Conformations of Reaction Products: Polymers and Organic Phenyl/Vinyl Linkages

Transcription

1 Conformations of Reaction Products: Polymers and Organic Phenyl/Vinyl Linkages Erin Shammel Baker, Jennifer Gidden, Glenn Bartholomew, Guillermo Bazan, and Michael T. Bowers (UCSB) James Scrivens and Anthony Jackson (ICI) William Simonsick (DuPont)

2 Introduction Understand the structures of reaction products that can not be determined using methods such as NMR and FTMS Characterize structures with ion mobility eperiments and molecular mechanics Help synthetic chemists understand the abundance of the reaction products and impurities

3 MALDI-TOF hν Source TOF Detector TOF Quadrupole Drift Cell Glass l = 20 cm p = ~1.5 torr He

4 m/z MALDI-TOF hν TOF Mode TOF Detector TOF Drift Cell Quadrupole Source Mass Spectrum

5 MALDI-TOF hν Ion Mobility Mode TOF Drift Cell Quadrupole Detector Source Arrival Time Distributions Single Conformer Multiple Conformers

6 Ethylene Oide/ Propylene Oide (EO / PO) Copolymers Erin Baker, Jennifer Gidden, and Michael Bowers (UCSB) James Scrivens and Anthony Jackson (ICI) Industrial important class of surfactants Used in detergents, foams, lubricants, and drug delivery PO has a hydrophobic character EO has a more hydrophilic character Vary the amount and sequence of EO and PO to get desired characteristics EO PO C 13 H 27 O ( CH 2 CH 2 O ) ( CH 2 CH O ) y H CH 3

7 Block vs Random EO / PO Copolymer Mass Spectra 4-mer 16-mer Na + Block 4-mer 20-mer Na + Random m/z

8 Block Na + EOPO5 ATDs at 300 K Arrival Time (µs) EO0 PO5 σ = 169 Å 2 EO3 PO5 σ = 190 Å 2 EO5 PO5 σ = 206 Å 2 EO7 PO5 σ = 224 Å 2 EO11 PO5 σ = 252 Å 2

9 Na + EOPO5 Theoretical Structures C 13 H 27 O-EO0-PO5 H σ Theory = 171 Å 2 C 13 H 27 O-EO7-PO5-H σ Theory = 223 Å 2 C 13 H 27 O-EO11-PO5-H σ Theory = 253 Å 2 = Oygen from C 13 H 27 = EO Oygen = PO Oygen = Oygen Coordinating to Na +

10 Block Na + EO / PO Collision Cross-Sections (Å 2 ) Copolymer Eperiment (Na + ) Theory (Na + ) EO = 5 PO = EO = 5 PO = EO = 5 PO = EO = 0 PO = EO = 3 PO = EO = 5 PO = EO = 7 PO = EO =11 PO =

11 Block vs Random Na + EO / PO Eperimental Cross-Sections (Å 2 ) Copolymer Block (Na + ) Random (Na + ) EO = 5 PO = EO = 5 PO = EO = 5 PO = EO = 0 PO = EO = 3 PO = EO = 5 PO = EO = 7 PO = EO =11 PO =

12 Na + EO5PO5 Theoretical Structures (Sequence Dependent) C 13 H 27 O-EO5-PO5-H (block) σ Theory = 205 Å 2 C 13 H 27 O-PO5-EO5-H (block) σ Theory = 205 Å 2 C 13 H 27 O-EO5-PO5-H (alternating) σ Theory = 205 Å 2 = Oygen from C 13 H 27 = EO Oygen = PO Oygen = Oygen Coordinating to Na +

13 EO / PO Copolymers Summary 1. Ion mobility determined that the the conformations of the block and random copolymers are similar 2. The difference in the physical properties of random versus block must be a result of other factors EO PO C 13 H 27 O ( CH 2 CH 2 O ) ( CH 2 CH O ) y H CH 3

14 Glycidyl Methacrylate/Butyl Methacrylate (GMA / BMA) Copolymers Erin Baker and Michael Bowers (UCSB) William Simonsick (DuPont) Polymers used in paint which produces high performance coatings GMA and BMA have the same nominal mass but differ in the eact mass by Da (CH 4 vs O) CH 3 C H 2 CH 3 O O C H 2 O O O GMA BMA

15 GMA / BMA Copolymers H H H O CH 3 O R n O CH 2 O R H 3 C H 3 C H 3 C N O CH 3 O R n O CH 2 O R H-end Polymer Vaso-end Polymer O R =

16 GMA / BMA Copolymers Mass Spectrum Na + H-Trimer Na + H-Tetramer Na + V-Trimer Na + H-Pentamer Na + V-Tetramer Na + V-Pentamer Na + H-Heamer Na + V-Heamer Na + H-Heptamer m/z 1050

17 Na + GMA / BMA Trimer ATDs at 300 K H-end Trimer σ = 138 Å 2 σ = 146 Å 2 σ = 152 Å 2 σ = 130 Å 2 Vaso-end Trimer σ = 164 Å 2 σ = 171 Å 2 σ = 175 Å 2 σ = 184 Å 2 Arrival Time (µs) Arrival Time (µs)

18 GMA / BMA Collision Cross-Sections and Theoretical Structures H-end Trimer Sequence Collision Cross-Sections (Å 2 ) Theory (Na + ) Eperiment (Na + ) % Abundance from ATD H-GGG % H-GBG % H-BGG 142 H-GGB H-BBG % H-GMA-GMA-GMA σ Theory = 133 Å 2 H-BGB H-GBB % H-BBB 159 0% H-BMA-BMA-BMA σ Theory = 159 Å 2

19 GMA / BMA Collision Cross-Sections and Theoretical Structures Vaso-end Trimer Collision Cross-Sections (Å 2 ) Sequence Theory (Na + ) V-GGG 161 Eperiment (Na + ) 164 % Abundance from ATD 27% V-BGG 163 V-GBG % V-GGB % V-GMA-GMA-GMA σ Theory = 161 Å 2 V-BBG 178 V-BGB % V-GBB 186 V-BBB 191 0% V-BMA-BMA-BMA σ Theory = 191 Å 2

20 GMA / BMA Copolymers Summary 1. The overall oligomeric distributions for the hydrogen and vaso end groups can be determined (Mass Spectrum) 2. The abundance and sequence for the GMA and BMA side chains can be identified (Ion Mobility) CH 3 C H 2 CH 3 O O C H 2 O O O GMA BMA

21 para-cyclophanes Erin Baker, Glenn Bartholomew, Guillermo Bazan, and Michael Bowers (UCSB) Allows 2 organic substituents (chromophores) to be in close proimity for optoelectronic application Displays better transport properties and lower operating voltages because of the alignment

22 para-cyclophanes (pcp) A B?

23 para-cyclophanes (pcp) H H H H Molecule A Molecule B

24 pcp Mass Spectrum Na + pcp m/z

25 300 K Na + pcp ATDs σ EXPT = 137 Å K Arrival Time (µs)

26 Na + pcp ATD Theoretical Structures Na + B Na + A Arrival Time (µs) σ EXPT = 137 Å 2 Molecule A σ Theory = 144 Å 2 % Error = 5.1% Molecule B σ Theory = 139 Å 2 % Error = 1.5%

27 Diheyl para-benzamine para-cyclophanes para-nitrobenzene in Trans Form (DpCpN) N A B NO 2

28 H + DpCpN ATD at 300 K 300 K σ = 233 Å 2 σ = 273 Å 2 Arrival Time (µs)

29 DpCpN Collision Cross-Sections Molecule A Cross-Sections (Å 2 ) Molecule B Cross-Section (Å 2 ) Pi Bond Arrangement Theory (H + ) Eperiment (H + ) Pi Bond Arrangement Theory (H + ) Eperiment (H + ) Cis-Cis-Cis Cis-Trans-Cis 233, , 273 Cis-Cis-Trans Cis-Cis-Cis Cis-Trans-Cis Cis-Cis-Trans Cis-Trans-Trans 283 Cis-Trans-Trans 281 Trans-Trans-Cis 291 Trans-Trans-Cis 288 Trans-Cis-Cis 293 Trans-Cis-Cis 289 Trans-Cis-Trans 295 Trans-Cis-Trans 292 Trans-Trans-Trans 299 Trans-Trans-Trans 295

30 H + DpCpN ATD and Theoretical Structures Folded Open Arrival Time (µs) Folded Cis-Trans-Cis σ Theory = 233 Å 2 Open Cis-Trans-Cis σ Theory = 277 Å 2

31 H + DpCpN Temperature Dependent ATDs Arrival Time (µs) 110 K 300 K 470 K

32 Arrival Time (µs) H + DpCpN Temperature Dependent ATDs 110 K σ = 6 Å 2 σ = 15 Å K 470 K

33 H + DpCpN Folded Theoretical Structures 1.9 Å 4.9 Å F1 Folded Cis-Trans-Cis σ Theory = 233 Å 2 F2 Folded Cis-Trans-Cis σ Theory = 239 Å 2 σ = 6 Å 2

34 H + DpCpN Open Theoretical Structures O1 Open Cis-Trans-Cis σ Theory = 262 Å 2 σ = 15 Å 2 O2 Open Cis-Trans-Cis σ Theory = 277 Å 2

35 H + DpCpN ATDs 110 K F1 F2 O1 O2 Arrival Time (µs) F1 F2 O1 O2

36 H + DpCpN ATDs Arrival Time (µs) 110 K 300 K 470 K

37 para-cyclophanes Summary 1. The σ bond connectivity between para-cyclophane units can be analyzed (Can not be determined from NMR) 2. Cis/Trans distributions for each vinyl linkages can be determined

38 Conclusion Ion Mobility is a ecellent tool for determining the conformations of reaction products which are too comple for other analysis methods. - Geometric isomers can be quantified - Cis/Trans linkages can be determined - Polymer sequences and distributions can be obtained

39 Acknowledgements Dr. Jennifer Gidden Dr. Paul Kemper Prof. Michael T. Bowers Bowers Group Dr. Glenn Bartholomew Dr. William Simonsick Prof. Guillermo Bazan Dr. James Scrivens Dr. Anthony Jackson

40 Eperimental Setup gate (1-10 µs) Ion Source Mass Spectrometer Drift Cell Mass Analyzer Detector Arrival Time Distributions MALDI Time-of-Flight l = 20 cm V = 8-16 V/cm p = ~1.5 torr He Quadrupole single conformer multiple conformers EXPT: ATDs mobilities (K) l v = = C d = t K E d Ω THEORY: molecular mechanics structures (AMBER) collision cross-sections (Ω) collision cross-sections (Ω)

41 Eperiment versus Theory ATDs Mobilities (K) Collision Cross-Sections Molecular Mechanics/Dynamics Structures Collision Cross-Sections AMBER

42 DpCpN Mass Spectrum H + DpCpN m/z

43 Cis-Trans-Cis Theoretical Structures Open 270 Cross Section (Å 2 ) Folded Relative Energy (kcal/mol)