Transcript Titan, Tholins et la chimie Physique, Projet d

Orbitrap Mass Analyser: a Tool for Titan
Complex Molecular Content Exploration
Roland Thissen
Stefano Cornelli
Pascal Puget
Grenoble
Grenoble
Grenoble
Christelle Briois
Laurent Thirkell
Amirouche Boukrara
Jean-Pierre Lebreton
Orléans
Orléans
Orléans
Orléans
Patricia Beauchamp
Evan Neidholdt
Jack Beauchamp
Pasadena
Pasadena
Pasadena
Hervé Cottin
Noel Grand
Creteil
Creteil
Cyril Szopa
Nathalie Carrasco
Claude Chapuis
Abdel Bouabdellah
Versailles
Versailles
Versailles
Versailles
Cécile Engrand
Orsay
Alexander Makarov
Bremen
Toulouse
Paris
High mass-resolution for Titan?
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Cassini (INMS)
ionic densities in Titan ionosphere
 Quad
masse filter
C7NH+
99.0109
resolution
 60 uma luckily upgraded in 100
+
amu
C
99.0235
7857
8H3
N3H9+
99.0797
1761
 C4Resolution
limited to 1 amu
C5N2H11+
C6NH
N132++,
C7H15+
m/z 28
99.0923
7857
C299.1049
H4+, HCNH+7853
99.1174
7920
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Big molecule synthesis …
+
-
m/z
Positive ions <350
Negative ions >1000
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
070511_Lot1MeOH_b #663-697 RT: 19,32-20,28 AV: 35 NL: 1,02E5
T: FTMS + p ESI Full ms [50,00-500,00]
262,1774
100
C9H16N7
10090
C=12.0000
H= 1.0078
N=14.0031
100
80
80
80
ISOTOPES
60
3
x10
C7H12N9
262,1526
60
60
x10
3
70
50
40
40
40
2030
C11H20N5
262,2026
C7H12N5O2
262,1412
20
0
10
262.00
262.05
262,0216
262.10
262.15
262,1275
262,1004
20
0
262.20
262.25
262.30
262,2161
262,3478
0
262,0
262,1
262,2
m/z
262.35
262,3
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Isotopical abundancies,
example on complex mixture…
fulvique pos SIM700-800FT #6-336 RT: 0.15-9.77 AV: 331 NL: 5.08E3
T: FTMS + p ESI SIM m s [700.00-800.00]
773.30243
C 39 H 49 O 16
100
775.28195
C 38 H 47 O 17
95
90
85
773.33907
C 40 H 53 O 15
773.26603
C 38 H 45 O 17
80
75
775.24527
C 37 H 43 O 18
70
65
773.22966
C 37 H 41 O 18
60
775.35458
C 40 H 55 O 15
55
775.20911
C 36 H 39 O 19
50
45
775.13636
C 34 H 31 O 21
40
773.37535
C 41 H 57 O 14
35
13C
775.10005
C 33 H 27 O 22
774.30463
30
774.34089
25
774.26786
20
774.22613
774.37241
10
5
774.51638
774.12421
773.41210
C 42 H 61 O 13
774.59469
774.08702
773.89316
0
773
773.2
773.4
773.6
775.39105
C 41 H 59 O 14
775.06434
C 50 H 15 O 10
774.19037
15
773.8
774.0
775.51910
C 41 H 75 O 13
774.69143
774m /z
774.2
774.4
774.6
774.8
775.0
775
775.2
775.4
775.6
C 36 H 39 O 19
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775.13636
C 34 H 31 O 21
775.10005
C 33 H 27 O 22
18O
775.39105
C 41 H 59 O 14
775.06434
C 50 H 15 O 10
638
774.59469
775.51910
C 41 H 75 O 13
774.69143
774.6
774.8
775.0
775.2
775.4
775.6
Orbitrap mass Analyser ?
11 / 46
Preliminary remark,
what is orbitrap…
Mass Spectrometry :
12 / 46
Perfect quadro logarithmic potential
k

m/ z
record movement of
unperturbed ions during
>500ms
pressure <10-9 mbar!
13 / 46
How to inject and stabilize ions in this
perfect potential? “Electrodynamic squeezing”
•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!
(r,φ)
(r,z)
Need for very stable HV potential
During measurement!
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Orbitrap, potential
Ultra high resolution: 100 000 at mass 400, adjustable
during mission, as it depends only on the integration time
Very small volume, lightweight : l=4 , f= 4 cm
Good detection Dynamic : 50 000 per spectrum
Positive or negative Ions as only one potential to invert
All ions are analysed simultaneously
No detector, no saturation, …
no RF, no moving part
Ideal for solids or aerosols
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Orbitrap for Titan
Orbitrap prototype
in Orléans
Sample handling
ionization
Ion accumulation
Study of optimized
MS instrument for the analysis of
aerosols/solids/liquids present in
the deep atmosphere/surface of
Titan
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Performances of prototype…
Without laser
With laser
FREQUENCY /KHz
17 / 46
1 laser shot
on Stainless steel
R=280 000
m/z
18 / 46
Tholins survive the laser
desorption/ionization
19 / 46
Conclusions
Going back to Titan, we need to do much better than Cassini.
We know that very large (bio)organic molecules are
produced/present in


Atmosphere
Surface
Aerosols
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/B
Briois, Cornelli and Thirkell