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7/29/2014
1
Mass Spectrometry of Synthetic Polymers
Árpád Somogyi
CCIC MSP
OSU Summer Workshop
Problems with polymer analysis• Sample preparation
– Several polymers are not well soluble in conventional solvents
– Solventless technique– Cationizing with Na+, K+, and Ag+ by spiking– Synthesis of tailor (home) made matrices
• Degradation during ionization (especially with MALDI)– Photodissociation in MALDI (MALDI/ESI comparison
desirable)
• End group analysis reliable but better to have high resolution/accurate mass (FT-ICR)
7/29/2014
2
Molecular weight distribution defines polydispersity of polymers
Polydispersity (PD) = Mw/Mn
Polystyrenewith Ag+
Zhu, H.; Yalcin, T.; Li, L. JASMS, 1998, 9, 275-281.
829.987
991.986
1143.205
1313.231
1433.246
1553.257
1723.288
1123.212
2013.333
2303.4052593.467
2933.604
* NB_89_M4\0_M16\1\1SRef, "Baseline subt."
0.0
0.5
1.0
1.5
2.0
5x10
Inte
ns.
[a.u
.]
1000 1500 2000 2500 3000 3500 4000 4500m/z
Trancated Vectra Polymer (Somogyi et. al.,)
PD > 1.05
PD≈1.01
Zhu, H.; Yalcin, T.; Li, L. JASMS, 1998, 9, 275-281.
MS is an absolute method for MW determination(but remember possible degradation!)
7/29/2014
3
http://www.polymerprocessing.com/polymers/alpha.html
Poly(ethylene terephtalate) (PET)C10H8O4 (192.042259)
Polystyrene (PS)C8H8(192.042259)
Poly(methyl methacrylate) (PET)C5H8O2 (100.052430)
Poly(vinyl alcohol) (PVA)
C2H4O (44.026215)
- CH2-CH2-O-Poly(ethylene glycol) (PEG)
Repeating unit masses of polymers
0
1000
2000
3000
4000
Inte
ns.
[a.u
.]
500 1000 1500 2000 2500 3000 3500m/z
0
500
1000
1500
2000
Inte
ns.
[a.u
.]
1675 1700 1725 1750 1775 1800 1825 1850 1875m/z
Synthetic Polymer Analysis by MS (MALDI-TOF)
1684.205
1728.2311772.260
1816.2921660.310
4444
4444
7/29/2014
4
CH3OH exact mass: 32.0262 u
3 7 4 3 7 6 3 7 8 3 8 0 3 8 20
2 0
4 0
6 0
8 0
1 0 0
Re
lati
ve
In
ten
sit
y
m / z
3 5 7 0 3 5 7 2 3 5 7 4 3 5 7 6 3 5 7 80
2 0
4 0
6 0
8 0
1 0 0
Re
lati
ve
In
ten
sit
y
m / z
a
b
374.4183 (average mass)
374.2040 (exact mass)
3570.8741 (exact mass)
3572.9742 (average mass)
0 2 0 0 0 4 0 0 0 6 0 0 0 8 0 0 0
0
1
2
3
4
5
6
7
8
De
via
nc
efr
om
no
min
al
ma
ss
(d
alt
on
)
m / z
c
[Ala5+H]+
[Ala50+H]+
exact mass
average mass
C15H28O6N5
C150H253O51N50
7/29/2014
5
854.2870
856.2832
857.2855
858.2872
859.2904 860.2930
861.2377
862.2416
3_OEB_000001.d: +MS
861.2365
862.2399
863.2428
864.2455
3_OEB_000001.d: C 45 H 42 Na 1 O 16 ,861.24
856.2811
857.2845
858.2873
859.2900
3_OEB_000001.d: C 45 H 46 N 1 O 16 ,856.28
0
1
2
3
7x10Intens.
0.00
0.25
0.50
0.75
1.00
1.25
7x10
0
1
2
3
4
7x10
854 856 858 860 862 864 m/z
FT-ICR - Accurate Mass Measurements(ESI Ionization, MeOH:ACN 1:1)
C45H42O16Na+
C45H42O16NH4+
FT-ICR - Accurate Mass Measurements
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6
MS/MS spectra of polymers depend on
• The cationizing agent (sample preparation)
• Instrument type, ion activation method
– Low energy (eV) collisions (Q-TOF, FT-ICR (SORI, IRMPD)
– High energy (keV) collisions (TOF-TOF)
MS/MS studies of synthetic polymers date back to early 90s (Jackson, A. T.; Yates, H. T.; Bowers, M. T.; Lattimer, R. P.; Wesdemiotis, C., etc.)
Renaissance, due to sophisticated instrumentation
Main goal is to determine polymer structure but basic studies such as comparison of different activation methods are emerging
Survival yield curveM/(M+F)
SY50: characteristic;easy spectra evaluation
low energy spectrum, little fragmentation
correct MW distribution
high energy spectrum, lot of fragments
good “fingerprint”
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7
Results for PEGsMemboeuf, IMMS 2009 (Retz)
Anal. Chem. 82 2294 (2010)
very good linear relationship
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8
96.8853
165.0539
237.5432
329.1004
381.2949
493.1461
537.4941613.1692
657.1901
777.2073
3_OEB_812_QCID_12eV_000002.d: +MS2(812.0)
0
2
4
6
6x10Intens.
100 200 300 400 500 600 700 800 900 m/z
111.9153.6
280.7 329.1
457.1
489.1 612.4
817.2
3_OEB_817_QCID_12eV_000001.d: +MS2(817.0)
0.00
0.25
0.50
0.75
1.00
1.25
1.50
7x10
100 200 300 400 500 600 700 800 900 m/z
96.9
165.1
263.4
329.1
357.2
457.1
493.1
657.2
817.2
3_OEB_817_QCID_30eV_000001.d: +MS2(817.0)
0
2
4
6
6x10
100 200 300 400 500 600 700 800 900 m/z
81212 eV
81712 eV
81730 eV
Na+
Na+
NH4+
O
O CH2 CH2 *m
nO
3-OEB polymerESI, MeOH:ACN 1:1
Q‐CID MS/MS spectra of ammoniated (NH4+) and sodiated (Na+) ions of 3‐OEB polymers in
a FT‐ICR instrument (ApexQh)
Somogyi et al., unpublished
7/29/2014
9
817.308
328.705492.776186.682 657.011
120.738 284.652 354.682 544.397443.72066.510 240.848
0
1
2
3
4
5
4x10
Inte
ns.
[a.u
.]
100 200 300 400 500 600 700 800 900m/z
100 200 300 400 500 600 700 800 900 m/z100 200 300 400 500 600 700 800 900 m/z
96.9
165.1
263.4
329.1
357.2
457.1
493.1
657.2
817.2
0
2
4
6
100 200 300 400 500 600 700 800 900 m/z
QCID30 eV
MALDITOF-TOF(keV)
328.705
492.776
186.682
657.011
120.738514.780
284.652146.719
672.727
679.028
310.689 456.55290.823 354.682 544.397208.735 400.629248.685
0
0
0
0
0
100 200 300 400 500 600 700m/z
Some Examples for Tailor-Made Matrices
NN
FF
F F
HOCOOH
M-1
NN
FF
F F
FF
FF
F FM-3
FF
F F
HOCOOCH3
M-2
NN
FF
F F
HOOH
FF
F FM-4
FF
F F
HOOH
FF
F F
M-5
FF
F F
FF
FF
F F
M-6
FF
F F
FCOOCH3
M-7
NN
FF
F F
H3COOCH3
FF
F FM-9
NN
FF
F F
HOCOOCH3
M-8
Somogyi, et al., Macromolecules, 2007, 40, 5311-5321.
7/29/2014
10
Figure 2. Ethyl isobutyrate POSS PMA oligomers synthesized using ATRP techniques.
O
O CH3
CH3
CH3
CH3
R' =
X = Br
Si
O
Si
Si
SiO
O
OSi
O
Si
Si
SiO
O
O
OO
OO
R R
R
R
R
R
R
OO
(CH2)3
C
CH3
CH2
XR'
n
CH3 S
O
O
CH3
R = C6H5, i-C4H9
O
O CH3
CH3
CH3
CH3
R' =
X = Br
Si
O
Si
Si
SiO
O
OSi
O
Si
Si
SiO
O
O
OO
OO
R R
R
R
R
R
R
OO
(CH2)3
C
CH3
CH2
XR'
n
CH3 S
O
O
CH3
R = C6H5, i-C4H9
m/z2000 2500 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500
%
0
100 2042
2058
20593002
2126
2156
2705
2175 2676 2916
3945
3929
3020
3100
3887
3416 3847
4891
39644873
4044
4350 4831
5833
49085818
49565359
5417
67765851
6759
63045902 6721
67947737
73117162 7411 7835
m/z
m/z2000 2500 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500
%
0
100 2042
2058
20593002
2126
2156
2705
2175 2676 2916
3945
3929
3020
3100
3887
3416 3847
4891
39644873
4044
4350 4831
5833
49085818
49565359
5417
67765851
6759
63045902 6721
67947737
73117162 7411 7835
m/zFigure 3. ESI mass spectrum of [(i‐butyl)7T7propylmethacrylate]n . Most intense peaks are assigned to sodiated and potassiated parent species, the terminal Br being replaced with OH.
Synthesis and MALDI-TOF analysis of non-conventionalPolymers (Polyhedral Oligomeric Silsesquioxanes, POSS)
Anderson, Somogyi, et al.; International Journal of Mass Spectrometry, 2010, 292 (1), 38-47
Practical importances of phenanthroline-functionalized PEGs
stabilization of magnetic nanoparticles(e.g. Fe3O4)
hydrofilic networks by complex formation
Kéki, S.; Kuki, Á. Kuki; Nagy, M.; Nagy, L.; Zsuga, M.JASMS, 2010, 21, 1561-1564.
7/29/2014
11
Change of the absorbance at 515 nm versus molar ratio of the added
Fe(II)-ions and phenanthroline functions of PEGs
0
0.2
0.4
0.6
0.8
1
1.2
350 450 550 650
(nm)
Ab
so
rba
nc
e
CT transition
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 0.2 0.4 0.6 0.8 1
[Fe2+]/[phen]
Ab
sorb
an
ce
(515
nm
)
▲≈10300 M-1cm-1≈11090 M-1cm-1
Fe2+ : PEG_phen = 1: 3
Fe2+ : phen_PEG_phen = 2: 3
Synthesis of phenanthroline-functionalized PEGs
N N
HO
N N N N
HOO
cc. H2SO4, reflux, 1 h
50% NaOH, pH=7
reflux, 72 h
SOCl2, abs. tolueneCH3 O CH2 CH2 OH
n
Cl
n
CH3 O CH2 CH2
N
N
OCH3 O CH2 CH2
nn
CH3 O CH2 CH2 Cl NaH, abs. DMF
reflux, 48 h+
N N
HO
NaH, abs. DMF
reflux, 48 h+
n-1
CH2 O CH2 CH2 ClCH2Cl
nN
N N
NCH2 CH2 OO
2
(PEG_phen)
(phen_PEG_phen)
(Mn = 1100 g/mol)
(Mn = 1500 g/mol)
7/29/2014
12
ESI-MS spectrum of Fe(PEG_phen)32+
0.0
0.5
1.0
1.5
2.0
2.5
4x10Intensity
600 800 1000 1200 1400 1600 1800 2000 2200 2400 m/z
FeL32+
[FeL3+NH4]3+
[FeL3+2NH4]4+
[FeL3+2NH4+Na]5+
[FeL3+3NH4+Na]6+
L = PEG_phen
ESI-MS intensity distribution of PEG_phen and Fe(PEG_phen)32+
+Fe(II)
Fe2+ + Li + Lj + Lk FeLi+j+k2+ (n=i+j+k)
Theoretical model:
0
0.02
0.04
0.06
0.08
0.1
0.12
15 20 25 30 35 40
number of EO units
Pro
ba
bil
ity
0.0
0.2
0.4
0.6
0.8
1.0
60 80 100 120
number of EO units
No
rma
lize
d i
nte
ns
ity measured
simulated
kjkji
in PPPP
1,,
7/29/2014
13
ESI-MS/MS of Fe(PEG_phen)32+
727.
35
1493
.31
2193
.30
0
100
200
300
Intensity
200 400 600 800 1000 1200 1400 1600 1800 2000 m/z
Fe(PEG_phen)32+ Fe(PEG_phen)2
2+ + PEG_phen
Fe(PEG_phen)22+ Fe(PEG_phen)2+ + PEG_phen
0
0.2
0.4
0.6
0.8
1
10 30 50 70
number of EO units
no
rma
lze
d in
ten
sit
y80 V
90 V
simulated
7/29/2014
14
7/29/2014
15
7/29/2014
16
A few recent polymer MS and MS/MS articles in JASMS (April, 2011)
Szyszka, R.; Hanton, S. D.; Henning, D.; Owends, K.G. “Development of a CombinedStandard Additions/Internal Standards Method to Quantify Residual PEG in Ethoxylated
Surfactants by MALDI TOFMS” JASMS, 2011, 22, 633-640.
Song, J.; Siskova, A.; Simons, M. G.; Kowalski, W. J.; Kowalczuk, M. M.; van den BrinkO. F. “LC-Multistage Mass Spectrometry for the Characterization of Poly(Butylene
Adipate-co-Butylene Terephtalate) Copolyester” JASMS, 2011, 22, 641-648.
Fouquet, T.; Humbel, S.; Charles, L. “Tandem Mass Spectrometry of Trimethylsilyl-TerminatedPoly(Dimethylsiloxane) Ammonium Adducts Generated by Electrospray Ionization”
JASMS, 2011, 22, 649-658.
7/29/2014
17
Astrobiology
Anybody else is out there in the Galaxy??
Motivation and Aims“Titan is an Organic Paradise”
Why?
Origin of Color – Origin of Life????Pre-biotic Earth: pre-biotic chemistry?
The Role of Tholin?
7/29/2014
18
Why to use Mass Spectrometry in Space Science?
Lots of charged particles out there in space (not only H+ and e-)
Small neutrals also there (in the gas phase), easy to ionize
Need to shoot mass specs into space
“Visitors” (meteorites) from space come to us
Experimentally modeling (atmospheric) ion-molecule reactionsand checking chemical potential of atmospheric products onthe planet surface
No need to shoot and we can use “fancy” mass specs, e.g., with ultrahigh resolution
7/29/2014
19
General Conclusions on the Role of MS in Atmospheric (Space) Science and
Astrobiology• MS in space
– Provides data from “real” environment
– Kg/$$$$ expensive– Long travel time
(advance design desirable)
– Resolution limited, ambiguous assignments
– m/z limit
• MS on Earth– Does not provide data on
“real” environment– Nevertheless, model
reactions can be easily varied and/or modified and these studies are useful for mission design
(Intelligent? Design!)– Ultrahigh resolution,
accurate mass, repetitive measurements
– Expensive but much cheaper than in space
One of the great successful missions: INMS Data from Titan atmosphere
INMS data from Titan
Ambiguous assignments due to low resolution; “isobaric” ions are not resolved
7/29/2014
20
Questions and Answers
• Why Titan?
• What (and where) is Organic Paradise?
• Why Ultrahigh Resolution MS and MS/MS?
• Why laboratory (model) experiments?
• Why do we care about “simple” organic (?) reactions in the gas-phase (or the origin of life)?
• Atmosphere (N2/CH4) and NH3/ice on surface
• Wide variety of chemical reactions (mass specs!)
• Individual (and not bulk) properties/information
• Titan is too far (far away)
• Just because we are curious human beings
PAHs ?Dinelli et al.Geophys ResLett. 2013
Aerosol growthLavvas et al.PNAS, 2013
7/29/2014
21
Ionization and dissociation of N2 – not so simple….Lavancier, J. et al., “Multiphoton ionization and dissociation of N2 at high laserJ. Phys. B. At. Mol. Opt. Phys. 1990, 23, 1839-1851
Chemical Ionization
• Ion-molecule reaction(s) between a reagent gas and the sample at a relatively high pressure
• Most common reagent gases– methane, isobutane, ammonia
• Mechanisms– CH4 + e- → CH4
+., CH3+, CH2
+., …– CH4
+ + CH4 → CH5+ + CH3
– CH3+ + CH4 → C2H5
+ + H2
– CH5+ + M → [M+H]+ + CH4
– C2H5+ + M → [M-H]+ + C2H6
– C2H5+ + M → [M+ C2H5]+
7/29/2014
22
The 11th Commandment…
The Second Law of Thermodynamics
For spontaneous processes:
ΔG=ΔH-TΔS < 0
For isolated systems:
ΔS > 0
Of course, we also need a “good” Big Bang,“heavy” atoms (C, N, O…) from first generations stars,
at least second generation stars and compressed dust (planets, rocks), and a lot of time and luck….
UHV Discharge reactorMark Smith’s lab (Tucson/Houston)Low temperature tholins
Tholins : Analog material producedin plasma reactors
Pampre cold plasma reactorNathalie Carrasco’s lab (LATMOS - Versailles)Tholins in levitation
95% N2:5% CH4
with adjustableflow rate
Glass tube to collect tholinsat 195 K
VAC
7/29/2014
23
95% N2:5% CH4
with adjustableflow rate
Vacuum pump
Glass tube to collect tholinsat 195 K
VAC
Ultrahigh vacuum (UHV) plasma generator tosynthesize “tholins” (CxHyNz) in oxygen free environment(Mark Smith’s lab)
The Necessity of Ultrahigh Resolution and MS/MS:
Organic Environment on Saturn’s Moon, Titan
• Somogyi, Á.; Oh, C-H.; Smith, M. A.; Lunine, J. I., J. Am. Soc. Mass Spectrom. 2005, 16, 850-859.
• Sarker, N.; Somogyi, Á.; Lunine, J. I.; Smith, M. A. Astrobiology, 2003, 3, 719-726.
• Neish, C. D.; Somogyi, Á.; Imanaka, H.; Lunine, J. L.; Smith, M. A. Astrobiology, 2008, 8, 273-287.
• Neish, C. D.; Somogyi, Á.; Lunine, J. L.; Smith M. A. "Low temperature hydrolysis of laboratory tholins in ammonia-water solutions: Implications for prebiotic chemistry on Titan" Icarus 2009, 201, 412-421.
• Neish, D.; Somogyi, Á.; Smith, M. A. "Titan's Primordial Soup: Formation of Amino Acids via Low Temperature Hydrolysis of Tholins" Astrobiology2010, 10, 337-347.
• Somogyi, Á.; Vuitton, V.; Thissen, R.; Komáromi, I. “Chemical ionization in the atmosphere? A Model Study on Negatively Charged “Exotic” Ions Generated from Titan’s Tholins by Ultrahigh Resolution MS and MS/MS?” Int. J. Mass Spectrom., 2012, 316-318, 157-163.
The Cassini-Huygens mission is a great success!
7/29/2014
24
ESI
(MA)LDIQCID (eV) MS/MS IRMPD and SORI
MS/M in ICR cell
ESI/APCI
Bruker 9.4 T Apex Qh FT-ICR with a dual source (Tucson,
Thermo LTQ-Orbitrap (Grenoble, France)
HRMS is mandatory for Tholinsanalysis
Early works: Somogyi et al., JASMS 2005
Tholinomics data reduction tools:Pernot et al., Anal. Chem. 2010
7/29/2014
25
FT-ICR of Complex Organic Aggregates (UHVT_001)
99.06649
114.07742
126.07743
141.08831
156.09921
168.09922
181.09448
195.11009
207.11004
222.12071
235.11570
249.15641
259.11514 277.13673
288.14130 301.13655312.14132 341.30364
UHVT_001_ESI_pos_000001.d: +MS
96.88399
114.07766
127.09793
141.08834
155.10399
169.09449
183.11014
195.11020
207.11015
222.12083
234.12064
248.13624
260.13632273.13169
287.14753
300.14296
327.15441 341.17031
UHVT_001_LDI_pos_0_H24_000002.d: +MS0.0
0.5
1.0
1.5
2.0
2.5
8x10Intens.
0.0
0.5
1.0
1.5
2.0
8x10
100 150 200 250 300 350 m/z
Positive Ions: ESI
Positive Ions: LDI
108.03146
119.03627
141.02065
160.03772
185.05814
198.05341
209.03302
224.06911
239.08001 251.08001
265.14795
283.26429
293.17921
306.09696
321.21053 347.12280
UHVT_001_ESI_neg_000001.d: -MS
141.02059
165.02070
192.03152
209.03285
224.06904
233.03311 251.05489
264.07533275.05486 306.09696 318.09726328.10639
345.10840
UHVT_001_LDI_neg_0_I24_000003.d: -MS0.00
0.25
0.50
0.75
1.00
1.25
1.50
9x10Intens.
0
1
2
3
4
9x10
100 150 200 250 300 350 m/z
Negative Ions: ESI
Negative Ions: LDI
Not the same protonated/deprotonated neutral species in +/- modes
7/29/2014
26
Modified van Krevelen diagram for LDI ions
QCID MS/MS spectra of C7HN4
7/29/2014
27
MS/MS fragmentation matrix
C7HN4‐ (141.02067) C6N3
‐ (114.00977)
C2H3N4‐ (83.03632) C3HN4
‐ (93.02067)C3H2N5‐ (108.03157)
C4H2N3‐ (92.02542)
C2N3‐ (66.00978)
‐HCN
7/29/2014
28
CLIO, variable wavelength IRMPD in a FTICR cell (7T Bruker)
• Action spectroscopy of ions in the cell,
« only ions which absorb photons will fragment »Lemaire et al., Phys. Rev. Lett., 2002
Maitre et al., Nucl. Inst. & Meth., 2003
13 June 2013 ASMS ThOE Session - R Thissen 55
CLIO Free Electron Laser
1000 1200 1400 1600 1800 2000 2200
Inte
nsi
ty (
a.u
.)
wavenumber (cm-1)
C:\Tholin_Stuff\from_CLIO\2011-06-22-thissen\PolyCN_Grenoble_ESI_neg_smallmass_newtune_IRMPD_107_000001.d
45.42593
54.00400 71.97536
80.01356
94.40734
107.02566
-MS2(), 73.2-77.1min #(282-297)
0
1
2
3
5x10Intens.
50 60 70 80 90 100 110 m/z
C4H3N4
C3H2N3
Vw IRMPD (FT-ICR) measurements at CLIO (Orsay, France)
7/29/2014
29
Gupta, V.P.; Tandon, P. “Conformational and vibrational studies of isomericHydrogen cyanide tetramers by quantum chemical methods”, Spectrochim. Acta A2012, 89, 55-66
1000 1200 1400 1600 1800 2000 2200
Inte
nsi
ty (
a.u
.)
wavenumber (cm-1)
Good agreement with ourCLIO gas-phase spectrumof the deprotonated HCNtetramer
7/29/2014
30
13 June 2013 ASMS ThOE Session - R Thissen 59
C3H2N5‐ (108.03157) C2N3
‐ (66.00978)
C2N3- (15N)
C2N3- (13C)
Blue-shift due to isotope effect !
(66.00978)
(67.00699)
(67.01324)
C2N3-
1400 1500 1600 1700 1800
Inte
nsi
ty (
a.u
.)
wavenumber (cm-1)
114.077_UA001_ESI_pos_IRMPD_114_000001 72.0554_UA001_ESI_pos_IRMPD_114_000001 85.0508_UA001_ESI_pos_IRMPD_114_000001
1400 1600 1800
Inte
nsity
(a.
u.)
Wavenumber (cm-1)
57.0444_UA001_ESI_pos_IRMPD_114_000001 86.0712_UA001_ESI_pos_IRMPD_114_000001
7/29/2014
31
C3H8N5+ C4H9N4
+
Two positively charged ionsTwo different spectroscopy
Congested spectra, very rich info113,0821114,0773
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72.05544
86.07115
114.07730
+MS2(), 39.6-42.1min #(157-167)
0
2
4
6
5x10Intens.
60 70 80 90 100 110 m/z
72.0554485.05076
113.08206
+MS2(), 35.5-38.0min #(141-151)
0
2
4
6
5x10Intens.
60 70 80 90 100 110 m/z
λ ≈ 1550 cm-1
λ ≈ 1610 cm-1
C4H9N4+
- CH2=NH- H2N-CN
- HCN
113,0821
114,0773
C3H8N5+
HN N
HNHN CH3
H
H
Red arrows indicate possible
protonation sites
C3H7N5C4H8N4
Large scale Quantum chemical calculations are needed
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Neish, C.D., Somogyi, A., Lunine, J.I., and Smith, M.A. (2009) Low temperature hydrolysis of laboratory tholins in ammonia‐water solutions: Implications for prebiotic chemistry on Titan. Icarus 201, 412‐421.
Quantitative kinetic studies to determine hydrolysis rate constants and Arrhenius activation energies in 14% NH3/water
Source of oxygen is water
Oxygen incorporation is fasterand higher in ammonia solutionthan in pure water
Tholin reacts with NH3
Kinetic “growing” curvesat four different temperatures
Arrhenius plot from hydrolysisrate constants
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The distribution of Arrhenius activation energies
Incorporation of oxygen atoms can occur in 3,000-10,000 yearson the surface of Titan
Titan is planet-scale chemical laboratory, with astrobiological relevance
Interpretation of Cassini-Huygens data requests for permanent feedback of information from Physical Chemistry and MS community
Tholins appear as a good analog to study the potential composition of Titan aerosols. High resolution mass spectrometry is mandatory to evaluate their composition
Positive and negative ion spectra are characteristically different indicating more saturated amino/imino compounds (positive mode) and highly unsaturated (CN containing) species with H/C < 1(negative mode)
Chemical formulae can be unambiguously determined but structural isomerism exists
MS/MS with vw IRMPD and theoretical calculations are requiredto determine fine structural details
Studies of new concepts of ion handling and analysis are required for future space exploration
Conclusion
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(The Funny) Conclusions
All we are just dust in the wind…
Come from gas and return to gas
Str
uct
ura
l In
form
atio
n C
on
ten
t
Telescope (the object is there)
Naked eye (cloudless) planet and “intelligent” beings
Optical Spectroscopy (“interesting” atmosphere is there, bulk properties)
Low resolution mass specs in space (blurry individuals are there)
Ultrahigh res mass spec in lab (individuals are there)
Ion spectroscopy /ion mobility in lab (structural isomerism)
Chirality
Non-covalent Aggregation
Polymer formation (covalent “aggregation”)
Self-reproduction
Life????
Intelligent Design???