Tandem mass spectrometry of incompletely and fully condensed POSS – folding and unfolding routes
38
Tandem mass spectrometry of incompletely and fully condensed POSS – folding and unfolding routes. Thierry Fouquet, Laurence Charles, David Ruch
Transcript of Tandem mass spectrometry of incompletely and fully condensed POSS – folding and unfolding routes
Tandem mass spectrometry of
incompletely and fully condensed POSS – folding and unfolding routes.
Thierry Fouquet, Laurence Charles, David Ruch
Polyhedral oligomeric silsesquioxanes POSS
August 25, 2014 MS/MS of POSS: folding and unfolding
Alternative to nanoparticles
- Mechanical reinforcement
- Composites
- Support for catalysts
- Electronics…
Octagonal structure
R. Bakhtiar, F. J. Feher. Rapid Commun. Mass Spectrom. 1999, 13, 687.
D. P. Fasce, R. J. J. Williams, R. Erra-Balsells, Y. Ishikawa, H. Nonami. Macromolecules 2001, 34, 3534.
R. J. J. Williams, R. Erra-Balsells, Y. Ishikawa, H. Nonami, A. N.Mauri, C. C. Riccardi. Chem. Phys. 2001, 202, 2425.
H. Chen, R. E. Tecklenburg. J. Am. Soc. Mass Spectrom. 2006, 17, 1437.
W. Zhang, R. Yang. J. Appl. Polym. Sci. 2011, 122, 3383.
H. Araki, K. Naka. Polym. J. 2012, 44, 340.
V. Ervithayasuporn, S. Chimjarn. Inorg. Chem. 2013, 52, 13108.
In MS:
Polyhedral oligomeric silsesquioxanes POSS
August 25, 2014 3
Alternative to nanoparticles
- Mechanical reinforcement
- Composites
- Support for catalysts
- Electronics…
Octagonal structure
J. De Winter, A. L. Goffin, O. Coulembier, P. Dubois, R. Flammang, P. Gerbaux. Eur. J. Mass Spectrom. 2009, 15, 431.
In MS/MS:
MS/MS of POSS: folding and unfolding [email protected]
Polyhedral oligomeric silsesquioxanes POSS
Synthesis: condensation of RSi(OX)3
August 25, 2014 4
Incompletely
condensed
Fully
condensed
MS/MS of POSS: folding and unfolding [email protected]
Polyhedral oligomeric silsesquioxanes POSS
Synthesis: condensation of RSi(OX)3
August 25, 2014 5
Fully
condensed
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 6
m/z 863
m/z 845
m/z 827
m/z 809
Fully condensed POSS propylamine POSS
Dehydration
- H2O
- H2O
- H2O
- H2O
O
Si
O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
O
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NH2
m/z 881
H+
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 7
Dehydration
- H2O
- H2O
- H2O
- H2O
Unfolding
Fully condensed POSS propylamine POSS
MS/MS of POSS: folding and unfolding [email protected]
POSS ↔ PDMS
August 25, 2014 8
O
Si
O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
O
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NHSi OO
NHSi
+H
7
Dehydration Si OO
X
Y
Si+
X
Y
POSS
polysiloxane
Generic fragmentation route of a PDMS ammonium adduct :
D3 (D4, D5)
T. Fouquet, S. Humbel and L. Charles Journal of the American Society for Mass Spectrometry 2011, 22 (4), 649-658.
Unfolding
MS/MS of POSS: folding and unfolding [email protected]
POSS ↔ PDMS
August 25, 2014 9
O
Si
O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
O
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NHSi OO
NHSi
+H
7
Dehydration
POSS
NHSi OO
NHSi
+H
4
NHSi
O
O
NHSi
O
NH
Si
Generic fragmentation route of a PDMS ammonium adduct :
D3 (D4, D5)
MS/MS of POSS: folding and unfolding [email protected]
POSS ↔ PDMS
August 25, 2014 10
O
Si
O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
O
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NHSi OO
NHSi
+H
7
Dehydration
POSS
NHSi OO
NHSi
+H
4
NHSi
O
O
NHSi
O
NH
Si
n=2
n=3 n=4 NH
Si
O
O
NHSi
O
NH
Si
D3
MS/MS of POSS: folding and unfolding [email protected]
POSS ↔ PDMS
August 25, 2014 11
O
Si
O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
O
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NHSi OO
NHSi
+H
7
Dehydration
POSS
NHSi OO
NHSi
+H
4
NHSi
O
O
NHSi
O
NH
Si
n=2
n=3 n=4
NH
Si
O
O
NHSi
O
NH
Si
O
NHSi
D4
MS/MS of POSS: folding and unfolding [email protected]
POSS ↔ PDMS
August 25, 2014 12
O
Si
O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
O
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NHSi OO
NHSi
+H
7
Dehydration
POSS
NHSi OO
NHSi
+H
4
NHSi
O
O
NHSi
O
NH
Si
n=2
n=3 n=4
NH
Si
O
O
NHSi
O
NH
Si
ONH
Si
O
NH Si
D5
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 14
Fully condensed POSS Q8M8
Cage unfolding (Charge remote process) Random
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 15
Fully condensed POSS Q8M8
Cage unfolding (Charge remote process) Random
Alternative route
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 16
Fully condensed POSS Q8M8
Cage unfolding (Charge remote process) Si O
O O
Si
Si O
O O
Si
Si
O
Si
Random copolymer
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 17
Fully condensed POSS Q8M8
Si O
O O
Si
Si O
O O
Si
Si
O
SiSi-O cleavage
TMS loss
T. Fouquet, S. Humbel and L. Charles Journal of the American Society for Mass Spectrometry 2011, 22 (4), 649-658.
MS/MS of POSS: folding and unfolding [email protected]
What about incompletely condensed POSS ?
August 25, 2014 18
Incompletely
condensed
MS/MS of POSS: folding and unfolding [email protected]
Diol and triol: condensation
- NH3 - H2O - H2O - NH3 - H2O - isobutane
Diol and triol: butene evaporation
- 7* isobutene- 7* isobutene
- 7* isobutene
Diol and triol: butene evaporation
August 25, 2014 22
Capping of hydroxy groups by iBuMe2SiCl
iBu
iBu
iBu
O
Si
O
Si
OH
OHSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
Si CliBu
Triethylamine
iBu
iBu
iBu
O
Si
O
Si
O
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si
iBu
Si iBu
iBu
iBu
iBuiBu
O
Si
O OH
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
iBu
iBu
iBuiBu
O
Si
O O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si iBu
Si CliBu
Triethylamine
An attempt to make the unfolding possible…
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 23
Capping of hydroxy groups by iBuMe2SiCl
iBu
iBu
iBu
O
Si
O
Si
OH
OHSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
Si CliBu
Triethylamine
iBu
iBu
iBu
O
Si
O
Si
O
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si
iBu
Si iBu
iBu
iBu
iBuiBu
O
Si
O OH
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
iBu
iBu
iBuiBu
O
Si
O O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si iBu
Si CliBu
Triethylamine
An attempt to make the unfolding possible…
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 24
Capping of hydroxy groups by iBuMe2SiCl
iBu
iBu
iBu
O
Si
O
Si
OH
OHSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
Si CliBu
Triethylamine
iBu
iBu
iBu
O
Si
O
Si
O
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si
iBu
Si iBu
iBu
iBu
iBuiBu
O
Si
O OH
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
iBu
iBu
iBuiBu
O
Si
O O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si iBu
Si CliBu
Triethylamine
An attempt to make the unfolding possible…
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 25
Capping of hydroxy groups by iBuMe2SiCl
iBu
iBu
iBu
O
Si
O
Si
OH
OHSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
Si CliBu
Triethylamine
iBu
iBu
iBu
O
Si
O
Si
O
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si
iBu
Si iBu
iBu
iBu
iBuiBu
O
Si
O OH
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
iBu
iBu
iBuiBu
O
Si
O O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si iBu
Si CliBu
Triethylamine
An attempt to make the unfolding possible…
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 26
Capping of hydroxy groups by iBuMe2SiCl
iBu
iBu
iBu
O
Si
O
Si
OH
OHSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
Si CliBu
Triethylamine
iBu
iBu
iBu
O
Si
O
Si
O
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si
iBu
Si iBu
Four cycles
Two « long » arms
iBu
iBu
iBuiBu
O
Si
O OH
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
iBu
iBu
iBuiBu
O
Si
O O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si iBu
Si CliBu
Triethylamine
An attempt to make the unfolding possible…
MS/MS of POSS: folding and unfolding [email protected]
An attempt to make the unfolding possible…
August 25, 2014 27
Capping of hydroxy groups by iBuMe2SiCl
iBu
iBu
iBu
O
Si
O
Si
OH
OHSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
Si CliBu
Triethylamine
iBu
iBu
iBu
O
Si
O
Si
O
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si
iBu
Si iBu
Three cycles
Three « long » arms
iBu
iBu
iBuiBu
O
Si
O OH
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
OH
iBu
iBu
iBuiBu
O
Si
O O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
iBu
iBu
iBuiBu
O
Si iBu
Si iBu
Si CliBu
Triethylamine
Four cycles
Two « long » arms
MS/MS of POSS: folding and unfolding [email protected]
… And a failure.
August 25, 2014 29
Si OO
R
Si+
R
SiR
R=iBu, Me, H
MS/MS of POSS: folding and unfolding [email protected]
… And a failure.
August 25, 2014 30
Si OO
R
Si+
R
SiR
R=iBu, Me, H
Butene / Propene loss
T. Fouquet, L. Charles, David Ruch Rapid Communication in Mass Spectrometry 2014, 28, 1849-1852.
MS/MS of POSS: folding and unfolding [email protected]
-OH termination: deprotonation for negative ESI
A digression: negative MS/MS
August 25, 2014 31
T. Fouquet, C. Barrère, L. Charles, D. Ruch, unpublished results.
Deprotonation
Formate adduction
MS/MS of POSS: folding and unfolding [email protected]
A digression: negative MS/MS
August 25, 2014 32
-OH termination: deprotonation for negative ESI
T. Fouquet, C. Barrère, L. Charles, D. Ruch, unpublished results.
MS/MS of POSS: folding and unfolding [email protected]
August 25, 2014 33
A digression: negative MS/MS
MS/MS of POSS: folding and unfolding [email protected]
Perspectives and future work
August 25, 2014 34
T. Fouquet, S. Humbel and L. Charles Journal of the American Society for Mass Spectrometry 2011, 22 (4), 649-658.
T. Fouquet, S. Humbel and L. Charles International Journal of Mass Spectrometry 2011, 306, 70-76.
T. Fouquet, J. Petersen, J.A.S. Bomfim, F. Ziarelli, J. Bour, D. Ruch and L. Charles International Journal of Mass Spectrometry 2012, 313, 58-67.
T. Fouquet, J. Bour, V. Toniazzo, D. Ruch and L. Charles Rapid Communication in Mass Spectrometry 2012, 26. 2057-2067.
T. Fouquet, C. Chendo, V. Toniazzo, D. Ruch and L. Charles Rapid Communications in Mass Spectrometry 2013, 27, 88-96.
T. Fouquet, J. Petersen, F. Ziarelli, J. Bour, V. Toniazzo, D. Ruch and L. Charles Cover Article, Plasma processes and polymers 2013, 10, 271-284.
T. Fouquet, V. Toniazzo, D. Ruch and L. Charles Journal of the American Society for Mass Spectrometry 2013, 24, 1123-1129.
Young Scientist Feature International Journal of Mass Spectrometry
O Si
X Y3+z+
MS/MS of POSS: folding and unfolding [email protected]
Perspectives and future work
August 25, 2014 35
T. Fouquet, T.N.T. Phan and L. Charles Rapid Communications in Mass Spectrometry 2012, 26, 765.
T. Fouquet, L. Charles, David Ruch Rapid Communication in Mass Spectrometry 2014, 28, 1849-1852.
…
X
X
OH
Si
OOH
Si
O
Si OH
OH
SiOHO
SiO
O
X
XX
X
X
X
O
Si
O
Si
OH
OHSi
O
Si O
Si
O
SiOO
SiO
O
X
X
XX
OH
X
iBu
XX
O
Si
O OH
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
X
X
XX
OH
X
X
XX
O
Si
O
Si
OSi
OSi
O
Si O
Si
O
SiOO
SiO
O
X
X
XX
O
Y3+z+
Y3+z+
Y3+z+ Y
3+z+
MS/MS of POSS: folding and unfolding [email protected]
Perspectives and future work
August 25, 2014 36
J. Daum, G. Ergodi, J.P. Kennedy, Journal of Polymer Science: Part A: Polymer Chemistry 2006, 44, 4039–4052.
Y. Tada, H. Yoshida, Y. Ishida, T. Hirai, J. K. Bosworth, E. Dobisz, R. Ruiz, M. Takenaka, T. Hayakawa, H. Hasegawa, Macromolecules 2012, 45, 292-304.
« Comb-like » polymers POSS as side-group
CLP and eCLP Cyclolinear polysiloxanes and extended cyclolinear polysiloxanes POSS within the chain
MS/MS of POSS: folding and unfolding [email protected]
The personal column: classified ads
Poster
"TOF-SIMS / MALDI-TOF combination for the molecular
weight depth profiling of a polymeric bilayer“
Session: MPS02 - Synthetic Macromolecules
Date: 25/08/2014
Time: 11:00-15:00
Looking for new job opportunities
August 25, 2014 37 MS/MS of POSS: folding and unfolding
Special Thanks
Pr Laurence Charles, Aix-Marseille University
(+ Congrats on speakers of this Macromolecules session)
Thank you for your attention
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