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6/10/2011
1
Tandem Mass Spectrometry of Synthetic Polymers
Árpád Somogyi
Department of Chemistry and BiochemistryUniversity of Arizona
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)
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2
Molecular weight distribution defines polydispersit y 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 al., unpublished)
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!)
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3
http://www.polymerprocessing.com/polymers/alpha.htm l
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
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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
(da
lto
n)
m / z
c
[Ala 5+H]+
[Ala 50+H]+
exact mass
average mass
C15H28O6N5
C150H253O51N50
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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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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 ea rly 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 bas ic studies such as comparison of different activation methods are emerging
Survival yield curveM/(M+ΣF)
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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Results for PEGsMemboeuf, IMMS 2009 (Retz)
Anal. Chem. 82 2294 (2010)
very good linear relationship
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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
812
12 eV
817
12 eV
817
30 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
6/10/2011
9
817.308
328.705 492.776186.682 657.011120.738 284.652 354.682 544.397443.72066.510 240.848
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
679.028310.689 456.55290.823 354.682 544.397208.735 400.629248.685
0
1000
2000
3000
4000
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.
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Practical importances of phenanthrolinePractical importances of phenanthroline--functional ized PEGsfunctionalized PEGs
� stabilization of magnetic nanoparticles(e.g. Fe3O4)
�hydrofilic networks by complex formation
KékiKéki, , S.; S.; KukiKuki, , ÁÁ.. KukiKuki;; Nagy, Nagy, M.; M.; Nagy, L.; Nagy, L.; ZsugaZsuga, M., M.JASMSJASMS, 2010, , 2010, 2121, 1561, 1561--1564.1564.
Change of Change of the the absorbance at 515 nm absorbance at 515 nm versus versus molar ratio of the added molar ratio of the added Fe(II)Fe(II)--ions and phenanthroline functions of ions and phenanthroline functions of PEGsPEGs
0
0.2
0.4
0.6
0.8
1
1.2
350 450 550 650
λλλλ (nm)
Abs
orba
nce
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]
Abs
orba
nce
(515
nm
)
▲εεεε≈10300 M-1cm-1♦εεεε≈11090 M-1cm-1
Fe2+ : PEG_phen = 1: 3
Fe2+ : phen_PEG_phen = 2: 3
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Synthesis of phenanthrolineSynthesis of phenanthroline--functionalized PEGsfunctionalized 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)
ESIESI--MS spectrum of Fe(PEG_phen)MS spectrum of Fe(PEG_phen) 332+2+
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
FeLFeL332+2+
[FeL[FeL 33+NH+NH44]]3+3+
[FeL[FeL 33+2NH+2NH44]]4+4+
[FeL[FeL 33+2NH+2NH44+Na]+Na]5+5+
[FeL[FeL 33+3NH+3NH44+Na]+Na]6+6+
L = PEG_phenL = PEG_phen
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12
ESIESI--MS intensity distribution of PEG_phen and Fe(P EG_phen)MS intensity distribution of PEG_phen and Fe(PEG_ph en)332+2+
+Fe(II)+Fe(II)
Fe2+ + L i + L j + Lk FeL i+j+k2+ (n=i+j+k)
Theoretical model: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
babi
lity
0.0
0.2
0.4
0.6
0.8
1.0
60 80 100 120
number of EO unitsN
orm
aliz
ed in
tens
ity
measured
simulated
kj
kjiin PPPP ∑
∞
==
1,,
ESIESI--MS/MS of Fe(PEG_phen)MS/MS of Fe(PEG_phen) 332+2+
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
norm
alze
d in
tens
ity
80 V
90 V
simulated
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16
Very 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 Qua ntify 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 Char acterization of Poly(Butylene
Adipate-co-Butylene Terephtalate) Copolyester” JASMS, 2011, 22, 641-648.
Fouquet, T.; Humbel, S.; Charles, L. “Tandem Mass S pectrometry of Trimethylsilyl-TerminatedPoly(Dimethylsiloxane) Ammonium Adducts Generated b y Electrospray Ionization”
JASMS, 2011, 22, 649-658.
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