Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions
Abstract
Abstract Multiple active individual molecular ruthenium catalysts have been pinpointed within growing polynorbornene, thereby revealing information on the reaction dynamics and location that is unavailable through traditional ensemble experiments. This is the first single‐turnover imaging of a molecular catalyst by fluorescence microscopy and allows detection of individual monomer reactions at an industrially important molecular ruthenium ring‐opening metathesis polymerization (ROMP) catalyst under synthetically relevant conditions (e.g. unmodified industrial catalyst, ambient pressure, condensed phase, ca. 0.03 m monomer). These results further establish the key fundamentals of this imaging technique for characterizing the reactivity and location of active molecular catalysts even when they are the minor components.
- Publication Date:
- Research Org.:
- Univ. of California, Irvine, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1836176
- Alternate Identifier(s):
- OSTI ID: 1394671
- Grant/Contract Number:
- SC0016467
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 44; Related Information: https://onlinelibrary.wiley.com/action/downloadSupplement?doi=10.1002%2Fanie.201708284&file=anie201708284-sup-0001-misc_information.pdf; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; fluorescence microscopy; molecular catalysts; reaction mechanisms; single molecules
Citation Formats
Easter, Quinn T., and Blum, Suzanne A. Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions. United States: N. p., 2017.
Web. doi:10.1002/anie.201708284.
Easter, Quinn T., & Blum, Suzanne A. Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions. United States. https://doi.org/10.1002/anie.201708284
Easter, Quinn T., and Blum, Suzanne A. Mon .
"Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions". United States. https://doi.org/10.1002/anie.201708284. https://www.osti.gov/servlets/purl/1836176.
@article{osti_1836176,
title = {Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions},
author = {Easter, Quinn T. and Blum, Suzanne A.},
abstractNote = {Abstract Multiple active individual molecular ruthenium catalysts have been pinpointed within growing polynorbornene, thereby revealing information on the reaction dynamics and location that is unavailable through traditional ensemble experiments. This is the first single‐turnover imaging of a molecular catalyst by fluorescence microscopy and allows detection of individual monomer reactions at an industrially important molecular ruthenium ring‐opening metathesis polymerization (ROMP) catalyst under synthetically relevant conditions (e.g. unmodified industrial catalyst, ambient pressure, condensed phase, ca. 0.03 m monomer). These results further establish the key fundamentals of this imaging technique for characterizing the reactivity and location of active molecular catalysts even when they are the minor components.},
doi = {10.1002/anie.201708284},
journal = {Angewandte Chemie (International Edition)},
number = 44,
volume = 56,
place = {United States},
year = {Mon Sep 11 00:00:00 EDT 2017},
month = {Mon Sep 11 00:00:00 EDT 2017}
}
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Works referenced in this record:
Size-Dependent Catalytic Activity and Dynamics of Gold Nanoparticles at the Single-Molecule Level
journal, January 2010
- Zhou, Xiaochun; Xu, Weilin; Liu, Guokun
- Journal of the American Chemical Society, Vol. 132, Issue 1
Grubbs’ Ruthenium-Carbenes Beyond the Metathesis Reaction: Less Conventional Non-Metathetic Utility
journal, August 2009
- Alcaide, Benito; Almendros, Pedro; Luna, Amparo
- Chemical Reviews, Vol. 109, Issue 8
Distinguishing Alternative Reaction Pathways by Single-Molecule Fluorescence Spectroscopy
journal, April 2013
- Rybina, Arina; Lang, Carolin; Wirtz, Marcel
- Angewandte Chemie International Edition, Vol. 52, Issue 24
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
Chemical Imaging of Spatial Heterogeneities in Catalytic Solids at Different Length and Time Scales
journal, June 2009
- Weckhuysen, Bert M.
- Angewandte Chemie International Edition, Vol. 48, Issue 27
Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy
journal, October 2012
- Buurmans, Inge L. C.; Weckhuysen, Bert M.
- Nature Chemistry, Vol. 4, Issue 11
Verfolgung der radikalischen Polymerisation mit Einzelmolekülspektroskopie
journal, January 2008
- Wöll, Dominik; Uji-i, Hiroshi; Schnitzler, Tobias
- Angewandte Chemie, Vol. 120, Issue 4
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
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
Highly Selective Ring-Opening/Cross-Metathesis Reactions of Norbornene Derivatives Using Selenocarbene Complexes as Catalysts
journal, December 2000
- Katayama, Hiroyuki; Urushima, Hideto; Nishioka, Tsuneo
- Angewandte Chemie, Vol. 112, Issue 24
Principles of Fluorescence Spectroscopy
book, January 2006
- Lakowicz, Joseph R.
- Springer New York, NY
Single-Molecule Catalysis Mapping Quantifies Site-Specific Activity and Uncovers Radial Activity Gradient on Single 2D Nanocrystals
journal, January 2013
- Andoy, Nesha May; Zhou, Xiaochun; Choudhary, Eric
- Journal of the American Chemical Society, Vol. 135, Issue 5
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
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
Highly Selective Ring-Opening/Cross-Metathesis Reactions of Norbornene Derivatives Using Selenocarbene Complexes as Catalysts
journal, December 2000
- Katayama, Hiroyuki; Urushima, Hideto; Nishioka, Tsuneo
- Angewandte Chemie International Edition, Vol. 39, Issue 24
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
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
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
High-Resolution Single-Molecule Fluorescence Imaging of Zeolite Aggregates within Real-Life Fluid Catalytic Cracking Particles
journal, December 2014
- Ristanović, Zoran; Kerssens, Marleen M.; Kubarev, Alexey V.
- Angewandte Chemie International Edition, Vol. 54, Issue 6
Quantitative 3D Fluorescence Imaging of Single Catalytic Turnovers Reveals Spatiotemporal Gradients in Reactivity of Zeolite H-ZSM-5 Crystals upon Steaming
journal, April 2015
- Ristanović, Zoran; Hofmann, Jan P.; De Cremer, Gert
- Journal of the American Chemical Society, Vol. 137, Issue 20
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
Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder
journal, February 2017
- Feng, Chao; Easter, Quinn T.; Blum, Suzanne A.
- Organometallics, Vol. 36, Issue 13
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
Toward the Single-Molecule Investigation of Organometallic Reaction Mechanisms: Single-Molecule Imaging of Fluorophore-Tagged Palladium(II) Complexes
journal, May 2008
- Canham, Stephen M.; Bass, Jonathan Y.; Navarro, Oscar
- Organometallics, Vol. 27, Issue 10
Desmethyl Macrolides Synthesis and Evaluation of 4,8,10-Tridesmethyl Telithromycin
journal, January 2011
- Velvadapu, Venkata; Paul, Tapas; Wagh, Bharat
- ACS Medicinal Chemistry Letters, Vol. 2, Issue 1, p. 68-72
Chemische Bildgebung von räumlichen Heterogenitäten in katalytischen Festkörpern auf unterschiedlichen Längen- und Zeitskalen
journal, June 2009
- Weckhuysen, Bert M.
- Angewandte Chemie, Vol. 121, Issue 27
Deconvoluting Subensemble Chemical Reaction Kinetics of Platinum–Sulfur Ligand Exchange Detected with Single-Molecule Fluorescence Microscopy
journal, October 2011
- Esfandiari, N. Melody; Wang, Yong; Bass, Jonathan Y.
- Inorganic Chemistry, Vol. 50, Issue 19
Dye synthesis in the Pechmann reaction: catalytic behaviour of samarium oxide nanoparticles studied using single molecule fluorescence microscopy
journal, January 2016
- Hodgson, Gregory K.; Impellizzeri, Stefania; Scaiano, Juan C.
- Chemical Science, Vol. 7, Issue 2
Sub-particle reaction and photocurrent mapping to optimize catalyst-modified photoanodes
journal, February 2016
- Sambur, Justin B.; Chen, Tai-Yen; Choudhary, Eric
- Nature, Vol. 530, Issue 7588
Nanoscopic heterogeneities in adsorption and electron transfer processes of perylene diimide dye on TiO2 nanoparticles studied by single-molecule fluorescence spectroscopy
journal, August 2007
- Tachikawa, Takashi; Cui, Shi-Cong; Tojo, Sachiko
- Chemical Physics Letters, Vol. 443, Issue 4-6
Super-Resolution Reactivity Mapping of Nanostructured Catalyst Particles
journal, November 2009
- Roeffaers, Maartenâ B. â J.; Deâ Cremer, Gert; Libeert, Julien
- Angewandte Chemie, Vol. 121, Issue 49
Synthesis of Styrenes Using Ruthenium-Catalyzed Ring-Closing Enyne Metathesis
journal, July 2008
- Yoshida, Kazuhiro; Shishikura, Yuka; Takahashi, Hidetoshi
- Organic Letters, Vol. 10, Issue 13
Direkte Beobachtung alternativer Reaktionswege an einzelnen Molekülen
journal, April 2013
- Rybina, Arina; Lang, Carolin; Wirtz, Marcel
- Angewandte Chemie, Vol. 125, Issue 24
Labeling and Single-Molecule Methods To Monitor G Protein-Coupled Receptor Dynamics
journal, June 2016
- Tian, He; Fürstenberg, Alexandre; Huber, Thomas
- Chemical Reviews, Vol. 117, Issue 1
Location change method for imaging chemical reactivity and catalysis with single-molecule and -particle fluorescence microscopy
journal, January 2014
- Blum, S. A.
- Physical Chemistry Chemical Physics, Vol. 16, Issue 31
High-Resolution Single-Molecule Fluorescence Imaging of Zeolite Aggregates within Real-Life Fluid Catalytic Cracking Particles
journal, December 2014
- Ristanović, Zoran; Kerssens, Marleen M.; Kubarev, Alexey V.
- Angewandte Chemie, Vol. 127, Issue 6
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
Towards direct monitoring of discrete events in a catalytic cycle at the single molecule level
journal, January 2009
- Ameloot, Rob; Roeffaers, Maarten; Baruah, Mukulesh
- Photochemical & Photobiological Sciences, Vol. 8, Issue 4
Highly Efficient Ring-Opening Metathesis Polymerization (ROMP) Using New Ruthenium Catalysts Containing N-Heterocyclic Carbene Ligands
journal, August 2000
- Bielawski, Christopher W.; Grubbs, Robert H.
- Angewandte Chemie, Vol. 39, Issue 16
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
Study of Single Catalytic Events at Copper-in-Charcoal: Localization of Click Activity Through Subdiffraction Observation of Single Catalytic Events
journal, September 2015
- Decan, Matthew R.; Scaiano, Juan C.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 20
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
Super-Resolution Reactivity Mapping of Nanostructured Catalyst Particles
journal, November 2009
- Roeffaers, Maartenâ B. â J.; Deâ Cremer, Gert; Libeert, Julien
- Angewandte Chemie International Edition, Vol. 48, Issue 49
Fluorescence Spectroscopy of Single Biomolecules
journal, March 1999
- Weiss, S.
- Science, Vol. 283, Issue 5408
Radical Polymerization Tracked by Single Molecule Spectroscopy
journal, January 2008
- Wöll, Dominik; Uji-i, Hiroshi; Schnitzler, Tobias
- Angewandte Chemie International Edition, Vol. 47, Issue 4
Highly Efficient Ring-Opening Metathesis Polymerization (ROMP) Using New Ruthenium Catalysts Containing N-Heterocyclic Carbene Ligands
journal, August 2000
- Bielawski, Christopher W.; Grubbs, Robert H.
- Angewandte Chemie, Vol. 112, Issue 16
Industrial applications of olefin metathesis
journal, April 2004
- Mol, J.
- Journal of Molecular Catalysis A: Chemical, Vol. 213, Issue 1
Real-Time Imaging of Platinum−Sulfur Ligand Exchange Reactions at the Single-Molecule Level via a General Chemical Technique
journal, June 2011
- Esfandiari, N. Melody; Wang, Yong; McIntire, Theresa M.
- Organometallics, Vol. 30, Issue 11
Works referencing / citing this record:
Cooperative communication within and between single nanocatalysts
journal, March 2018
- Zou, Ningmu; Zhou, Xiaochun; Chen, Guanqun
- Nature Chemistry, Vol. 10, Issue 6
Copper(II)-induced Fluorescence Quenching of a BODIPY Fluorophore: Copper(II)-induced Fluorescence Quenching of a BODIPY Fluorophore
journal, June 2018
- Herten, Dirk-Peter; Haderspeck, Andreas; Braun, Felix
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 644, Issue 14
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, Vol. 130, Issue 37
Catalytic single-chain polymeric nanoparticles at work: from ensemble towards single-particle kinetics
journal, January 2018
- Liu, Yiliu; Turunen, Petri; de Waal, Bas F. M.
- Molecular Systems Design & Engineering, Vol. 3, Issue 4
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