orbitrap mass analyser: a tool for titan complex molecular content exploration roland...
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Orbitrap Mass Analyser: a Tool for Titan Complex Molecular Content
Exploration
Roland Thissen GrenobleStefano Cornelli GrenoblePascal Puget Grenoble
Christelle Briois OrléansLaurent Thirkell OrléansAmirouche Boukrara OrléansJean-Pierre Lebreton Orléans
Patricia Beauchamp PasadenaEvan Neidholdt PasadenaJack Beauchamp Pasadena
Hervé Cottin CreteilNoel Grand Creteil
Cyril Szopa VersaillesNathalie Carrasco VersaillesClaude Chapuis VersaillesAbdel Bouabdellah Versailles
Cécile Engrand Orsay
Alexander Makarov Bremen
ToulouseParis
High mass-resolution for Titan?
3 / 46
Quad masse filter
60 uma luckily upgraded in 100 amu
Resolution limited to 1 amu
m/z 28
N2+, C2H4
+, HCNH+
Cassini (INMS) ionic densities in Titan ionosphere
C7NH+ 99.0109 resolution
C8H3+ 99.0235 7857
C4N3H9+ 99.0797 1761
C5N2H11+ 99.0923 7857
C6NH13+ 99.1049 7853
C7H15+ 99.1174 7920
4 / 46
Big molecule synthesis …
Positive ions <350 Negative ions >1000
m/z
+ -
5 / 46
Bio molecules synthesis…
Horst et al. Accepted in Astrobiology
6 / 46 Tholins mass spectrum at high resolution
7 / 46
Zoom on mass 262
100
80
60
40
20
0
x10
3
262.35262.30262.25262.20262.15262.10262.05262.00
100
80
60
40
20
0
x103
070511_Lot1MeOH_b #663-697 RT: 19,32-20,28 AV: 35 NL: 1,02E5T: FTMS + p ESI Full ms [50,00-500,00]
262,0 262,1 262,2 262,3m/z
0
10
20
30
40
50
60
70
80
90
100
Rela
tive A
bundance
262,1774
262,1526
262,2026
262,1412
262,1275262,1004262,0216 262,2161 262,3478
C9H16N7
C11H20N5
C7H12N9
C=12.0000H= 1.0078N=14.0031
C7H12N5O2
ISOTOPES
8 / 46
fulvique pos SIM700-800FT #6-336 RT: 0.15-9.77 AV: 331 NL: 5.08E3T: FTMS + p ESI SIM ms [700.00-800.00]
773.2 773.4 773.6 773.8 774.0 774.2 774.4 774.6 774.8 775.0 775.2 775.4 775.6
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
un
da
nce
773.30243C39 H49 O16
775.28195C38 H47 O17
773.33907C40 H53 O15
773.26603C38 H45 O17
775.24527C37 H43 O18
773.22966C37 H41 O18
775.35458C40 H55 O15
775.20911C36 H39 O19
775.13636C34 H31 O21
773.37535C41 H57 O14
774.30463
774.34089
775.10005C33 H27 O22
774.26786
774.22613
774.19037775.39105
C41 H59 O14
774.51638
774.37241
774.12421
774.59469773.41210
C42 H61 O13
775.06434C50 H15 O10
774.08702775.51910
C41 H75 O13774.69143773.89316
773 774 775
13C
Isotopical abundancies,example on complex mixture…
9 / 46
fulvique pos SIM700-800FT #6-336 RT: 0.15-9.77 AV: 331 NL: 5.08E3T: FTMS + p ESI SIM ms [700.00-800.00]
773.2 773.4 773.6 773.8 774.0 774.2 774.4 774.6 774.8 775.0 775.2 775.4 775.6
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
un
da
nce
773.30243C39 H49 O16
775.28195C38 H47 O17
773.33907C40 H53 O15
773.26603C38 H45 O17
775.24527C37 H43 O18
773.22966C37 H41 O18
775.35458C40 H55 O15
775.20911C36 H39 O19
775.13636C34 H31 O21
773.37535C41 H57 O14
774.30463
774.34089
775.10005C33 H27 O22
774.26786
774.22613
774.19037775.39105
C41 H59 O14
774.51638
774.37241
774.12421
774.59469773.41210
C42 H61 O13
775.06434C50 H15 O10
774.08702775.51910
C41 H75 O13774.69143773.89316
18O
Orbitrap mass Analyser ?
11 / 46 Preliminary remark, what is orbitrap…
Mass Spectrometry :
12 / 46
Perfect quadro logarithmic potential
zm
k
/
record movement of unperturbed ions during
>500mspressure <10-9 mbar!
13 / 46
How to inject and stabilize ions in this perfect potential? “Electrodynamic squeezing”
(r,φ) (r,z)
•a bunch of ions enters in the field, tangentially
•ions are squeezed towards central electrode by variation of its potential (deepening of well)
•The excitation of quadratic movement is inherent to “off axis” injection
Need to pulse ions in the trap!
Need for very stable HV potential
During measurement!
14 / 46 Orbitrap, potential
Ultra high resolution: 100 000 at mass 400, adjustable during mission, as it depends only on the integration timeVery small volume, lightweight : l=4 , = 4 cmGood detection Dynamic : 50 000 per spectrumPositive or negative Ions as only one potential to invertAll ions are analysed simultaneouslyNo detector, no saturation, …no RF, no moving partIdeal for solids or aerosols
15 / 46
Study of optimizedMS instrument for the analysis of aerosols/solids/liquids present in the deep atmosphere/surface of
Titan
Orbitrap for Titan
Orbitrap prototype in
OrléansSample handling
ionization
Ion accumulation
16 / 46
Performances of prototype…
Without laser
With laser
FREQUENCY /KHz
17 / 46 1 laser shot on Stainless steel
m/z
R=280 000
18 / 46 Tholins survive the laser desorption/ionization
19 / 46
ConclusionsGoing back to Titan, we need to do much better than Cassini.We know that very large (bio)organic molecules are produced/present in Atmosphere Aerosols Surface Liquids / solids
Request for very high resolution mass spectrometry to be characterized.Orbitrap is a very promising analyser/detector for this purpose.However big challenges remain:
Sample handling ? Ionization method ? High-Vacuum generation/maintenance ? Beyond formulas, what about structural analysis ? …
Further info ? Come & visit posters 7A/BBriois, Cornelli and Thirkell