6TH Thermo Scientific HR GC/MS MeetingBarcelona (Spain) April 29-30 2010
ENHANCED MASS RESOLUTION TANDEMENHANCED MASS RESOLUTION –TANDEM
MASS SPECTROMETRY AND ACCURATE MASS
MEASUREMENTS: TOOLS FOR IMPROVING
ENVIRONMENTAL AND FOOD ANALYSIS
Maria Teresa Galceran
Departament de Química AnalíticaUniversitat de BarcelonaUniversitat de Barcelona
OUTLINE
Instrumentation TSQ Quantum Ultra Accurate MassTSQ Quantum Ultra Accurate Mass
Characteristics Sensitivity
Enhanced Mass resolutionH-SRMH-SRM
SensitivitySelectivity
Mass accuracyIdentification of nkno ns
University of BarcelonaUniversity of Barcelona
Identification of unknownsFragmentation pathways
InstrumentationEnhanced Mass Resolution system:TSQ Quantum Ultra Accurate MassH b li d 6 L 250
Fast Chromatography (U-HPLC) :Accela High Speed Liquid Chromatography
Hyperbolic rods r0 = 6 mm, L = 250 mm
Mass Range: m/z 30 to 1.500
High Scan Speed:0.1s/scan (m/z 30 -1.500),
< 0.07ms/u
Enhanced mass resolution in Q1 and/or Q3 (m/z 0.1 – 0.04 FWHM)
High selective-Selected Ion Monitoring (H-SIM)
Hi h l ti S l t d R ti M it i (H SRM)High selective-Selected Reaction Monitoring (H-SRM)
Instrumentation CHARACTERISTICS
Council Directive 96/23/EC HRMS: “the resolution shall typically be greater than 10.000 for the entire mass range at 10% valley”
Enhanced Mass Resolution:m/z : 0.04 (FWHM)
Mass Accuracy:± 5 mDa
m/z = 1.000 25.000m/z = 500 12.500
m∆ m
Mass Resolving
Power
m/z = 1.000 5 ppmm/z = 500 10 ppm
m/z = 125 3.125m/z 500 10 ppmm/z = 125 40 ppm
C0-100, H3-74, O0-4, N0-4: m/z 118 only 1 candidate formula within 34 ppm m/z 750 626 candidate formula are possible within 5 ppm
to eliminate all extraneous possibilities 0.018 ppm are required q
RESOLUTION vs. INTENSITYInstrumentation
ESI (-)
H3C CH3
HO OH
InfussionDCBPA Mw: 294 Da
NL: 4 66E7 NL: 3 35E70.7 FWHM 0.2 FWHM 0.05 FWHM
Cl ClQ1 0.7 #6-45 RT: 0.06-0.46 AV:40 SM: 3G NL: 5.77E7T: - p ESI sid=14.00 Q1MS [30.070-600.000]
90
95
100 294.82
Q1 0.2 #5-39 RT: 0.05-0.43 AV:35 SM: 3G NL: 4.66E7T: - p ESI sid=14.00 Q1MS [30.020-600.000]
90
95
100 295.00
Q1 0.05 #3-20 RT: 0.11-0.83 AV:18 SM: 3G NL: 3.35E7T: - p ESI sid=14.00 Q1MS [30.006-600.000]
90
95
100 295.06
NL: 5.77E7 NL: 4.66E7 NL: 3.35E7
65
70
75
80
85
296.78 65
70
75
80
85
297.00 65
70
75
80
85
297.05
35
40
45
50
55
60
Rel
ativ
e Ab
unda
nce
35
40
45
50
55
60
Rel
ativ
e Ab
unda
nce
35
40
45
50
55
60
Rel
ativ
e Ab
unda
nce
10
15
20
25
30
35
298.8110
15
20
25
30
35
296.00
298.9610
15
20
25
30
296.07
299.06
m/z m/z m/z290 292 294 296 298 300 3020
5
290 292 294 296 298 300 3020
5
290 292 294 296 298 300 3020
5
122.07RESOLUTION vs. INTENSITYInstrumentationChlormequat
CC
N+CH3
H H
Cl070918_05 02 HRC#53-121RT:0.45-1.03AV:69SM:5BNL:8.39E6T:+ p ESI Q1MS [118.020-128.000]
070918_04 07 HRC#9-16RT:0.07-0.13AV:8 NL:1.65E7T:+ p ESI Q1MS [118.070-128.000]
80
85
90
95
100122.2
NL: 1.61E7 m/z 122 C N+
CH3
CH3
H
H
70
75
80
85
90
95
100122.2
50
55
60
65
70
75
Rel
ativ
e A
bund
ance
0.4 FWHM
NL: 8.39E6
070918_06 01 HRC#11-57RT:0.09-0.49AV:47SM:5BNL:1.69E5T:+ p ESI Q1MS [118.010-128.000]
75
80
85
90
95
100122.2
NL: 1.69E5
40
45
50
55
60
65
70
Rel
ativ
e A
bund
ance
20
25
30
35
40
45
R
124.0
0.1 FWHM
45
50
55
60
65
70
75
Rel
ativ
e A
bund
ance
m/z 0.04 FWHM5
10
15
20
25
30
35124.2
123.2
119 120 121 122 123 124 125 126 127 128m/z
0
5
10
15
123.0
125.0
10
15
20
25
30
35
40124.2
ESI (+) m/z
119 120 121 122 123 124 125 126 127 128m/z
0
5
119 120 121 122 123 124 125 126 127 128m/z
0
5
10123.2
125.2
m/z
m/zInfussion
OUTLINE
Instrumentation TSQ Quantum Ultra Accurate MassTSQ Quantum Ultra Accurate Mass
Characteristics Sensitivity
Enhanced Mass resolutionH-SRMH-SRM
SensitivitySelectivity
Mass accuracyIdentification of nkno ns
University of BarcelonaUniversity of Barcelona
Identification of unknownsFragmentation pathways
H-SRM vs SRM SensitivityEnhanced mass resolution
Sample: Pears Target analyte: Chlormequat Concentration: 70 µg/kg
RT: 1.00 - 3.00 SM: 7G
100
RT: 2.37SN: 481
NL: 1.73E4m/z=
RT: 1.00 - 3.00 SM: 7G
100
RT: 2.37SN: 481
NL: 1.73E4m/z=
RT: 1.00 - 3.00 SM: 7G
100
RT: 2.37SN: 271
NL: 6.06E4m/z= 57.7000-58.7000
RT: 1.00 - 3.00 SM: 7G
100
RT: 2.37SN: 271
NL: 6.06E4m/z= 57.7000-58.7000
70
80
90
100 58.1500-58.2500 F: + c ESI SRM ms2 [email protected] [57.651-58.651] MS 071213_25
70
80
90
100 58.1500-58.2500 F: + c ESI SRM ms2 [email protected] [57.651-58.651] MS 071213_25
70
80
90
100 F: + c ESI SRM ms2 [email protected] [57.651-58.651] MS ICIS 071213_27
70
80
90
100 F: + c ESI SRM ms2 [email protected] [57.651-58.651] MS ICIS 071213_27
SRMQ1: 0.7 FWHMQ3: 0.7 FWHM
H-SRMQ1: 0.1 FWHMQ3: 0.7 FWHM
40
50
60
70
ativ
e Ab
unda
nce
40
50
60
70
ativ
e Ab
unda
nce
40
50
60
70
ativ
e Ab
unda
nce
40
50
60
70
ativ
e Ab
unda
nce
10
20
30
40
Rel
a
10
20
30
40
Rel
a
10
20
30
40
Rel
a
10
20
30
40
Rel
a
Isobaric chemical noise can be filtered and the high transmission of ions
1.0 1.5 2.0 2.5 3.0Time (min)
0
10
1.0 1.5 2.0 2.5 3.0Time (min)
0
10
1.0 1.5 2.0 2.5 3.0Time (min)
0
10
1.0 1.5 2.0 2.5 3.0Time (min)
0
10
gat enhanced mass resolution provides a higher signal/noise ratio
CECEMEnhanced mass resolutionH-SRM vs SRM Sensitivity
Ascentis express HILIC (100 mm x 2.1 i.d., 2.7 µm) 45:55 Acetonitrile:formic acid-ammonium formate, pH.3.75
DADMAC (Diallyldimethylammonium)
SRM H‐SRMRiver waterNQ1: 0.7, Q3: 0.7 Q1: 0.1, Q3: 0.7
NL: 1.65E4
m/z 126.12 > 84
1.02NL: 1.65E4100
1.01NL: 2.82E4 1001.01NL: 2.82E4
m/z 126 > 84
98 ng/LN
DADMAC
PolyDADMAC: cationic polyelectrolyteused as:- Filter and anti-static in paper industry S/N 150an
ce
ndan
ce
50 50
S/N 90
m/z : 126.1277
- Additive for dyestuff in textileindustry.- Flocculant in water and wastewatertreatment plants
1.02 NL: 2.39E3R
elat
ive
Abu
nda
Rel
ativ
eA
bun
1.02 NL: 2.39E31.01 NL: 5.71E3 100
0
100
01.01 NL: 5.71E3
m/z 126.12 > 70 m/z 126 > 70
No sample treatment. 10 µL injected in the LC-MS/MS system
LODs: 15 ng/L 0
50
0
50
LODs: 15 ng/L (tap water and wastewater)
0.0 0.5 1.0 1.5 2.0Time (min)
0.0 0.5 1.0 1.5 2.0Time (min)
0.0 0.5 1.0 1.5 2.0 2.5Time (min)
0.0 0.5 1.0 1.5 2.0 2.5Time (min)
X. Esparza , E. Moyano, F.Ventura, M.T. Galceran, J.Chromatogr.A. (submitted)
CECEMEnhanced mass resolutionH-SRM vs SRM Selectivity
SRMQ1: 0.7, Q3: 0.7
H‐SRMQ1: 0.7, Q3: 0.1
Raw material in production of polycarbonate plastics
and epoxy resins
Surface water100 ng/L
100 100
Liquid Chromatography- LC system: ACCELA UHPLC (Thermo)
Bisphenol A
and epoxy resins
50
100 NL: 1.67E4
50
100 NL: 1.04E4
BPA
m/z 227 → 212.08
BPA
m/z 227 → 212.08m/z 227 → 212 m/z 227 → 212.08
- LC system: ACCELA UHPLC (Thermo)- Column: Ascentis Express C18 Fused Core
(50 mm x 2.1 mm, 2.7 µm)- Mobile phase: Acetonitrile:Methanol:Water - Flow rate: 0 6 mL/min 1000e
Ab
un
da
nce
NL: 6 34E3 1000
NL: 3 29E3
S/N: 50 S/N: 110
abun
danc
e
- Flow rate: 0.6 mL/minOn-line SPE- SPE column: Hypersil Gold C18
(20 mm x 2.1 mm, 12 µm)Sample volumen: 1 mL
50
Re
lativ
e NL: 6.34E3
50
NL: 3.29E3BPA
m/z 227 → 133.06 BPA
m/z 227 → 133.06m/z 227 → 133
m/z 227 → 133.06
Rel
ativ
e H-SRM on Q3 improves sensitivity and selectivity
- Sample volumen: 1 mL
4.5 5.5 6.5 7.50
4.5 5.5 6.5 7.50
S/N: 75S/N: 2
LODs: 17 ng/L Surface Water H. Gallart-Ayala, E. Moyano, M.T. Galceran, J.Chromatogr.A.,1217 (2010) 3511
Time (min) Time (min)
CECEMEnhanced mass resolutionH-SRM vs SRM Selectivity
Toltrazuril (TOL)100 m/z 371 371
H‐SRMQ1:0.1 Q3:0.7
Veterinary drug Toltrazuril and its metabolites in a frankfurt sausage
100SRMAPCI (-)
Q1:0.7 Q3:0.7
m/z 371 371Toltrazuril (TOL)
Toltrazuril Sulfoxide (TOLX)1000
1000
1.6
m/z 371 271
m/z 388 288S/N:14
TOLX
1000
1000
e
1.6
m/z 371 271
S/N:8 m/z 388 288
m/z 371 371
Toltrazuril Sulfoxide (TOLX)
0
1000
1.6
100 1.8
m/z 388 248
m/z 356 256S/N:14
S/N:15TOL0
1000
ative Abu
ndance
1.6
100 1.8
m/z 388 248
m/z 356 256S/N:2
S/N:11
/
Toltrazuril Sulfone (TOLS)
Liquid Chromatography• LC system: ACCELA UHPLC• Column: Ascentis Express C18
1000
1000 1.8
1.8
m/z 356 124
m/z 359 256
S/N:11TOLS Re
la
1000
1000
1.8
1.8
/
m/z 356 124
m/z 359 256
S/N:3
• Column: Ascentis Express C18(150 mm x 2.1 mm, 2.7 µm) • Temperature: 40 ºC• Mobile phase: MeOH:H2O60% to 100% MeOH in 0 9 min
0.0 1.0 2.0 3.0 4.0Time (min)
0
1000
1.8m/z 359 124
TOL-
D3
1.0 2.0 3.0 4.0Time (min)
0
1000
1.8
/
m/z 359 124
60% to 100% MeOH in 0.9 min• Flow rate: 500 µL min‐1 A. Martinez-Villalba , E. Moyano, M.T. Galceran, Anal.Bioanal.Chem. (accepted)
Time (min)Time (min)
Enhanced mass resolutionH-SRM vs SRM Preventing interfering problems
Q1: 0.7Q3: 0.7
RT: 1.00 ‐ 7.52 SM: 15G
1003.28 NL: 2.19E5
m/z 54 9951 55 1951Unknown
Q1: 0.04Q3: 0.7
RT: 0.00 ‐ 10.01 SM: 15B
100 4.34 NL: 4.71E3TIC F + c ESI
AcrylamideH-SRM Column:
S i i ODS 80 TS
SRMAnalysis of acrylamide in potato chips
60
100
ive Abu
ndan
ce
m/z= 54.9951‐55.1951 F: + c ESI sid=10.00 SRM ms2 [email protected] [55.085‐55.185] MS mostra Q1 0.7
80
m/z 72 5560
80
100 TIC F: + c ESI sid=10.00 SRM ms2 [email protected] [55.085‐55.185] MS mostra q1 0.04
ive Abu
ndan
ce
m/z 72.04 55
y
Unknown
Semi-micro ODS-80 TS column (Tosohaas)5 μm, 150 x 2.1 mm I.D.Mobile phase: 100% Water Fl t 300 L/ i
100
0
20
40
Relati
4.34
4.33 NL: 4.09E4
Acrylamide
0
20
40
4.34 NL: 5.76E2
Relati Unknown
3.28
500 µg/kg
Flow rate: 300 µL/min
118.1100 Unknown
Full scan
TIC F: + c ESI sid=10.00
60
80
100 4.33SRM ms2 [email protected] [58.085‐58.185] MS mostra Q1 0.7
bund
ance
d3-Acrylamide
60
80
1004.34
TIC F: + c ESI sid=10.00 SRM ms2 [email protected] [58.085‐58.185] MS mostra q1 0.04
bund
ance
d3-Acrylamide
m/z 75.10 58
40
60
80
lative Abundance
148.1162.1
133 0
1 2 3 4 5 6 70
20
40
Relative
Ab
m/z 75 58
0 1 2 3 4 5 6 7 8 9 100
20
40
Relative
Ab
40 60 80 100 120 140 160 180 200m/z
0
20
Rel 133.0
74.051.0
1 2 3 4 5 6 7Time (min)
0 1 2 3 4 5 6 7 8 9 10Time (min)
Working at H‐SRM, the effect of the interfering compound decreases and AA can be determined
OUTLINE
Instrumentation TSQ Quantum Ultra Accurate MassTSQ Quantum Ultra Accurate Mass
Characteristics Sensitivity
Enhanced Mass resolutionH-SRMH-SRM
SensitivitySelectivity
Mass accuracyIdentification of unknowns
University of BarcelonaUniversity of Barcelona
Fragmentation pathways
IDENTIFICATION OF UNKNOWNS Mass Accuracy
Potato sample
Interfering compound:O
NH2
A l id
118.0902100
x10 x10
Lock Mass:DMA
Q1:0.04Interfering compound:m/z 118 and 72 accurate mass measurement
L: 74.0964
Acrylamide
60
80
72 0801 L: 74.0964
L: 114.1277
DEAMQCQ
Relative Abundance4040
72.0801
mass accuracy: 5 mDaElemental composition:
C5H11NO2
L: 46.0651Acrilamide
mass accuracy: 3.5 mDa
Acrylamide0
2020
L: 46.0651
L: 122.0731
72.048446.05 46.10m/z
72.00 72.05m/z
74.05 74.10m/z
114.10 114.15m/z
118.05 118.10m/z
122.05 122.10m/z
0
Data base : 7 compounds. Of them only 4 can give fragments of m/z 72 and 55
Compounds related with Valine and Norvaline. Valine has been described as a precursor of AA and it is present in potatoes
m/z m/z m/z46.05 46.10 72.00 72.05 74.05 74.10as a precursor of AA and it is present in potatoes.
IDENTIFICATION OF UNKNOWNS Mass Accuracy
Liquid Chromatography- LC system: ACCELA UHPLC (Thermo)- Column: Ascentis Express HILIC (50 mm x 2.1 mm, 2.7 µm)- Mobile phase: Acetonitrile/50 mM Formic acid-ammonium formate
m/z 243Amprolium
pH 3.75 (60:40)- Flow rate: 0.6 mL/min m/z 94m/z 150
AreaH-ESI in positive mode Matrix enhancement
m/z 243 > 150
ng/g
Enhancement produced by an unknown compoundA. Martinez-Villalba , E. Moyano, M.T. Galceran, J. Chromatogr. (submitted)
p y p
Q1 0 7 Q3 0 7Q1 0 7 Q3 0 04
IDENTIFICATION OF UNKNOWNS Mass Accuracy
100da
nce
0.641.32
1.500.96100
bund
ance
1.60100
ance
162.1 100
ance
103.0
162.1MS/MSMSRt AMP
AM 162.1167 AM 103.0371
AM 85.0329
Q1:0.7, Q3:0.7Q1:0.7, Q3:0.04
TIC
Rel
ativ
e A
bund
1.64
2.432 020 43
0.0 1.0 2.0Time (min)
0Rel
ativ
e A
b
Rel
ativ
e A
bund
a
Rel
ativ
e A
bund
a
85.0
60.1 102.1
0
R 2.020.430.16
0.0 0.5 1.0 1.5 2.0 2.5Time (min)
100 200 300 400 500m/z0
R60 80 100 120 140 160 180 200m/z
0
R
666 structuresAll without charge12 structures
0 possible structuresAll Quaternary Amines
4. ESPECTROMETRIA DE MASSES
IDENTIFICATION OF UNKNOWNS Mass Accuracy
Identification of the unknown
100 1 64 100 103.0
Deng, J. Henion, J. Li, P. Thibault, C. Wang, J. Harrison. Anal. Chem. 73 (2001) 639‐646C. Tallarico, S. Pace, A. Longo. Rapid Commun. Mass Spectrom. 12 (1998) 403‐409
100Ab
unda
nce
1.64 100
e A
bund
ance
103.0
85.1162.260 1
MS/MS
m/z 85
0
Rel
ativ
e A
0
Rel
ativ
e 60.1102.0
m/z 103m/z 60
L-CarnitineMw=162.1
0.0 0.5 1.0 1.5 2.0 2.5Time (min)
0 60 80 100 120 140 160 180 200m/z
0
FRAGMENTATION PATHWAYS Mass Accuracy
• Starters in the synthesis of epoxy resins
Analysis of bisphenol diglycydil ethers
OO O
O
HH
• Additives in PVC organosolsAs scavengers for the HCl formed during the heat treatment in the coating procedure
p,p-BFDGE
O O
O
O
HH
• BFDGE is the monomer of NOGE (novolacglycidyl ether)
O
OO
o,p-BFDGE SunFireTM C18 column (150 x 2.1 mm i.d., 3.5 µm)
M bil h M OH 25 M HCOOH/NH COOH ( H
Liquid chromatography
O OOH
H
o o BFDGE
Mobile phase: MeOH:25 mM HCOOH/NH4COOH (pH 3.75; 40 ºC); 300 µL min-1
0-2 min: 50% MeOH isocratic
2 7 i 75% M OHo,o-BFDGE 2-7 min: 75% MeOHH. Gallart-Ayala, E. Moyano, M.T. Galceran, Rapid Commun.Mass Spectrom, (submitted)
FRAGMENTATION PATHWAYS Mass AccuracyESI (+)MS/MS
100ance 163 Isomer 1
50
100
Abun
danc
e
Multiple-stage mass spectrometry (MSn): Ion trap
MS/MS163
100
nce
I 3
ESI (+)
50
Rel
ativ
e A
bund
133
3.0 4.0 5.00
50
Rel
ativ
e
Time (min)50
elat
ive
Abu
nda 133
147239
171 277211
Isomer 3
ce 189
MS3
107
ance
100
200 300 400m/z
0
R
105
133
nce100
119MS3
150 200 250 300 350 400m/z
Re
0
50
100at
ive
Abu
ndan
c 189
163295
265133
MS/MS Isomer 2
Rel
ativ
e A
bund
a
50
100
lativ
e A
bund
an
50MS3
100ce
133m/z
400150 200 250 300 3500
Rel
265207177133 237147 313
60 100 140 180m/z
R
0
MSn of BFDGE
Re
m/z60 100 140 1800
50
100
ativ
e A
bund
anc
171189
Precursor ion [M+NH4]+ m/z:330m/z60 100 140 1800R
ela 89
FRAGMENTATION PATHWAYS Mass Accuracy
NH4+
o,o-BFDGE
NH
50
100
lativ
e A
bund
ance
p,p-BFDGE
MS/MS
m/z 330MS/MS MS/MSNH4
+o,p-BFDGE
NH4+ 3.0 4.0 5.0Time (min)
0Rel
m/z 330
m/z 239 m/z 147
MS3
MS/MS
H+ H+
m/z 330
MS/MS MS/MS MS/MSMS/MS
/ 119
m/z 163 m/z 189m/z 295
MS3
m/z 163
MS3
m/z 119m/z 163
MS3 MS3
H+
MS3 MS3 MS3MS3
/ 107
m/z 121m/z 107m/z 121 m/z 133 m/z 171m/z 107
m/z 107
FRAGMENTATION PATHWAYS Mass Accuracy
100LAS-MON
ESI(+) Coccidiostats
Liquid Chromatography
- LC system: Alliance 2695 (Waters)Column: C18 Hypersil Gold (50 x 2 1 mmNAR - Column: C18 Hypersil Gold (50 x 2.1 mm
1.9 µm) (Thermo Fisher Scientific)- Mobile phase: Acetonitrile:Water (0.1% formic acid in each phase)
Gradient: From 40% to 70% Acetonitrile in
SAL
NAR
- Gradient: From 40% to 70% Acetonitrile in 0.75 min and 6 min of isocratic step- Column Temperature: 50ºC- Flow rate: 0.6 mL/minROB
DNC DICMADESI (-)
ESI(+)
0
NIG
0 2 4 6 8 10
Full scan ESI MS in positive ornegative mode (compound dependent)
Time (min)
H
FRAGMENTATION PATHWAYS Mass Accuracy
MASS SPECTROMETRY
- MS system: LCQ Classic (Thermo Finnigan)I i ti S ESI O O
OO
O
O
H
H
H
m/z 599m/z 461
Monensin
- Ionization Source : ESI- Mass Analyser: Ion Trap- Acquisition mode: Product ion scan - Polarity: Positive
O
O O
OO
O
O
H
m/z 483
MS/MS
100675
100675
100693
100693
[M+Na]+ [M+Na‐H2O]+
MS 3100657
100657
[M+Na‐H2O‐H2O]+OH
[M+Na-H2O-(H2O+ COO)]+Abu
ndance
Abu
ndance
Abu
ndance
Abu
ndance
Abu
ndance
599 613Abu
ndance
599
[M+Na-H2O-(CH3O)2]+
Relative
693
Relative
693
Relative
Relative
[M+Na‐H2O]+
Relative
443 675461
483
581
6 3
639Relative
443 675461
483
581
639
m/zm/z300 500 700 900
0
693
300 500 700 9000
693
200 400 600 800m/z
0200 400 600 800 1000
m/z
0
m/zm/z300 500 700 900
0300 500 700 900
0
FRAGMENTATION PATHWAYS High Resolution/Mass AccuracyHigh Resolution/Mass Accuracy
LTQMS/MS conditions:Normalized Collision Energy: 27
Working Conditions
LTQ Orbitrap XL (ThermoFinnigan)Activation Q: 0.3
Activation time: 30 msecOrbitrap: MS3Orbitrap:High mass resolution conditions:Resolving Power: 60,000Mass accuracy: < 1-2 ppm m/z: 693 m/z: 675 m/z: 613
Ion assigment Calculatedmass(Da)
AccurateMass(Da)
Error (ppm)
M iMonensin
[M+Na‐H2O‐(H2O+ COO)]+ 613.4075 613.4045 ‐4.9
[M+Na‐H2O‐(CH3O)2]+ 613.3711 613.4045 +54.4
A Martínez‐Villalba E Moyano M T GalceranA. Martínez Villalba, E. Moyano, M.T. GalceranRapid Commun. Mass Spectrom. 2009; 23: 1255–1263
6TH Thermo Scientific HR GC/MS MeetingBarcelona (Spain) April 29-30 2010
ACKNOWLEDGMENTSUniversity of Barcelona
CIBIR Research Center, SpainJosé Antonio Allué
Elisabeth Bermudo
Encarna Moyano
ThermoFisher ScientificJoan SoléClaudia Martins
Hector Gallart
Xavier EsparzaThank you for your attention
Claudia Martins
Financial support:
Anna Martinez
Ministerio de Educacion y Ciencia CTQ2006-26237E/BQUMinisterio de Ciencia e Innovación CTQ2009-09253Generalitat de Catalunya PIER 2006Ministerio de Educación y Ciencia CTM2006-00753y