massenspektrometrie und methodenentwicklung · 2016. 9. 2. · 3 76.0 2 1 0 80 100 120 140 160 180...
TRANSCRIPT
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Massenspektrometrie und
Methodenentwicklung
Dr. Volker Gnau
Produktspezialist LC/MS
Hamburg 02. Oktober 2012
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Agenda
Page 2
• Ionization Sources
• 6100 Single Quad Series
• 6500 QTOF Series
• 6400 QQQ Series
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Ionization Techniques
Page 3
ESI APCI APPI
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Electrospray Ionization - ESI
Page 4
• polar compounds
• small and large molecules
• (multiple) charged compounds
• thermal labile compounds
• Samples with small amounts
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Agilent Jet Stream
Off On
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Atmospheric Pressure Chemical Ionization
(APCI)
Page 6
• apolar compounds
• small molecules
• single charged compounds
• thermal stable compounds
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Atmospheric Pressure with Multimode Source
ESI and APCI Ionization
Page 7
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Atmospheric Pressure Photo Ionization
(APPI)
Page 8
• compounds with inadequate
ESI and APCI
• small molecules
• mainly single charged compounds
• thermal stable compounds
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Atmospheric Pressure Ionization
Solvents and Buffers
Page 9
• Acetonitrile, Methanol, THF, Aceton
• Acetate acid and salts, pH 3-4
• Formate acid and salts, pH 2-3
• TFA, pH 1-2
• Ammonia, pH >7
• TEA, pH > 7
Use only volatile
solvents and buffers
TFA (neg, m/z 113), TEA (pos, m/z 102) cause high background
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Influence of non-volatile buffers and samples
on API Signal
Page 10
APCI-SprayChamber after 6hrs
with 25mmol phosphate buffer
(0.7mL/min)
HBSS Injection
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Singlequadrupol - Aufrüstbarkeit
Infinity LC
6120B
3 Models
Most Flexible
Easiest to Use
Highest
Performance
6130B
6150B
Growth Path
Performance
Lab Needs
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Specification G6120B G6130B G6150B
Mass Range 10-2000 m/z 2-3000 m/z
AJS ready
10-1350 m/z
Scan Speed 5000u/s 2500 u/s, 5000 u/s 10000 u/s,
2500 u/s
POS/NEG Switching 30 msec 30 msec 20 msec
SIM Sensitivity ESI
POS
reserpine
---------------10 pg
50:1 p-p
1 pg
20:1 p-p
----------------10 pg
200:1 p-p
1 pg
100:1 p-p
-------------------10 pg
1000:1 p-p
Scan Sensitivity
reserpine
None 50pg
20:1 p-p
50pg
100:1 p-p
Mass Accuracy Mass
Axis Stab.
+-0.13u
+-0.1u or 100ppm
12hrs
+-0.13u
+-0.1u or 100ppm
12hrs
+-0.13u
+-0.1u or 100ppm
12hrs
Enhanced 6100B Installation Specifications
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min0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Norm.
0
20000
40000
60000
80000
100000
120000
140000
160000
MSD1 271, EIC=270.7:271.7 (C:\DATA STORE\CHEM32_DATA\DATA\G6120B_FASTSCAN\SULFAS_FAST 2011-04-27 18-22-59\SULFAFAST000
0.4
98
MSD1 279, EIC=278.7:279.7 (C:\DATA STORE\CHEM32_DATA\DATA\G6120B_FASTSCAN\SULFAS_FAST 2011-04-27 18-22-59\SULFAFAST000
0.5
46
MSD1 285, EIC=284.7:285.7 (C:\DATA STORE\CHEM32_DATA\DATA\G6120B_FASTSCAN\SULFAS_FAST 2011-04-27 18-22-59\SULFAFAST000
0.5
98
MSD1 311, EIC=310.7:311.7 (C:\DATA STORE\CHEM32_DATA\DATA\G6120B_FASTSCAN\SULFAS_FAST 2011-04-27 18-22-59\SULFAFAST000
0.6
83
Improved Peak Widths with Faster Scanning
Improved chromatographic resolution and compound identification
Sulfachloropyridazine
13 spectra
min0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Norm.
0
50000
100000
150000
200000
0.5
05
MSD1 271, EIC=270.7:271.7 (C:\DATA STORE\CHEM32_DATA\DATA\G6120B_FASTSCAN\SULFAS_FAST 2011-04-27 18-22-59\SULFAFAST000
0.5
55
MSD1 279, EIC=278.7:279.7 (C:\DATA STORE\CHEM32_DATA\DATA\G6120B_FASTSCAN\SULFAS_FAST 2011-04-27 18-22-59\SULFAFAST000
0.6
07
MSD1 285, EIC=284.7:285.7 (C:\DATA STORE\CHEM32_DATA\DATA\G6120B_FASTSCAN\SULFAS_FAST 2011-04-27 18-22-59\SULFAFAST000
0.6
90
MSD1 311, EIC=310.7:311.7 (C:\DATA STORE\CHEM32_DATA\DATA\G6120B_FASTSCAN\SULFAS_FAST 2011-04-27 18-22-59\SULFAFAST000
Sulfamethizole
Sulfamethazine
Sulfachloropyridazine
Sulfadimethoxine
2500 u/sec
5250 u/sec
2.28 sec FWHM
1.48 sec FWHM
(14 data points)
35% Improvement
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Page 15
6500 QTOF Product Line Excellent Value and Performance -
6530 QTOF LC/MS Agilent JetStream for greatest sensitivity
Robust, easy to use
Wide dynamic range for qual/quan applications
6540 UHD QTOF LC/MS Sub 1-ppm mass accuracy for highest confidence
compound identification
Versatile system with highest resolution
Fast scan speed to match UHPLC separations
6550 iFunnel QTOF LC/MS Agilent iFunnel for highest sensitivity
Perfect for most demanding applications
Wide dynamic range for qual/quan applications
Fastest scan speed to match UHPLC separations
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Informationsgehalt Analyse unbekannter Verbindungen mit hochauflösender
MS/MS
Beispiel für Strukturvielfalt: M = 149 Massengenauigkeit von 2 ppm = 0,0003
Zugelassene Elemente: Anzahl an Strukturformeln * C, H, N, O, S, P, F, Cl, Br: 120 C, H, N, O, S, P: 38 C, H, N, O: 27
*Number of isomers according to MOLGEN (Molecular structure generation; http://molgen.de)
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Beispiel für Strukturisomere von Cathinon (www.chemspider.com, 829 Treffer) Insgesammt sind 25 895 621 Strukturisomere möglich (Stereoisomere kommen noch dazu!!!)
C9H11NO
October,
2010
Page 14
Agilent Restricted
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Page 21
Monoisotopic mass
(varies in ppm)
Isotope spacing
(varies in ppm)
Isotope distribution
(varies in %)
Calculation of chemical formular
Scoring based on:
Q-TOF Software Tools
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MS- oder
MS/MS-Daten
(Q)TOF Software: Screening und Profiling
Molecular
Feature Extraction
Mass Profiler
(Professional)
Liste aller
„interessanten“
Komponenten
Find by
Formula
Komponenten Datenbank oder
Bibliothek
MS- oder
MS/MS-Daten
Identifizierung
Identifizierung
Komponenten
Molecular Structure
Correlator
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Find by Formula
Compound information from formula or Database
Ion Information
Ion chromatogram drawn from information
Spectra extracted from integrated peak
Spectral performance calculated
Data Find
Compounds Identify
Compounds
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Find by Auto MS/MS or Targeted MS/MS
Find by Auto MS/MS or
Targeted MS/MS
automatically extract the MS
and MS/MS information,
aligns the spectra sorts and
display the according
spectra as a single
compound. The data can be
used to calculate empirical
formulas for MS and
MS/MS. In addition the
information can be used to
search the database with
the MS data and library
search the MS/MS data
using the accurate mass
MS/MS spectral library.
Qual B.04 extracts MFE from Auto MSMS and aligns possible product ion spectra to found features. This
allows for a database search of accurate MFE compounds and an MSMS library search of the attached
product ion spectra.
Data Find
Compounds Identify
Compounds
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Molecular Feature Extractor (MFE) • MFE is extremely fast
• Does not use exhaustive EIC extraction
• Uses total ion count abundance
information, not just base peak
• Can yield more false negatives than
exhaustive approach
• Find chromatographic peaks
• Subtract background
• Locate the groups of co-variant ions in
each chromatogram;
• Adducts, dimers, isotopes ([M+H]+,
[M+H+1]+,…
• Sum all ion signals into one value
Raw data Background noise removed
Individual m/z peaks grouped into isotope clusters
Isotopes grouped into features
Data Find
Compounds Identify
Compounds
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Databases and Libraries
Database
Consists of
• Name
• Empirical formula
• Accurate monoisotopic mass
Optional
• Structure
• CAS_Number
• Chemspider Number
• Retention time
Library
Same as database plus
structure
In addition it contains
• Spectra from
• Different collision energies
• Different ion sources
• Different polarities
Data Find
Compounds Identify
Compounds
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Q-TOF- Software Tools
MassHunter B.05. (Windows 64 bit)
MassHunter Aquisition
Auto MS/MS
MassHunter Qual
MFE (Molecular Feature Extractor)
Find by formular
MSC (Molecular Structure Correlator)
PCDL Manager
MassHunter Quant
PCDLs (Datenbanken und Bibliotheken)
Met ID
MPP (Mass Profiler Professional)
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Qualitative und Quantitative Analyse Bekannt, Unbekannt und Unerwartet
„unknown screening“ “Target Screening “ Quantifizierung
nicht-selektiv selektiv
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Agilent QQQ-Systeme - Aufrüstbarkeit…
Infinity LC
6420
Easy Choice
Spurenanalyse in der Routine
6430
6460
Leis
tun
gsfä
hig
keit
Quantifizierung in der Routine
iFunnel
Technologie
Ultraspuren & schnelle
Analyse
6490
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Specification 6460 6490
S/N 1 pg reserpine 1,000:1 10,000:1
Mass Range (m/z) 3,000 1,400
Mass Resolution 0.7 Da 0.4 Da
Scan Speed, Da/s 5,000 10,000
Polarity Switching 30 msec 30 msec
MRMs/Sec
no cross-talk 200 300
Data Dependent YES YES
Triggered MRM
YES
YES
6460 und 6490 Spezifikationen
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31
Der neue 6490: Verbesserung der Empfindlichkeit
um Faktor 50 in 4 Jahren
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
2006 2007 2008 2009 2010
6410 6460
6490 S
/R-V
erh
. 1 p
g R
eserp
in
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QQQ- Softwaretools
MassHunter
Optimizer
d-MRM Datenbanken
MassHunter Aquisition
dynamic MRM
Triggered MRM
MassHunter Quant
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Optimizer
QQQ Software: Entwicklung neuer Methoden
Messung
Standard-
substanzen
Retentions-
zeiten
Messung
eines
Probensets
Datenbank mit
MRM-
Übergängen
Parameter Messmethode
Rohdaten der
Analyse
Dynamic MRM
und/oder t-MRM-
Methode
Benutzereigene t-MRM
Bibliothek
Rohdaten des
Sets
Auswertemethode
Ergebnisse
Parameter
Report
„Spektren“
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MRM viewer makes optimizing pesticides easy
Page 38
C
O
N
C
U
R
R
E
N
T
M
R
M
s
Min Dwell
Time/method
2 msec
Max Dwell
Time/method
33 msec
Max
concurrent
MRMs = 131
Min
concurrent
MRMs - 9
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tMRM Product Ion Spectrum
39
x103
8
7
6
5
4
3
2
1
0 80 100 120 140 160 180 200 220 240 260 280 300 320 340
334.2 171.1
145.0
132.1
117.0
105.1 91.1 76.0
tMRM Product Ion Spectrum
x103 8
7
6
5
4
3
2
1
0 80
76.0
x103 8
7
6
5
4
3
2
1
0 80 100
91.1
x103 8
7
6
5
4
3
2
1
0 80 100 120
105.1
x103 8
7
6
5
4
3
2
1
0 80 100 120
117.0
x103 8
7
6
5
4
3
2
1
0 100 140
132.1
x103 8
7
6
5
4
3
2
1
0 80 100 120
119.0
x103 8
7
6
5
4
3
2
1
0 100 140 180
145.0 x103
8
7
6
5
4
3
2
1
0 100 140 180
147.0
x103 8
7
6
5
4
3
2
1
0 80 100 120 140 160 180
171.1
334 > 76 334 > 91 334 > 105 334 > 117 334 > 119
334 > 132 334 > 145 334 > 147 334 > 171
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tMRM Library Searching
Tebufenpyrad Standard 50 ppb
40
Library match score: 96.75
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Summary
Page 41
• Ionization Sources
• 6100 Single Quad Series
• 6500 QTOF Series
• 6400 QQQ Series
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7200 Series Q-TOF for GC/MS Das GC-QTOF zeigt neue Wege in der GC-MS
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240 IT 7000 TQ
220 IT
5975E SQ 5975T LTM SQ
5975C SQ
7200 Q-TOF
More Choices – Better Solutions
Agilent GC/MS & GC/MS/MS
ASMS 2011
43
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Was kann dieses System leisten?
TOF mode
• Hoch Auflösende Full Scan Spektren
• Genaue Massenbestimmung
• Schnelles Scannen von Spektren im FullScan
MS/MS mode
• Triple Quadrupol MS/MS Product Ionen Spektren
• Full Scan Product Ionen Spektren – Hochauflösung genaue
Massen
Ideales Werkzeug zur Lösung komplexer
analytischer Probleme
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= +
7890 + 7000 + 6500 = 7200 GC/Q-TOF
Agilent’s Chimera
Unser neuestes GC/MS . . .
besteht aus vielen äußerst bewährten
Teilen:
Fast eintausend 7000 TQs
Mehr als eintausend TOFs und Q-TOFs
Viele Tausend 7890 GCs
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Neu . . . und dennoch bewährt
Dual-stage ion mirror improves
second-order time focusing for
high mass resolution.
Hexapole collision cell accelerates
ion through the cell to enable faster
generation of high-quality MS/MS
spectra without cross-talk
Split-flow turbo differentially
pumps the ion source and
quadrupole analyzer compartments
4GHz ADC electronics enable a high
sampling rate (32 Gbit/s) which improves
the resolution, mass accuracy, and
sensitivity for low-abundance samples.
Dual gain amplifiers simultaneously
process detector signals through both low-
gain and high gain channels, extending the
dynamic range to 105.
Analog-to-digital (ADC) Detector:
Unlike time-to-digital (TDC) detectors
which record single ion events, ADC
detection records multiple ion events,
allowing very accurate mass
assignments over a wide mass range
and dynamic range of concentrations.
New Removable Ion Source
includes repeller, ion volume,
extraction lens and dual filaments
Proprietary INVAR flight tube
sealed in a vacuum-insulated
shell eliminates thermal mass
drift due to temperature changes
to maintain excellent mass
accuracy, 24/7. Added length
improves mass resolution.
Hot, quartz monolithic quadrupole
analyzer and collision cell identical
to the 7000 Quadrupole MS/MS
New Internal Reference Mass
can be delivered to the source at
a low and high concentration
Two 300L/s t urbos pump the
focusing optics and flight tube
From 3 pg of brochure
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Auflösung & Massengenauigkeit
R = 614/0.68 = 903
Δmz = 0.1/614
= 160 ppm
Pw=0.68
Mz=614 SQ
TQ
IT
TOF
Q-TOF
R = 614/0.0423 = 14522
Δmz = 0.0004/613.96
= 0.7 ppm
Auflösung “Resolving Power:”
R=mz/FWHM
(FWMH = full width at half maximum)
Massengenauigkeit:
Δmz=dm/mz*106, parts per million (ppm)
PFTBA mass 614
C12F24N=613.964203
1 Da.
1 Da.
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Viele mögliche Formeln mit MSD oder IT Aber nur einige wenige mit TOF
1
10
100
1000
10000
0.1 1 10 100 1000
# P
oss
ible
Ch
emic
al F
orm
ula
s
mass uncertainty, ppm
Possible Number of Chemical Formulas at m/z 272
Formulas made of:
C,H,N,O,F, & Cl
mass uncertainty
ppm amu # of Possible
Formulas 1000 0.3 7657
368 0.1 4050 100 0.03 1223
37 0.01 466 10 0.003 120
4 0.001 43 1 0.0003 11
0.4 0.0001 5 0.1 0.00003 2
Octafluoronaphthalene (CAS
313-72-4)
C10F8 = 271.98667
Genaue Massen verringern das Risiko in das falsche Molekül Arbeit zu investieren
Quad
4 ppm TOF
1 ppm
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7200 Instrument Performance Spezifkationen…
Auflösung: >12.5 K at m/z 272, typisch 13500
Massen Genauigkeit: <5 ppm at m/z 272
MS Empfindlichkeit ist zwischen SIM und Scan eines Single Quad Instrument
MS/MS Empfindlichkeit ist zwischen SRM und Produkt Ionen Scan eines Tandem Quad Instrument
Dynamischer Bereich: 3-5
Quad Massen Bereich: 20-1050 Da (0.7-4.0 Da FWHM)
TOF Massen Bereich : 20-1700 Da
Spektrale Rate: 1-50 Spektren/sec
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• Die Welt um uns ändert sich dauernd und neue Probleme können
jederzeit auftreten
• Neue Probleme erfordern oft neue Instrumente um eine Lösung zu
finden
• Das GC Q-TOF bietet Leistungsmerkmale um neue Probleme auf
neue Weise zu lösen
• Höhere Auflösung (HR), bessere Massen Genauigkeit (MA), und
schnellere Scan Geschwindigkeit verbessern immer
die analytischen Ergebnisse
• Erweitere MS/MS Produkt-Ionen durch HR und MA
und Strukturaufklärung wird möglich
• Agilent bietet die größte Palette leistungs-
fähiger GC/MS Geräte – SQ, IT, TQ, & Q-TOF
Zusammenfassung – was Sie beachten sollten