0.976 0.500 0.500 2.37 20.54 0.53 0.62 Mn 294.92 Na 589.592 P 24.94 % % % % % P 2 O 5 % P 2 O 5 B 0.5 0.48 0.94 0.94 0.5 0.50 Magruder 4B 0.036 0.039 0.3 0.29 8. 9. Magruder 6B 0.04 0.05 0.57 0.58 9. 9.9 Pb 220.353 Se 96.026 Zn 23.857 mg/kg mg/kg mg/kg mg/kg % % B 6.8 5.7 NA NA 0.0244 0.0249 Magruder 4B.6 2.8 0.43 0.44 0.043 0.048 Magruder 6B.88 2.5 0.3 0.2 0.003 0.003 (N) (P2O5) (K2O) / ICP-OES ICP-OES www.agilent.com/chem/jp 9
ICP-MS Agilent 7700 ICP-MS He ICP-MS QuickScan 7700 ICP-MS He MPP MPP Country B Japan Country C-4 PCA Country A MPP 2. MPP ( ). PCA 2 ICP-MS 2 MPP PCA (Japan) Country A Country C Country B Japan PCA 2 ( ) MPP ICP-MS 7700 ICP-MS He ( ) MPP 20
(ICP-MS) ICP-MS (GFAAS) 9 He Agilent 7700 ICP-MS Agilent LC GC As Sn Hg LC-ICP-MS As HPLC-ICP-MS As (As(III) As(V)) 5 2 0. µg/l / / GC-ICP-MS Sn 20 ng/ml (ppb) Sn MBT TPrT DBT MPhT TBT TeBT TPeT DPhT TPhT GC-ICP-MS Sn Hg (SS-IDMS) SS-IDMS www.agilent.com/chem/jp 2
(NMR) : : : : NMR : NMR 3.8 ml 0.2 ml DSS (5.3mM/D2O) 0.6 ml 30 ºC 5 0 ppm 9 DSS 0.5 mm 7.8 ppm 3.44 mm 8.5 ppm 3 0.56 mm 400-MR NMR Coffee + 5 % D2O + DSS Agilent 400-MR (400MHz) Presat-Noesy st increment 2.5 sec. acq. 2 sec. Pre-saturation 64 transients (5 min.) by onenmr probe 22
: (FTIR) Cary 600 FTIR / / 0.60 v(ch) & v(c=o) 0.40 0.20 0.00 (H 2 O ROH ROOH) v(c-h) v(c-h) 3500 3000 2500 2000 500 000 - (cm ) v(c=o) FFAs v(c=o) / & / CH 2 FTIR QC/QA QC/QA AOAC www.agilent.com/chem/jp 23
β- (β-lg) (ph 8.6) β-lg A (5 % w/v) 40 ºC 92 ºC (cm - ) : Cary Eclipse Cary Cary Eclipse / 96 384 24
: Cary UV-Vis UV-Vis-NIR UV-Vis QA/QC Cary 60 UV-Vis Cary Wine Analyzer 6 / www.agilent.com/chem/jp 25
PCR PAGE ( ) 2 (PCR ) PCR (qrcr) PCR PCR Mass Code/qPCR ( ) () DNA (qpcr ) 200 Agilent 200 qpcr end-point PCR DNA fragment MassCode/qPCR 26
( ) PCR- RFLP DNA DNA DNA :20 PCR DdeI DNA 2003 8 PCR DNA 74 % 7 % 3 / 4 2 RM20 y = _ 0.0745x + 4.482 R 2 = 0.9275 RM339 y = _ 0.0632x + 3.246 R 2 = 0.804 0 0 0 20 30 40 50 % PCR RM20 RM339 Agilent 200 RFLP Decoder (A) (B) A B www.agilent.com/chem/jp 27
Agilent QuEChERS ( ) Agilent QuEChERS QuEChERS SPE 2 ml 5 ml AOAC EN SPE Agilent SPE : 3 QC 96 28
Agilent EN 5 % FA Agilent SPE (25mg C8 50 mg MgSO4) LC/MS/ MS (LOQ) 5.0 ng/g 5.0 400 ng/g 0 90 0 % ( 65 %) RSD 2 3.4 % QuEChERS 2 g ( 0.05g) 50 ml IS 00 µl QC 50 µl 30 30 mm KH 2 PO 4 ph 7.0 8 ml 5 % FA 0 ml 30 EN QuEChERS 4,000 rpm 5 ACN ml QuEChERS SPE 2 ml 3,000 rpm 3 800 ml N 2 40 C 800 µl :9 MeOH/H 2 O (0. % FA) 0.22 µm LC/MS/MS Agilent QuEChERS www.agilent.com/chem/jp 29
20 a) C 8 20 b) MycoSep 00 00 80 80 (%) 60 40 B B2 G G2 (%) 60 40 B B2 G G2 20 20 0 0 a) C8 b) MycoSep B B2 G G2 QuEChERS B B2 G G2 4 0.5 µg/kg 0.5 µg/kg [%] RSD [%] 3 n = 3 DON NIV 3ADON 5ADON FUS T-2 HT-2 NEO DAS MAS T-2 T-2 ZEA 90 5.2 67 5.9 89 9.3 92 3 9 0 87 7.6 82 7.3 9 2.6 82 8.3 86 3 69 9. 69 2 0 5.9 93 2.8 74 2.5 88 7.6 87 5 94 4.2 88 8.8 9 3.3 78 89 3.6 85 2 66.2 75 6.8 3 5.0 98 3.8 67 6.3 97 6.6 89 9 7.8 84 2.2 85 5.0 68 8 85 5.2 93 4.2 83 2.8 73 0 08 4.8 96 5. 73 0 93 89 9 7.8 84 2.2 85 5.0 68 8 85 5.2 93 4.2 83 2.8 73 0 08 4.8 87.7 65 5.7 00 5.5 96 9.5 98 8.5 83 8.2 79 3.3 80 2.0 75 3.7 86 76 9.3 65 6.0 87 3.7 7 3 0 7. 98 8.3 97 6.4 75 70 7.7 04 0 82 6.8 88 6 82 3.3 67 7 02 2.7 88 2 66 0 9 9.4 96 6.6 6 4.3 70 7.3 74 0 7 6.3 68 4.6 9 4 7 7.9 70 6 6 6.7 DONPrep IAC MycoSep 227 Bond Elut Mycotoxin 6 (n=3) Klötzel [0] Bond Elut Mycotoxin 2 ZEA RSD / 3 % DON NIV 3ADON T-2 30
x0 2 0.95 0.9 0.85 0.8 0.75 0.7 0.65 0.6 0.55 0.5 0.45 0.4 0.35 0.3 0.25 0.2 0.5 0. 0.05 0 + MRM (92.000 & 60.00000) low QC -.d 2 2 3 8 3 4 4 4 6 0 3 5 2 3 9 2 4 5 7 6 0.5.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 0 0.5.5 2 2.5 3 (%) vs. ( ) :. 0. 2.. 3. 2. 4. 3. 5. 4. 6. 5. 7. 6. 8. 9. 0 ng/g Agilent AOAC Agilent AOAC SPE LOQ MRL 48000 46000 44000 42000 38000 36000 34000 32000 30000 28000 26000 24000 22000 20000 8000 6000 4000 2000 0000 8000 6000 4000 2000 0 2 3 4 5,6 7 TIC: 06030b-9.D\DATASIM.MS 8 9,0 3,2 4 5 6,7,8 4.00 6.00 8.00 0.00 2.00 4.00 6.00 8.00 20.00. 2. 3. 4. 5. 6. 7. 8. 9. [a] 0.. [b] 2. [k] 3. 4. [a] 5. 6. [,2,3-c,d] 7. [a,h ] 8. [g,h,i] QuEChERS GC/MS GC/MS/MS QuEChERS DB-5ms 20 m x 0.8 mm 0.8 µm GC/MS SIM 50 ppb EPA PAH www.agilent.com/chem/jp 3
0 3.5 : 2 2 3 3 4 4 A. 2. 3. 4. 5. 6. 7. 8. 9. IS () 0.5 0 3 2 IS 2 2 3 3 4 4 B.5 5 6 9 0.5 2 3 4 7 8 2 3 4 5 6 Counts vs. Acquisition vs. Time ( ) (min) A) B) 00 ng/g LC/MS/MS Agilent QuEChERS LC/MS/MS LOQ (20-00 ng/g) MRL 32
2 0 LU 8 6 4 2 2 3 4 5 6 7 8 9 0 2 3 4 5 6 0 0 2 4 6 8 0 2 4 ( ) HPLC- FLD :. Nap 2. Acy 3. Ace 4. Flu 5. Phe 6. Ant 7. Fln 8. Pyr 9. BaA 0. Chr. BeP 2. BeA 3. BkF 4. DahA 5. BghiP 6. InP / 260-nm/352-nm 260-nm/420-nm 260-nm/440-nm 230-nm UV PAH (ng/g) (n = 6) 2 3 % %RSD % %RSD % %RSD 94.7.4 97.9. 93.8.4 * 87.8.7 96.3.2 85.6 0.8 92..5 93.0.8 96.7 0.8 98..5 89.9.0 97.2 0.9 90.6 0.9 93.8 0.8 83..7 96.7.0 87.6 0.8 92. 0.6 83.4.3 93.9.5 95.9.2 93.5.8 86..3 95.0.4,2-94.5.3 89.6.6 94.9.0 0.0.4 97.8.7 87.2.6 [e] 88.8.5 85.2.9 95.0.4 [e] 95.5 0.7 92.7 0.7 89.2 0.9 [k] 93.5 0.8 94.6 0.9 98.9 0.8 [a,h] 88.2 0.9 97.3. 97. 0.6 [g,h,i] 98.4 0.8 95.5.6 98.2 0.7 [,2,3-cd] 9.5.5 97.9 0.9 94.3 0.7 * 230 nm UV 6 RSD (n = 6) Agilent QuEChERS AOAC HPLC-FLD (RSD) 3 6 (n=6) 6 RSD www.agilent.com/chem/jp 33
GC Agilent GC Agilent GC LC Agilent ZORBAX HPLC Poroshell 20 2 2 µm Poroshell 20 2 2 µm GC 34
Web 90 GC / GC/MS MS / FID MSD PEEK/ LC Agilent Agilent ICP-MS Agilent ICP-MS ICP www.agilent.com/chem/jp 35
0 www.agilent.com/chem/jp : 020-477- www.agilent.com/chem/jp Agilent Technologies, Inc. 200 Printed in Japan September 5, 20 5990-6505JAJP