Single-Polymer–Particle Growth Kinetics with Molecular Catalyst Speciation and Single-Turnover Imaging
Abstract
The dynamics of the local environments surrounding molecular polymerization catalysts plausibly impact turnover kinetics, but the impact of and nature of such dynamics have previously been obscured by ensemble averaging. With Grubbs’ second generation ruthenium metathesis catalyst and a precipitation polymerization system, studies at the single-particle and -turnover level establish that (1) an inverse correlation exists between rate and duration of single-polymer–particle growth of aggregates, consistent with a local environment density model for the time-variable kinetics; (2) cross-linking additives produced a small, but detectible, reduction in overall monomer incorporation; (3) total ruthenium quantity within the polymer particles (as characterized by energy dispersive X-ray spectroscopy) is differentiable from the quantity that is catalytically active (as characterized by in situ fluorescence microscopy), providing catalyst speciation information; and (4) time-resolved enyne metathesis reactions can be imaged, corresponding to single turnovers at individual molecular catalysts during polymer growth under synthetically relevant conditions. Here, these findings identify and characterize reactivity distributions likely arising from the dynamics of local environments. As such, these data provide reactivity information that is unavailable through traditional ensemble analytical methods that obscure this type of information through averaging.
- Publication Date:
- Research Org.:
- Univ. of California, Irvine, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1836113
- Grant/Contract Number:
- SC0016467; CHE-082913
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polymerization; kinetics; molecular catalysis; fluorescence microscopy; ROMP; single turnover; single-molecule imaging
Citation Formats
Easter, Quinn T., Garcia, Antonio, and Blum, Suzanne A. Single-Polymer–Particle Growth Kinetics with Molecular Catalyst Speciation and Single-Turnover Imaging. United States: N. p., 2019.
Web. doi:10.1021/acscatal.9b00095.
Easter, Quinn T., Garcia, Antonio, & Blum, Suzanne A. Single-Polymer–Particle Growth Kinetics with Molecular Catalyst Speciation and Single-Turnover Imaging. United States. https://doi.org/10.1021/acscatal.9b00095
Easter, Quinn T., Garcia, Antonio, and Blum, Suzanne A. Mon .
"Single-Polymer–Particle Growth Kinetics with Molecular Catalyst Speciation and Single-Turnover Imaging". United States. https://doi.org/10.1021/acscatal.9b00095. https://www.osti.gov/servlets/purl/1836113.
@article{osti_1836113,
title = {Single-Polymer–Particle Growth Kinetics with Molecular Catalyst Speciation and Single-Turnover Imaging},
author = {Easter, Quinn T. and Garcia, Antonio and Blum, Suzanne A.},
abstractNote = {The dynamics of the local environments surrounding molecular polymerization catalysts plausibly impact turnover kinetics, but the impact of and nature of such dynamics have previously been obscured by ensemble averaging. With Grubbs’ second generation ruthenium metathesis catalyst and a precipitation polymerization system, studies at the single-particle and -turnover level establish that (1) an inverse correlation exists between rate and duration of single-polymer–particle growth of aggregates, consistent with a local environment density model for the time-variable kinetics; (2) cross-linking additives produced a small, but detectible, reduction in overall monomer incorporation; (3) total ruthenium quantity within the polymer particles (as characterized by energy dispersive X-ray spectroscopy) is differentiable from the quantity that is catalytically active (as characterized by in situ fluorescence microscopy), providing catalyst speciation information; and (4) time-resolved enyne metathesis reactions can be imaged, corresponding to single turnovers at individual molecular catalysts during polymer growth under synthetically relevant conditions. Here, these findings identify and characterize reactivity distributions likely arising from the dynamics of local environments. As such, these data provide reactivity information that is unavailable through traditional ensemble analytical methods that obscure this type of information through averaging.},
doi = {10.1021/acscatal.9b00095},
journal = {ACS Catalysis},
number = 4,
volume = 9,
place = {United States},
year = {Mon Mar 04 00:00:00 EST 2019},
month = {Mon Mar 04 00:00:00 EST 2019}
}
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Works referenced in this record:
Single molecule fluorescence microscopy investigations on heterogeneity of translational diffusion in thin polymer films
journal, January 2011
- Flier, Bente M. I.; Baier, Moritz; Huber, Johannes
- Phys. Chem. Chem. Phys., Vol. 13, Issue 5
Functional Block Copolymers: Nanostructured Materials with Emerging Applications
journal, July 2012
- Schacher, Felix H.; Rupar, Paul A.; Manners, Ian
- Angewandte Chemie International Edition, Vol. 51, Issue 32
Noninvasive Nanoscopy Uncovers the Impact of the Hierarchical Porous Structure on the Catalytic Activity of Single Dealuminated Mordenite Crystals
journal, August 2015
- Kubarev, Alexey V.; Janssen, Kris P. F.; Roeffaers, Maarten B. J.
- ChemCatChem, Vol. 7, Issue 22
Cooperative communication within and between single nanocatalysts
journal, March 2018
- Zou, Ningmu; Zhou, Xiaochun; Chen, Guanqun
- Nature Chemistry, Vol. 10, Issue 6
Integrated Transmission Electron and Single-Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle
journal, November 2017
- Hendriks, Frank C.; Mohammadian, Sajjad; Ristanović, Zoran
- Angewandte Chemie International Edition, Vol. 57, Issue 1
From the molecule to the mole: improving heterogeneous copper catalyzed click chemistry using single molecule spectroscopy
journal, January 2017
- Wang, Bowen; Durantini, Javier; Decan, Matthew R.
- Chem. Commun., Vol. 53, Issue 2
Porous Organic Materials: Strategic Design and Structure–Function Correlation
journal, December 2016
- Das, Saikat; Heasman, Patrick; Ben, Teng
- Chemical Reviews, Vol. 117, Issue 3
Homogeneous vs Heterogeneous Polymerization Catalysis Revealed by Single-Particle Fluorescence Microscopy
journal, November 2011
- Esfandiari, N. Melody; Blum, Suzanne A.
- Journal of the American Chemical Society, Vol. 133, Issue 45
Growth Kinetics Obtained from Single Particle Gas-Phase Ethene Homopolymerization with a Ziegler-Natta Catalyst: Growth Kinetics Obtained from Single Particle Gas-Phase …
journal, September 2013
- Mayrhofer, Leonhard; Paulik, Christian
- Macromolecular Reaction Engineering, Vol. 8, Issue 3
Single polymer growth dynamics
journal, October 2017
- Liu, Chunming; Kubo, Kaori; Wang, Endian
- Science, Vol. 358, Issue 6361
BODIPY Fluorophore Toolkit for Probing Chemical Reactivity and for Tagging Reactive Functional Groups: BODIPY Fluorophore Toolkit
journal, April 2014
- Hensle, Eva M.; Esfandiari, N. Melody; Lim, Sung-Gon
- European Journal of Organic Chemistry, Vol. 2014, Issue 16
X-ray transition energies: new approach to a comprehensive evaluation
journal, January 2003
- Deslattes, Richard D.; Kessler, Ernest G.; Indelicato, P.
- Reviews of Modern Physics, Vol. 75, Issue 1
Spin coating of thin and ultrathin polymer films
journal, December 1998
- Hall, David B.; Underhill, Patrick; Torkelson, John M.
- Polymer Engineering & Science, Vol. 38, Issue 12
Propylene polymerization through supported metallocene/ MAO catalysts: Kinetic analysis and modelling
journal, October 1995
- Bonini, F.; Fraaije, V.; Fink, G.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 33, Issue 14
Polymers and single molecule fluorescence spectroscopy, what can we learn?
journal, January 2009
- Wöll, Dominik; Braeken, Els; Deres, Ania
- Chem. Soc. Rev., Vol. 38, Issue 2
Single Molecule Nanospectroscopy Visualizes Proton-Transfer Processes within a Zeolite Crystal
journal, October 2016
- Ristanović, Zoran; Kubarev, Alexey V.; Hofkens, Johan
- Journal of the American Chemical Society, Vol. 138, Issue 41
The influence of cross-linking agents on ring-opening metathesis polymerized thermosets
journal, July 2007
- Sheng, X.; Kessler, M. R.; Lee, J. K.
- Journal of Thermal Analysis and Calorimetry, Vol. 89, Issue 2
Role of LiCl in Generating Soluble Organozinc Reagents
journal, August 2016
- Feng, Chao; Cunningham, Drew W.; Easter, Quinn T.
- Journal of the American Chemical Society, Vol. 138, Issue 35
Catalyst Inefficiencies: Supported Ring-Opening Metathesis Polymerization Catalyst Yields Its Ensemble Rate from a Small Number of Molecular Active Sites
journal, March 2015
- Easter, Quinn T.; Trauschke, Vanessa; Blum, Suzanne A.
- ACS Catalysis, Vol. 5, Issue 4
Cross-Linking–Effect on Physical Properties of Polymers
journal, January 1969
- Nielsen, Lawrence E.
- Journal of Macromolecular Science, Part C, Vol. 3, Issue 1
Propene Polymerization with Silica-Supported Metallocene/MAO Catalysts
journal, April 2000
- Fink, Gerhard; Steinmetz, Bernd; Zechlin, Joachim
- Chemical Reviews, Vol. 100, Issue 4
Crosslinked polynorbornene particles synthesis by ring-opening metathesis polymerization in dispersion
journal, February 2012
- Le Meur, Anne-Claire; Aymonier, Cyril; Heroguez, Valérie
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 50, Issue 9
Principles of Fluorescence Spectroscopy
book, January 2006
- Lakowicz, Joseph R.
- Springer New York, NY
Kinetics of the Same Reaction Monitored over Nine Orders of Magnitude in Concentration: When Are Unique Subensemble and Single‐Turnover Reactivity Displayed?
journal, August 2018
- Easter, Quinn T.; Blum, Suzanne A.
- Angewandte Chemie International Edition, Vol. 57, Issue 37
Spatiotemporal catalytic dynamics within single nanocatalysts revealed by single-molecule microscopy
journal, January 2014
- Chen, Peng; Zhou, Xiaochun; Andoy, Nesha May
- Chem. Soc. Rev., Vol. 43, Issue 4
Single-Molecule Imaging of Platinum Ligand Exchange Reaction Reveals Reactivity Distribution
journal, November 2010
- Esfandiari, N. Melody; Wang, Yong; Bass, Jonathan Y.
- Journal of the American Chemical Society, Vol. 132, Issue 43
Life and death of a single catalytic cracking particle
journal, April 2015
- Meirer, Florian; Kalirai, Sam; Morris, Darius
- Science Advances, Vol. 1, Issue 3
Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting
journal, February 2006
- Roeffaers, Maarten B. J.; Sels, Bert F.; Uji-i, Hiroshi
- Nature, Vol. 439, Issue 7076
Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts
journal, January 2018
- Easter, Quinn T.; Blum, Suzanne A.
- Angewandte Chemie International Edition, Vol. 57, Issue 6
Single-Molecule Fluorescence Detection of Effective Adsorption Sites at the Metal Oxide–Solution Interface
journal, May 2013
- Tachikawa, Takashi; Ohsaka, Tatsuya; Bian, Zhenfeng
- The Journal of Physical Chemistry C, Vol. 117, Issue 21
Single-Molecule Investigation of Initiation Dynamics of an Organometallic Catalyst
journal, March 2016
- Ng, James D.; Upadhyay, Sunil P.; Marquard, Angela N.
- Journal of the American Chemical Society, Vol. 138, Issue 11
A two-color fluorogenic carbene complex for tagging olefins via metathesis reaction
journal, September 2015
- Wirtz, Marcel; Grüter, Andreas; Heib, Florian
- Methods and Applications in Fluorescence, Vol. 3, Issue 4
Understanding Solidification of Polythiophene Thin Films during Spin-Coating: Effects of Spin-Coating Time and Processing Additives
journal, August 2015
- Na, Jin Yeong; Kang, Boseok; Sin, Dong Hun
- Scientific Reports, Vol. 5, Issue 1
Phase Separation Polymerization of Dicyclopentadiene Characterized by In Operando Fluorescence Microscopy
journal, August 2013
- Hensle, Eva M.; Blum, Suzanne A.
- Journal of the American Chemical Society, Vol. 135, Issue 33
Nanoscopic Visualization of Soft Matter Using Fluorescent Diarylethene Photoswitches
journal, September 2016
- Nevskyi, Oleksii; Sysoiev, Dmytro; Oppermann, Alex
- Angewandte Chemie International Edition, Vol. 55, Issue 41
Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts
journal, July 2001
- Sanford, Melanie S.; Love, Jennifer A.; Grubbs, Robert H.
- Journal of the American Chemical Society, Vol. 123, Issue 27
Single-Molecule, Single-Particle Approaches for Exploring the Structure and Kinetics of Nanocatalysts
journal, February 2012
- Tachikawa, Takashi; Majima, Tetsuro
- Langmuir, Vol. 28, Issue 24
Nanoscale Study of Polymer Dynamics
journal, December 2015
- Keshavarz, Masoumeh; Engelkamp, Hans; Xu, Jialiang
- ACS Nano, Vol. 10, Issue 1
Industrial applications of olefin metathesis
journal, April 2004
- Mol, J.
- Journal of Molecular Catalysis A: Chemical, Vol. 213, Issue 1
Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions
journal, September 2017
- Easter, Quinn T.; Blum, Suzanne A.
- Angewandte Chemie International Edition, Vol. 56, Issue 44
Opportunities and challenges in single-molecule and single-particle fluorescence microscopy for mechanistic studies of chemical reactions
journal, November 2013
- Cordes, Thorben; Blum, Suzanne A.
- Nature Chemistry, Vol. 5, Issue 12