MASS SPECTROMETRY IN POLYMER CHEMISTRY A sneak peak of research activities National Institute of Advanced Industrial Science and Technology (AIST) Feb 2nd 2015
A LITTLE BIT OF GEOGRAPHY
A LITTLE BIT OF GEOGRAPHY
A LITTLE BIT OF GEOGRAPHY
(Grand Duchy of) Luxembourg Constitutional Monarchy (Grand Duke Henri) Three official languages: French, German and Luxembourgish
Pop. 550,000 hab (2014) Industrial sector (steel) until the ‘60 Financial sector Since 2000: Scientific research CEPS/INSTEAD (Social & Economics) CRP Gabriel Lippmann CRP Henri Tudor CRP Santé National Health Laboratory (LNS) The University of Luxembourg
Hautcharage
BIOGRAPHICAL SKETCH Thierry Fouquet • 27 years old, French
• 2006 - 2009 Centrale Marseille Engineering School, class 2009 • 2008 - 2009 Master degree, Aix-Marseille university (first class honors) • 2009 - 2012 PhD, Aix-Marseille University + Public Research Centre Tudor (Summa cum laude) • 2013 - 2015 Luxembourg Institute of Science and Technology, Post-doc (R&D Engineer)
MASS SPECTROMETRY • Mass Spectrometry [mæs spɛk’trɒmɛtri] (noun, uncountable) (physics, analytical chemistry) An analytical technique that measures the mass-to-charge ratio of the ions formed when a molecule or atom is ionized, vaporized and introduced into a vacuum. Mass spectrometry may also involve breaking molecules into fragments thus enabling its structure to be determined. Sector Time-of-Flight (TOF) Quadrupole Ion trap Fourier transform ion cyclotron resonance (FT-ICR)
Ion source
Mass Analyzer
Detector Processing to mass spectra
Electron Impact (EI) Chemical Ionization (CI) Electrospray Ionization (ESI) Matrix-assisted Laser Desoprtion Ionization (MALDI) Secondary Ion Mass Spectrometry (SIMS)
Intensity
Sample introduction
m/z
TANDEM MASS SPECTROMETRY
Product ion scan
Intensity
• Tandem mass spectrometry, also known as MS/MS or MS2, involves multiple steps of mass spectrometry selection, with some form of fragmentation occurring in between the stages.
m/z
Sample introduction
Mass Analyzer
« Activation »
Collision induced Dissociation (CID) Infrared Multiphoton Dissociation (IRMPD) Electron Capture or Transfer Dissociation (ECD/ETD)
Mass Analyzer
Detector
Product ions
Intensity
Ion source
Precursor ion
m/z
ELECTROSPRAY IONIZATION
MATRIX ASSISTED LASED DESORPTION IONIZATION
OUTLINE • Spring 2009 - Summer 2009 (Master degree) •
Kinetic method for mono- and disaccharides isomeric distinction
• Fall 2009 - Fall 2012 (PhD) •
ESI-MS(/MS)
MS/MS of PDMS and silicon-based plasma polymers
ESI-MS(/MS)
OUTLINE • Spring 2009 - Summer 2009 (Master degree) •
Kinetic method for mono- and disaccharides isomeric distinction
• Fall 2009 - Fall 2012 (PhD) •
MS/MS of PDMS and silicon-based plasma polymers
• Winter 2013 - Summer 2014 (R&D engineer, post-doc) • • •
Depth Profiling MS of plasma polymers MS of PDMS
MALDI-MS SALDI-MS + SEC-MALDI-MS ASAP-MS
OUTLINE • Spring 2009 - Summer 2009 (Master degree) •
Kinetic method for mono- and disaccharides isomeric distinction
• Fall 2009 - Fall 2012 (PhD) •
MS/MS of PDMS and silicon-based plasma polymers
• Winter 2013 - Summer 2014 (R&D engineer, post-doc) • • •
Depth Profiling MS of plasma polymers MS of PDMS
• Summer 2014 - Winter 2015 (R&D engineer, post-doc) •
Cardanol chemistry
MALDI-MS + SEC-MALDI-MS
SPRING 2009 - SUMMER 2009 Master internship Quantitation of Sugar Isomers in Ternary mixtures Using the Kinetic Method Aix-Marseille University, France Pr L. Charles (
[email protected]) Pr S. Humbel (
[email protected]) “Distinction & quantitation of sugar isomers in ternary mixtures using the kinetic method” T. Fouquet, L. Charles, J. Am. Soc. Mass Spectrom. 2010, 21, 60. “Isomeric distinction of small oligosaccharides: bottom-up approach using the kinetic method” M. Major, T. Fouquet, L. Charles, J. Am. Soc. Mass Spectrom. 2011, 22, 1252.
Spring (South East France)
Summer (South East France)
FALL 2009 - FALL 2012 PhD dissertation Mass spectrometry of synthetic polysiloxanes: from linear models to plasma polymers networks Aix-Marseille University, France Pr L. Charles (
[email protected]) Public Research Centre Henri Tudor, Luxembourg Dr D. Ruch (
[email protected])
Fall (South East France)
Fall (Moselle river, Luxembourg)
FALL 2009 - FALL 2012 PhD dissertation • Excerpt from: EUPA 2013 Scientific meeting, Oct. 14-17, 2013, Saint Malo, France. French Society for Mass Spectrometry Best PhD thesis Prize 2013
BASIC RESEARCH VS. DAILY LIFE
Basic Research Low Molecular Weight Polymers
Real Life
Soluble
High Molecular Weight Polymers
Well - defined Linear backbone
Insoluble partly soluble
Known End-groups
Unknown Structures Branched Cross-linked
A Perfect World « Nobody’s Perfect »
BASIC RESEARCH VS. DAILY LIFE MS/MS of poly(siloxanes) Basic Research Low Molecular Weight Polymers
Real Life
Soluble
High Molecular Weight Polymers
Well - defined
Insoluble partly soluble
Linear backbone Known End-groups
Unknown Structures
a
Si O
Branched Cross-linked
w n
... Fragmentation routes
Si O
...
MS/MS RULES FOR SALE y « Generic » Fragmentation Pathway • Positive Mode • Ammonium Adduction • (a,w) End-groups
MS/MS RULES FOR SALE « Generic » Fragmentation Pathway • Positive Mode • Ammonium Adduction • (a,w) End-groups
CID
bi+3+
MS/MS RULES FOR SALE y « Generic » Fragmentation Pathway • Positive Mode • Ammonium Adduction • (a,w) End-groups
CID
bi+3+
CID
zj+3+
T. Fouquet, ChemistryOpen 2014, 3, 269.
MS/MS RULES FOR SALE y « Generic » Fragmentation Pathway • Positive Mode • Ammonium Adduction • (a,w) End-groups
CID
MS3
CID
bi+3+
bi +
zj+3+
zj +
T. Fouquet, ChemistryOpen 2014, 3, 269.
MS/MS RULES FOR SALE y « Generic » Fragmentation Pathway • Positive Mode • Ammonium Adduction • (Trimethylsilyl, Hydroxy) End-groups
a
z4+
Si
OH
CID
w
CID
b 3+ b 2+
Si O Si OH z5+
b 4+
n
bi+3+
zj+3+
z6+
bi +
zj +
T. Fouquet, ChemistryOpen 2014, 3, 269.
MS/MS RULES FOR SALE y « Generic » Fragmentation Pathway • Positive Mode • Ammonium Adduction • (Trimethylsilyl, Methyl) End-groups
a
b 2+ b 3+ b4+
Si
CH3
CID
w (=a) Si O Si CH3 n
bi+3+
bi + T. Fouquet, ChemistryOpen 2014, 3, 269. T. Fouquet, S. Humbel, L. Charles, J. Am. Soc. Mass Spectrom. 2011, 22, 649.
MS/MS RULES FOR SALE y « Generic » Fragmentation Pathway • Positive Mode • Ammonium Adduction • (Trimethylsilyl, Methyl) End-groups
Si
CH3
CID
b 2+ b 3+ b4+
Waterloo ! Waterloo ! Waterloo ! Gloomy plain !
bi+3+
bi +
MS/MS RULES FOR SALE y « Generic » Fragmentation Pathway • Positive Mode • Ammonium Adduction • (Trimethylsilyl, Methyl) End-groups
Si
CH3
CID
b 2+ b 3+
Large Ions
b4+
bi+3+ Dissociated ? Consecutive Dissociations
Not produced ?
Small Ions
bi+
MS/MS RULES FOR SALE y « Generic » Fragmentation Pathway • Positive Mode • Ammonium Adduction • (Trimethylsilyl, Methyl) End-groups
Si
CH3
b 2+
Large Neutral
b 3+ b4+ Dissociated ?
Not produced ?
bi+
Small Ions
MS/MS RULES FOR SALE How to take a closer look ?
MS/MS RULES FOR SALE How to take a closer look ? CID +1
+1
+
Neutral Loss
+1
MS/MS RULES FOR SALE How to take a closer look ? CID +1
+1
+
Neutral Loss
+1
+2
+2
MS/MS RULES FOR SALE « Two is better than one » CID +1
+1
+
Neutral Loss
+2
+2
+
+1
+
Neutral Loss
CID +1
Charge Separation
Wu et al, 2006
+1
+2
+2
JL. Wu, D.Q.Liu, Rapid Commun. Mass Spectrom. 2006, 21, 455.
MS/MS RULES FOR SALE « Two is better than one »
+1
Fouquet et al, 2013
+2
T. Fouquet, V. Toniazzo, D. Ruch, L. Charles, J. Am. Soc. Mass Spectrom. 2013, 24, 1123.
MS/MS RULES FOR SALE
<
« Two is better than one »
< Charge Separation
<
→ Large monohydroxy PDMS « neutrals » → Small bi+ ions directly produced
MS/MS RULES FOR SALE « Two is better than one »
<
Neutral Loss
< <
<
→ Large bi+ ions also produced
MS/MS RULES FOR SALE More Precisely CID of doubly charged PDMS
small bi+ (large neutral) Fragmentation pathways of singly charged PDMS
large bi+ (small neutral) & consecutive monomer evaporation
< <
REAL LIFE ISSUES Application of the fragmentation rules
§ Silicon in Petroleum Products
Chainet et al, 2012
§ Speciation
§ High Molecular Weight Industrial Silicones
Fouquet et al, 2015
§ Analysis with non conventional ionization sources (ASAP)
F. Chainet, J. Ponthus, C.P. Lienemann, M. Courtiade, O.F.X. Donard, Anal. Chem. 2012, 84, 3998. T Fouquet, C Barrère-Mangote, M Farenc, C Afonso, P Giusti. Rapid Commun. Mass Spectrom. 2015, under review.
REAL LIFE ISSUES Plasma-Polymerization
Tendero et al, 2003
Plasma used as an active medium § « More or less ionized gas » § Formed of electrons, ions, radicals & neutrals
« Plasma discharge » Electrode El
Discharge Dis
El Electrode
Kogelschatz, 2003
U. Kogelschatz, Plasma Chemistry and Plasma Processing 2003, 23, 1. C. Tendero, C. Tixier, P. Tristant, J. Desmaison, P. Leprince, Spectrochimica Acta Part B 2006, 61, 2.
REAL LIFE ISSUES Plasma-Polymers
Biederman et al, 2004
Plasma-polymerization (portmanteau word) Electrode El
D4 Si
O
Si
Electron Impact
Injection of precursor
Dissociations UV photodissociation
O
O Si
O
Recombinations
Si
Oxydation El Electrode
H. Biederman, Plasma Polymer Films, 2004, Imperial College Press, Covent Garden, UK.
REAL LIFE ISSUES Si
Silicon plasma polymers
O
HO Si Si
O
Si
O
Si
O
Si O
Si O HO
Si
O Si
Si HO
Si Si
O O
O
O
Si
O Si
O
O Si
Si
O
Si
O
Si
O
Si
O Si
Highly branched & cross-linked
Highly insoluble
Si
Si
Injection of precursor
Silicon-based Plasma-polymer
O
O Si
O
Silica ?
El Electrode
D4 O
PDMS ?
Si
El Electrode J. Bour, L. Charles, J. Petersen, M. Michel, J. Bardon, D. Ruch, Plasma Processes & Polymers 2010, 7, 687. J. Petersen, R. Bechara, J. Bardon, T. Fouquet, F. Ziarelli, L. Daheron, V. Ball, V. Toniazzo, M. Michel, A. Dinia, D. Ruch. Plasma Processes & Polymers 2011, 8 , 895.
PLASMA POLYMERS Structural elucidation Insoluble part Si
O
O
Si O
Si
O
D4
Si
ppD4 Soluble part
PLASMA POLYMERS Structural elucidation Insoluble part Si
O
Si
O
ppD4
O Si
Si
O
Soluble part
E ESI-MS
D4
Hypothetic copolymer-like structure (MS results) 282 Da 282 Da
74 Da 74 Da 74 Da The « How and Why » of a cyclic precursor
74 Da
282 Da
282 Da
Denis et al, 2010 Ward et al, 2003
L. Denis, P. Marsal, Y. Olivier, T. Godfroid, R. Lazzaroni, M. Hecq, J. Cornil, R. Snyders, Plasma Process Polym 2010, 7, 172. L.J. Ward, W.C.E. Schofield, J.P.S. Badyal, ACS Langmuir 2003, 19, 6.
PLASMA POLYMERS Mimic by wet chemistry
Wet synthesis of reference compounds to mimic a co-oligomeric distribution (n=1)
Fouquet et al, 2012
Hydroxy-ended PDMS
282 Da
74 Da
n n=1
T. Fouquet, J. Petersen, J.A.S Bomfim, F. Ziarelli, J. Bour, D. Ruch, L. Charles, Int J Mass Spectrom 2012, 313, 58.
PLASMA POLYMERS Mimic by wet chemistry ESISI MS MS/MS m=7 =7 Evaporation of D3 neutrals to form small bi+ ions
b2+
b1+ a+
bx+ b3+
O Si Si O O Si O Si O Si O Si O Si O Si O Si O Si O Si O Si O O Si Si O
a+
+
NH4
PLASMA POLYMERS When the fragmentation routes knowledge helps
Evaporation of D3 neutrals to form small bi+ ions
b2+
b1+ a+
bx+ b3+
O Si Si O O Si O Si O Si O Si O Si O Si O Si O Si O Si O Si O O Si Si O
+
NH4
Branched structures
a+
Reduced backbiting kbitin biting mechanism
+
b4 b + b6 5
b7+
+
Si O O Si Si Si O O O O Si O Si O Si O Si O Si O Si O O O Si Si O Si
Limited « monomer mer e evaporation » through consecutive cycle losses Si
Larger bn+ prod product ions
PLASMA POLYMERS Reference vs. Plasma-polymer
O Si Si O O Si O Si O Si O Si O Si O Si O Si O Si O Si O Si O O Si Si O
+
NH4
h(qi) h(pi) pi
Score=0.935
Score =
vs.
qi
PLASMA POLYMERS Reference vs. Plasma-polymer
Score as a function of polymerization degree
h(qi) h(pi) pi
Score=0.935
Score =
vs.
qi
PLASMA POLYMERS Raiders of the End-groups Soluble part
Si
O
O
Amenable to ESI-MS
Insoluble part
Si O
Si
O
Si
Partial solubilization of the insoluble plasma polymers
T. Fouquet, J. Petersen, F. Ziarelli, J. Bour, V. Toniazzo, D. Ruch and L. Charles, Plasma Process Polym, in press. T. Fouquet, J. Bour, V. Toniazzo, D. Ruch and L. Charles, Rapid Commun Mass Spectrom 2012, 26. 2057
PLASMA POLYMERS Raiders of the End-groups Soluble part
Si
O
O
Insights into the architecture of plasma-polymers
Insoluble part
Si O
Si
O
Si
Branching points / « backbone » Hydroxy / Ethoxy-terminated oligomers
T. Fouquet, J. Petersen, F. Ziarelli, J. Bour, V. Toniazzo, D. Ruch and L. Charles, Plasma Process Polym, in press. T. Fouquet, J. Bour, V. Toniazzo, D. Ruch and L. Charles, Rapid Commun Mass Spectrom 2012, 26. 2057
PLASMA POLYMERS Soluble part
Si
O
O
Insoluble part
Ethanolysis
Reconstruction of the original network connectivity § Spacers between branching points § Pendant groups § Embedded chains
Si O
Si
O
Si
PHD DISSERTATION Dissemination • Defense (Dec 14th 2012) Reviewers: C. Wesdemiotis (Univ. of Akron, US) and S. Weidner (BAM, Germany) • 15 publications T. Fouquet Int J Mass Spectrom 2014, under rev. (Young Scientist Feature). T. Fouquet ChemistryOpen 2014, 3, 269 (Thesis Treasury). T. Fouquet, L. Charles, D. Ruch Rapid Commun Mass Spectrom 2014, 28, 1849. T. Fouquet, V. Toniazzo, D. Ruch, L. Charles J Am Soc Mass Spectrom 2013, 24, 1123. T. Fouquet, J. Petersen, F. Ziarelli, J. Bour, V. Toniazzo, D. Ruch, L. Charles Plasma process Polym.2013, 10, 271 T. Fouquet, C. Chendo, V. Toniazzo, D. Ruch, L .Charles Rapid Commun Mass Spectrom 2013, 27, 88. *J. Petersen, C. Becker, T. Fouquet, F. Addiego, V Toniazzo, A. Dinia, D. Ruch RSC Advances 2013, 3, 4416. T Fouquet, J Bour, V Toniazzo, D Ruch, L Charles Rapid Commun Mass Spectrom 2012, 26, 2057. *C. Amorosi, T. Fouquet, D. Ruch, L. Averous, V. Ball, M. Michel, React Funct Polym 2012, 72, 341. *J. Petersen, T. Fouquet, M. Michel, V. Toniazzo, A. Dinia, D. Ruch, J.A.S. Bomfim Appl Mater Interfaces 2012, 4, 1072. T. Fouquet, J. Petersen, J.A.S. Bomfim, F. Ziarelli, J. Bour, D. Ruch, L. Charles Int J Mass Spectrom 2012, 313, 58. T. Fouquet, T.N.T. Phan, L. Charles Rapid Commun Mass Spectrom 2012, 26, 765. *J. Petersen, R. Bechara, J. Bardon, T. Fouquet, F. Ziarelli, L. Daheron, V. Ball, V. Toniazzo, M. Michel, A. Dinia, D. Ruch Plasma Process Polym 2011, 8, 895. T. Fouquet, S. Humbel, L. Charles Int J Mass Spectrom 2011, 306, 70. T. Fouquet, S. Humbel, L. Charles J Am Soc Mass Spectrom 2011, 22, 649. * In the framework of two other PhDs (J. Petersen and C. Amorosi)
PHD DISSERTATION Dissemination • 6 oral presentations (+ 7 posters) 20th Int. Mass Spectrom. Conf. (IMSC), Aug. 24-29, 2014, Geneva, Switzerland. 7th Eur. Proteomics Association (EUPA), Oct.14-17, 2013, Saint Malo, France. 60th American Soc. for Mass Spectrom., May 19-24, 2012, Vancouver, Canada. 28th French Soc. for Mass Spectrom., Sep. 19-23, 2011, Avignon, France. 14th Eur. Conf. on Applications of Surf. & Interface Anal., Sep. 4-9, 2011, Cardiff, Wales. 15th Young Sci. of the French Soc. for Mass Spectrom., Apr. 4-8, 2011, Pisos, France. 28th French Soc. for Mass Spectrom., Sep.13-16, 2010, Clermont-Ferrand, France.
• 4 Awards Aix-Marseille University Best Thesis Prize 2012 French Soc. For Mass Spectrom. Best Thesis Prize 2013 IUPAC Young Chemist Prize Honorable Mention Award 2013 Int. J. Mass Spectrom. Best Student Paper Award 2012
WINTER 2012 - SUMMER 2014 “R&D engineer, post-doc” • Depth profiling of polymeric bilayers • Mass spectrometry of plasma polymers • Mass spectrometry of PDMS
Winter (Gründ, Luxembourg) Summer
DEPTH PROFILING OF POLYMERS Public Research Centre Henri Tudor, Luxembourg Dr D. Ruch (
[email protected]) Public Research Centre Gabriel Lippmann, Luxembourg Dr G. Frache (
[email protected])
DEPTH PROFILING OF POLYMERS PS/PS bilayer of different MW
DEPTH PROFILING OF POLYMERS TOF-SIMS
nm depth resolution No molecular discrimination
PS 4kDa
Static (Cs+)
Dynamic (Cs+)
PS 2kDa
DEPTH PROFILING OF POLYMERS Surface Layer MALDI (C. Wesdemiotis)
< 2 nm depth resolution at 2 kDa (Rg of polymer) Up to 20 kDa (low polydispersity)
DEPTH PROFILING OF POLYMERS Sample preparation (PS/PS)
Ennis, D. et al
Ennis, D., Betz, H., Ade, H., J. Polym. Sci., part B: Polym. Phys. 2006, 44, 3234.
DEPTH PROFILING OF POLYMERS SIMS Etching
DEPTH PROFILING OF POLYMERS Surface Layer MALDI - Mw depth profile
DEPTH PROFILING OF POLYMERS Dissemination + Follow-up • Dissemination “TOF-SIMS/MALDI-TOF combination for the MW depth profile of polymeric bilayer" T. Fouquet, G. Mertz, N. Desbenoit, G. Frache, D. Ruch Materials Letters 2014, 128, 23. 20th Int. Mass Spectrom. Conf. IMSC, Aug. 24-29, 2014, Geneva, Switzerland (poster). • Follow-up Internal project proposal + internship (to be submitted)
MS OF PLASMA POLYMERS Public Research Centre H. Tudor, Luxembourg Dr D. Ruch (
[email protected]) Public Research Centre Gabriel Lippmann, Luxembourg Dr N. Boscher (
[email protected]) (Université Paul Sabatier, France Dr. N. Gherardi (
[email protected])
PLASMA POLYMERS Hydrolyzable plasma polymer Plasma polymerization
pp(Methacrylic anhydride) O O
O
O O
O
Methacrylic anhydride
El Electrode
in water
PLASMA POLYMERS Hydrolyzable plasma polymer Surface Assisted Laser Desorption Ionization SALDI-MS
OH
HO
O
O
H2O O O
O
pp(Methacrylic anhydride) O O
O
PLASMA POLYMERS Analysis of deposits
PLASMA POLYMERS Analysis of deposits Atom Transfer Radical Polymerization ATRP (Controlled Radical Polymerization CRP)
Plasma Zone
Plasma Polymerization
PLASMA POLYMERS Analysis of deposits Atom Transfer Radical Polymerization ATRP (Controlled Radical Polymerization CRP)
Plasma Zone
Plasma Polymerization
PLASMA POLYMERS Peculiar deposits • plasma polymers < ante plasma zone < radical polymerization
Ante Plasma Zone
PLASMA POLYMERS Peculiar deposits • plasma polymers < ante plasma zone < radical polymerization
Ante Plasma Zone
PLASMA POLYMERS Peculiar deposits • plasma polymers < ante plasma zone < radical polymerization
Ante Plasma Zone
MS OF PLASMA POLYMERS Dissemination + Follow-up • Dissemination •
•
In situ generation of plasma-polymers standards by plasma assisted free radical polymerization T. Fouquet, G. Mertz, C. Becker, F. Ziarelli, L. Fetzer, D. Ruch Plasma Processes and Polymers 2014, 11, 931. A Methacrylic Anhydride Difunctional Precursor to Produce a Hydrolysis-Sensitive Coating by Aerosol Assisted Atmospheric Plasma Process G. Mertz, T. Fouquet, C. Becker, F. Ziarelli, D. Ruch Plasma Processes and Polymers 2014, 11, 728 (Cover Article).
• Follow-up •
Internal project (cproco)
•
Deciphering the molecular weight of plasma polymery by thermal analysis T. Fouquet, G. Mertz, C. Becker, L. Fetzer, D. Ruch Plasma Processes and Polymers 2015, to be submitted.
•
+ 3 additional papers (hydrolyzable plasma polymers*2, fire proofing)
MS OF PDMS Three-way collaboration Public Research Centre H. Tudor, Luxembourg Dr D. Ruch (
[email protected]) Rouen University, France Pr C. Afonso (
[email protected]) Total petrochemicals, France Dr P. Giusti (
[email protected]) Dr C. Barrère-Mangote (
[email protected])
MASS SPECTROMETRY OF PDMS Atmospheric Solid Probe Analysis (ASAP)-MS
C.N. McEwen et al
~ pyrolysis-like process + ionization
C.N. McEwen, R.G. McKay, B.S. Larsen. Anal. Chem. 2005, 77, 7826.
MASS SPECTROMETRY OF PDMS ESI vs. Atmospheric Solid Probe Analysis (ASAP) • Hydroxy-ended PDMS, Mn 550 g/mol
Electrospray Tandem Mass Spectrometry ESI-MS/MS
ASAP-MS (single stage)
MASS SPECTROMETRY OF PDMS ASAP-MS for PDMS of industrial relevance OH-PDMS 4,200 g/mol
OH-PDMS 18,000 g/mol
OH-PDMS 49,000 g/mol
OH-PDMS 110,000 g/mol
MASS SPECTROMETRY OF PDMS ASAP-MS for a Mn evaluation of polydisperse PDMS 490
OH-PDMS 4,200 g/mol
470 450
Mn (b+)
430 410 390
370
OH-PDMS 18,000 g/mol
350 490 470 450 430
OH-PDMS 49,000 g/mol
Mn (b*+)
410
390 370 350
1.40 1.20 1.00
OH-PDMS 110,000 g/mol
0.80
I(m/z 371) / I(m/z 355)
0.60 0.40 0.20 0.00 0
50000
100000
150000
Mn (PDMS)
MASS SPECTROMETRY OF PDMS Dissemination + Follow-up
• Dissemination •
Atmospheric solid analysis probe mass spectrometry vs. electrospray tandem mass spectrometry of polydimethylsiloxanes in positive and negative ionization modes. T. Fouquet, C. Barrère-Mangote, M. Farenc, C. Afonso, P. Giusti Rapid Communication in Mass Spectrometry 2015, under review.
•
+ 1 research article « ASAP-MS for rapid MW evaluation of polydisperse PDMS »
SUMMER 2014 - WINTER 2015 “R&D engineer, post-doc” • Cardanol chemistry LIST, Luxembourg Dr D. Ruch (
[email protected])
Summer / Winter (Mullerthal, Luxembourg)
CARDANOL CHEMISTRY Basics about cardanol
Cardanol
Plasticizer Surfactant Substitute (Bisphenol A, Phenol, …)
OH
V.S. Balachandran, S.R. Jadhav, P.K. Vemula, G. John, Chem. Soc. Rev. 2013,42, 427.
CARDANOL CHEMISTRY Basics about cardanol 107Ag
109Ag
~ 40%
HPLC (reverse phase)
~ 20%
~ 35%
MALDI-MS (AgTFA) HPLC-MALDI-MS (off line)
CARDANOL CHEMISTRY Accelerated photo-ageing
Pristine cardanol
96h photo-aged cardanol < 15% soluble, dark yellow
Sun test (accelerated photo-ageing)
CARDANOL CHEMISTRY Photoageing of Cardanol
G. Mertz, Evolutions of physico-chemical & mechanical properties of rubber-based composites under photo-ageing, PhD dissertation, 2011.
CARDANOL CHEMISTRY MALDI-MS • Propensity of tri-unsaturated vs. monounsaturated to react under photo-ageing
CARDANOL CHEMISTRY Off-line SEC-MALDI-MS coupling • Nomenclature for the photo-products
CARDANOL CHEMISTRY Side chain functionalization & photo-ageing
Methoxylated cardanol
CARDANOL CHEMISTRY Side chain functionalization & photo-ageing Pristine Methoxylated cardanol
170h photo-aged methoxylated cardanol 100% soluble, dark yellow
CARDANOL CHEMISTRY Direct application • Synthesis of poly(MMA-co-(cardanol acrylate & methoxylated cardanol acrylate)) • Accelerated photo-ageing & SEC
Photocrosslinkable polymer K.I. Suresh et al
K.I. Suresh, M. Jaikrishna, Journal of Polymer Science part A: Polymer Chemistry 2005, 43, 5953.
CARDANOL CHEMISTRY Characterization of co- and terpolymers
CARDANOL CHEMISTRY Photoageing & SEC
CARDANOL CHEMISTRY Dissemination + Follow-up • Dissemination •
•
•
Organomodification of sepiolite clay using bio-sourced surfactants: compatibilization and dispersion into epoxy thermosets for properties enhancement P. Verge, T. Fouquet, C. Barrère, V. Toniazzo, D. Ruch, J.A.S Bomfim Composites Science and Technology 2013, 79, 126. Tailoring the reactivity of bio-surfactants as a tool for clay exfoliation in epoxy thermosets L. Puchot, P. Verge, T. Fouquet, J.A.S. Bomfim, V. Toniazzo, D. Ruch Applied Clay Science 2014, 99, 35. Exploration of cardanol-based phenolated and epoxidized resins by SEC and MALDI-MS T. Fouquet, L. Puchot, P. Verge, J.A.S. Bomfim, D. Ruch Analytica Chimica Acta 2014, 843, 46.
• Follow-up • • •
Photosensitivity of cardanol: blessing in disguise T. Fouquet, L. Fetzer, G. Mertz, L. Puchot, P. Verge, RSC Advances, to be submitted Biobased benzoxazines (PhD student + internship) + 2 other papers (cardanol-based composites + thermal/photo ageing)
LAST WORDS Additional activities • Senior Assistant Editor, De Gruyter Open (part time) Dr. Anna Rulka (
[email protected]) Team animation (9 assistant editors) + mass-mailing • Guest Editor, Plasma Processes and Polymers (Wiley) Special Issue on “Analytical tools for plasma deposits” (Summer 2015) with Pr. P.-L. Girard-Lauriault (McGill University, Canada) • Referee • • • •
Thin Solid Films (Elsevier) Materials Letters (Elsevier) Environmental Technology (Taylor & Francis) Plasma Processes and Polymers (Wiley)
• Voluntary service, Professional Education Organization International Dr. J. Petroff (
[email protected]) Translator – lectures in general chemistry (English to French)
THANK YOU
Eli, Jan. 9th 2015
Emily, Jan. 22nd 2015
