SEC-MALDI ToF/ToF MS - Waters Corporation · 2016. 6. 1. · MF_GPC_19 #393-544 RT: 16.69-21.15 AV: 76 SB: 1 6.44-6.46 NL: 2.13E7 T: + p ESI Full ms [ 150.00-2000.00] 500 550 600

SEC-MALDI ToF/ToF MS for the Advanced Characterization of Novel

Copolymers

Clemens Schwarzinger, October 2014

2

SEC/ESI-MS Hyphenation

DAD

HPLC

THF

CHCl3

Phenogel columns

5 µm, 4.6 mm

RT: 8.89 - 26.78

9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26Time (min)

0

50000

100000

150000

200000

250000

300000

350000

400000

450000

500000

550000

600000

650000

700000

750000

800000

850000

900000

950000

1000000

1050000

1100000

uAU

NL:1.15E6Channel A UV MF_GPC_19

Pump

ESI-

Mass Spec

MeOH

MF_GPC_19 #393-544 RT: 16.69-21.15 AV: 76 SB: 1 6.44-6.46 NL: 2.13E7T: + p ESI Full ms [ 150.00-2000.00]

500 550 600 650 700 750 800 850 900 950 1000 1050m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

687.13

717.13

673.13731.07

703.13657.13

643.13

747.07

761.07

613.13

629.07775.07

789.07599.20 925.33911.27 955.40581.20941.40 985.27881.33567.27

537.13 803.07 897.40835.20 999.27867.33521.20 559.07 1015.27819.13 1055.201095.13

3

Tetramethylmelamine resin

RN

N

N

N

N N

N

N

N

N

NH Nn

R = H, CH2OH, CH2OCH3

4

R2 = 0.9991

R2 = 0.9964

4.00

4.50

5.00

5.50

6.00

6.50

7.00

7.50

8.00

8.50

9.00

20 22 24 26 28 30 32 34 36

time / min

ln(M

M)

Tetramethylmelamine resin

Endgroups:

-NH

-NCH2OCH3 665 g.mol-1

257 g.mol-1

5

SEC-MALDI ToF MS

© pictures: ms-textbook.com, trendline.co.at

http://www.google.at/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=5D-xzt8xGUGSgM&tbnid=4EFfmyKKlW8JPM:&ved=0CAUQjRw&url=http://schaller.dcb.unibe.ch/protein_index.php?action=menu4&ei=mrCHUYWcMomFtAanzYHQCw&bvm=bv.45960087,d.Yms&psig=AFQjCNEsktFM1RuSoox8S6PmcqDZIYlIXw&ust=1367933376229662http://www.google.at/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=Y-XPhq2Nr7OvXM&tbnid=FZekKILnFuIkuM:&ved=0CAUQjRw&url=http://www.trendline.co.at/montessori006.html&ei=9rCHUZWSJsnGswaP_4CIAg&bvm=bv.45960087,d.Yms&psig=AFQjCNEzKqAlmY1cS7hNYGL3EWCqCyq9jg&ust=1367933537953170http://www.google.at/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=UuTquxh4rToMHM&tbnid=yX1HqUUYkFFanM:&ved=0CAUQjRw&url=http://www.ms-textbook.com/2nd/home/instructors.html&ei=9LSHUciJOo6Hswbcw4DgBw&psig=AFQjCNGycWuu765ImPJzPkEyGo1yJD12ow&ust=1367934558165027

6

Poly-APMM

-1

0

1

2

3

4

5

6

4 5 6 7 8 9 10 11 12 13 14retention volume / ml

inte

nsity

F1F2F3F4F5F6F7F8F9F10F11F12F13F14APMM

N

NN

NN

N

7

Poly-APMM

0.0

0.5

1.0

1.5

2.0

2.5

4x10

Inte

ns.[

a.u.

]

2000 3000 4000 5000 6000 7000 8000 9000m/z

0

1

2

3

4x10

Inte

ns.[

a.u

.]

1000 2000 3000 4000 5000 6000m/z

0

2000

4000

6000Inte

ns.[

a.u

.]

2000 4000 6000 8000 10000 12000 14000m/z

0

1000

2000

3000

Inte

ns.

[a.u

.]

5000 7500 10000 12500 15000 17500 20000 22500 25000 27500 30000m/z

F14 F13

F12 F11

8

Poly-APMM

3.0

3.5

4.0

4.5

7.8 8.0 8.2 8.4 8.6 8.8 9.0 9.2 9.4

retention volume / ml

lnM

F14

F13

F12

F11

SECfraction molar mass

F11 12.500

F12 7.600

F13 4.480

F14 2.300

Calibration for SEC

9

SEC-online-MALDI ToF MS

split

10


11


12

PEG 600 and 1500

13

PEG 600 and 1500

1538.102

1626.172

1450.0331670.206

1406.000

1714.241

1361.967

1758.275

1802.3101317.936

1846.3451273.900

1890.3801229.866

1934.4161185.834

1802.310

1846.345

1818.284

Resolution: 25000

14

Polystyrene 2430

mass spectrometry chromatography

15

Polyester Possible structures:

HO-R-OH

HO-R-COOH

HOOC-R-COOH

cyclic

O O

O

O

OOH

H

Phthalic anhydride + diethylene glycol

16

Polyester

17

Polyester

18

Polyester

HO-R-OH HO-R-COOH

19

Styrene-Vinylmelamine-Copolymer

N

N

N

N

NNToluene

N N CNNC

NC

R

N

N N

N N

N

+

20


2000 3000 4000 5000 6000 7000 8000 9000 10000 1000

21

Styrene-Vinylmelamine-Copolymer 2050.617

2155.142

2222.804 2259.359 2272.668

2168.819

2118.6002064.389

2014.704

2235.825

2132.726

2027.927

2286.9842183.398

2078.738

2300.9132196.468

2091.329

* PSVPMM_20130524\0_E21\1\1Lin, Smoothed, "Baseline subt."

IBN-S18-H IBN-S18-M-H IBN-S16-M2-H IBN-S14-M3-H IBN-S17-IBN IBN-S17-M-IBN

22

* PSVPMM_20130524\0_K24\1\1Lin Raw

4500-7500

* PSVPMM_20130524\0_E21\1\1Lin, "Baseline subt."

1500-4500


* PSVPMM_20130524\0_I11\1\1Lin Raw

3000-6000

23


198.693

421.185

595.487

1545.008

814.730919.074697.531

1129.423

1961.598

5243.855

2481.8572586.308

2899.5233107.039 3419.924

* PSVPMM_20130524\0_I21\1\5552.5588.LIFT\1SRef

MS/MS of m/z=5552.6

24


197.360

279.266

419.480

487.554

117.140

3053.017

3171.129

3192.799

606.668

813.011

3156.223

708.834

1645.9591023.2221437.792

1335.555

3148.686

1854.837

PSVPMM_20130524\0_I1\1\3313.0459.LIFT\1SRef

MS/MS of m/z=3313.1

25

Summary and Outlook

SEC/MS allows “deeper insight” into polymer structure

especially suitable for lower molar mass polymers

limitation is ionization of polymers

Application to complex copolymers and mixtures

26

* PMMV-MMA\0_C4\1\1SRef Raw




* PMMV-MMA\0_E21\1\1SRef Raw

* PMMV-MMA\0_F16\1\1SRef Raw



* PMMV-MMA\0_G1\1\1SRef Raw

* PMMV-MMA\0_J1\1\1SRef Raw





600 4000 m/z

MMA-Vinylmelamine-Copolymer

27


1200 2500 m/z


28

1726.000

1804.010

1757.029

1737.011

1748.042

1781.065

1793.032

1771.002 1815.061

* PMMV-MMA\0_F11\1\1SRef

1720 1820 m/z


29

Acknowledgement

Dr Herbert Gabriel

DI Stefan Gabriel

DI Michael Heschik

Leila Maringer

Karl Schütz

Slide Number 1SEC/ESI-MS HyphenationTetramethylmelamine resinTetramethylmelamine resinSEC-MALDI ToF MSPoly-APMMPoly-APMMPoly-APMMSEC-online-MALDI ToF MSSEC-online-MALDI ToF MSSEC-online-MALDI ToF MSPEG 600 and 1500PEG 600 and 1500Polystyrene 2430PolyesterPolyesterPolyesterPolyesterStyrene-Vinylmelamine-CopolymerStyrene-Vinylmelamine-CopolymerStyrene-Vinylmelamine-CopolymerStyrene-Vinylmelamine-CopolymerStyrene-Vinylmelamine-CopolymerStyrene-Vinylmelamine-CopolymerSummary and OutlookMMA-Vinylmelamine-CopolymerMMA-Vinylmelamine-CopolymerMMA-Vinylmelamine-CopolymerAcknowledgement

SEC-MALDI ToF/ToF MS - Waters Corporation · 2016. 6. 1. · MF_GPC_19 #393-544 RT: 16.69-21.15 AV: 76 SB: 1 6.44-6.46 NL: 2.13E7 T: + p ESI Full ms [ 150.00-2000.00] 500 550 600

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