skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesizing a Trefoil Knotted Block Copolymer via Ring-Expansion Strategy

Abstract

We synthesized a synthetic trefoil knotted poly(e-caprolatone) block-poly(L-lactide) (TK-PLA-b-PCL) via a ring expansion strategy from a trefoil knotted tin (Sn) initiator. Ring closing reaction between the bis-copper(I) templated phenanthro line complex and dibutyldimethoxytin results in a templated trefoil knotted initiator. Furthermore, the bis-copper(I) templated trefoil knotted poly(L-lactide) (TK-PLA) can be synthesized by ring-opening polymerization of L-lactide monomer, and decomplexation reaction of the templated TK-PLA will result in a geniune TK-PLA without constraint from the copper template. Subsequent insertion of e caprolactone in the bis-copper(I) templated TK-PLA forms the templated trefoil knotted block copolymer, i.e., TK-PLA-b-PCL, and the copper-free TK-PLA-b-PCL can be obtained by decomplexation reaction. Finally, both TK-PLA and TK-PLA-b-PCL are analyzed by the 1 H NMR, FT-IR, UV-vis, DLS, and GPC.

Authors:
 [1];  [2];  [2];  [1]
  1. ORNL
  2. Case Western Reserve University
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1354670
Grant/Contract Number:  
AC05-00OR22725; NSF-1608457; NSF-1333651
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 50; Journal Issue: 4; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Cao, Pengfei, Rong, Li-Han, Mangadlao, Joey, and Advincula, Rigoberto C. Synthesizing a Trefoil Knotted Block Copolymer via Ring-Expansion Strategy. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.macromol.6b02029.
Cao, Pengfei, Rong, Li-Han, Mangadlao, Joey, & Advincula, Rigoberto C. Synthesizing a Trefoil Knotted Block Copolymer via Ring-Expansion Strategy. United States. https://doi.org/10.1021/acs.macromol.6b02029
Cao, Pengfei, Rong, Li-Han, Mangadlao, Joey, and Advincula, Rigoberto C. Tue . "Synthesizing a Trefoil Knotted Block Copolymer via Ring-Expansion Strategy". United States. https://doi.org/10.1021/acs.macromol.6b02029. https://www.osti.gov/servlets/purl/1354670.
@article{osti_1354670,
title = {Synthesizing a Trefoil Knotted Block Copolymer via Ring-Expansion Strategy},
author = {Cao, Pengfei and Rong, Li-Han and Mangadlao, Joey and Advincula, Rigoberto C},
abstractNote = {We synthesized a synthetic trefoil knotted poly(e-caprolatone) block-poly(L-lactide) (TK-PLA-b-PCL) via a ring expansion strategy from a trefoil knotted tin (Sn) initiator. Ring closing reaction between the bis-copper(I) templated phenanthro line complex and dibutyldimethoxytin results in a templated trefoil knotted initiator. Furthermore, the bis-copper(I) templated trefoil knotted poly(L-lactide) (TK-PLA) can be synthesized by ring-opening polymerization of L-lactide monomer, and decomplexation reaction of the templated TK-PLA will result in a geniune TK-PLA without constraint from the copper template. Subsequent insertion of e caprolactone in the bis-copper(I) templated TK-PLA forms the templated trefoil knotted block copolymer, i.e., TK-PLA-b-PCL, and the copper-free TK-PLA-b-PCL can be obtained by decomplexation reaction. Finally, both TK-PLA and TK-PLA-b-PCL are analyzed by the 1 H NMR, FT-IR, UV-vis, DLS, and GPC.},
doi = {10.1021/acs.macromol.6b02029},
journal = {Macromolecules},
number = 4,
volume = 50,
place = {United States},
year = {2017},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Tying up some loose ends
journal, February 2010


DNA knots reveal a chiral organization of DNA in phage capsids
journal, June 2005

  • Arsuaga, J.; Vazquez, M.; McGuirk, P.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 26
  • DOI: 10.1073/pnas.0409323102

Frameshifting RNA pseudoknots: Structure and mechanism
journal, February 2009


Structures and folding pathways of topologically knotted proteins
journal, December 2010


A deeply knotted protein structure and how it might fold
journal, August 2000


Experimental detection of knotted conformations in denatured proteins
journal, April 2010

  • Mallam, A. L.; Rogers, J. M.; Jackson, S. E.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 18
  • DOI: 10.1073/pnas.0912161107

Identification of Rare Slipknots in Proteins and Their Implications for Stability and Folding
journal, October 2007

  • King, Neil P.; Yeates, Eric O.; Yeates, Todd O.
  • Journal of Molecular Biology, Vol. 373, Issue 1
  • DOI: 10.1016/j.jmb.2007.07.042

Chemical Topology: Complex Molecular Knots, Links, and Entanglements
journal, September 2011

  • Forgan, Ross S.; Sauvage, Jean-Pierre; Stoddart, J. Fraser
  • Chemical Reviews, Vol. 111, Issue 9
  • DOI: 10.1021/cr200034u

Template synthesis of molecular knots
journal, January 2013

  • Ayme, Jean-François; Beves, Jonathon E.; Campbell, Christopher J.
  • Chem. Soc. Rev., Vol. 42, Issue 4
  • DOI: 10.1039/C2CS35229J

Stereoselective Synthesis of a Topologically Chiral Molecule: The Trefoil Knot
journal, August 2004

  • Perret-Aebi, Laure-Emmanuelle; von Zelewsky, Alexander; Dietrich-Buchecker, Christiane
  • Angewandte Chemie International Edition, Vol. 43, Issue 34
  • DOI: 10.1002/anie.200460250

Synthesis of a molecular trefoil knot by folding and closing on an octahedral coordination template
journal, February 2010

  • Guo, Jun; Mayers, Paul C.; Breault, Gloria A.
  • Nature Chemistry, Vol. 2, Issue 3
  • DOI: 10.1038/nchem.544

Lanthanide Template Synthesis of Trefoil Knots of Single Handedness
journal, August 2015

  • Zhang, Gen; Gil-Ramírez, Guzmán; Markevicius, Augustinas
  • Journal of the American Chemical Society, Vol. 137, Issue 32
  • DOI: 10.1021/jacs.5b07069

Knot tied around an octahedral metal centre
journal, June 2001

  • Adams, Harry; Ashworth, Eleanor; Breault, Gloria A.
  • Nature, Vol. 411, Issue 6839
  • DOI: 10.1038/35081143

A Trefoil Knot Made of Amino Acids and Steroids
journal, August 2006

  • Feigel, Martin; Ladberg, Rüdiger; Engels, Simon
  • Angewandte Chemie International Edition, Vol. 45, Issue 34
  • DOI: 10.1002/anie.200601111

Discovery of an Organic Trefoil Knot
journal, November 2012


The application of CuAAC ‘click’ chemistry to catenane and rotaxane synthesis
journal, January 2010

  • Hänni, Kevin D.; Leigh, David A.
  • Chem. Soc. Rev., Vol. 39, Issue 4
  • DOI: 10.1039/B901974J

Topological polymer chemistry: a cyclic approach toward novel polymer properties and functions
journal, January 2011

  • Yamamoto, Takuya; Tezuka, Yasuyuki
  • Polymer Chemistry, Vol. 2, Issue 9
  • DOI: 10.1039/c1py00088h

Architectural Differentiation of Linear and Cyclic Polymeric Isomers by Ion Mobility Spectrometry-Mass Spectrometry
journal, September 2011

  • Hoskins, Jessica N.; Trimpin, Sarah; Grayson, Scott M.
  • Macromolecules, Vol. 44, Issue 17
  • DOI: 10.1021/ma2012046

Gels Based on Cyclic Polymers
journal, March 2011

  • Zhang, Ke; Lackey, Melissa A.; Cui, Jun
  • Journal of the American Chemical Society, Vol. 133, Issue 11, p. 4140-4148
  • DOI: 10.1021/ja111391z

Cyclic poly(vinylcarbazole) via ring-expansion polymerization-RAFT (REP-RAFT)
journal, July 2014


Cyclic polyesters: synthetic approaches and potential applications
journal, January 2011

  • Hoskins, Jessica N.; Grayson, Scott M.
  • Polym. Chem., Vol. 2, Issue 2
  • DOI: 10.1039/C0PY00102C

The Synthesis of Cyclic Poly(ethylene imine) and Exact Linear Analogues: An Evaluation of Gene Delivery Comparing Polymer Architectures
journal, May 2015

  • Cortez, Mallory A.; Godbey, W. T.; Fang, Yunlan
  • Journal of the American Chemical Society, Vol. 137, Issue 20
  • DOI: 10.1021/jacs.5b00980

Recent progress on cyclic polymers: Synthesis, bioproperties, and biomedical applications
journal, February 2016

  • Tu, Xiao-Yan; Liu, Ming-Zhu; Wei, Hua
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 54, Issue 11
  • DOI: 10.1002/pola.28051

Effective Synthesis of Polymer Catenanes by Cooperative Electrostatic/Hydrogen-Bonding Self-Assembly and Covalent Fixation
journal, November 2009

  • Ishikawa, Kazuyuki; Yamamoto, Takuya; Asakawa, Masumi
  • Macromolecules, Vol. 43, Issue 1
  • DOI: 10.1021/ma902031j

Preparation, Characterization, and Nanophase-Separated Structure of Catenated Polystyrene−Polyisoprene
journal, May 2008

  • Ohta, Yutaka; Kushida, Yuuki; Kawaguchi, Daisuke
  • Macromolecules, Vol. 41, Issue 11
  • DOI: 10.1021/ma7028852

A supramolecularly templated catenane initiator and a controlled ring expansion strategy
journal, January 2012

  • Cao, Peng-Fei; Bunha, Ajaykumar; Mangadlao, Joey
  • Chemical Communications, Vol. 48, Issue 99
  • DOI: 10.1039/c2cc35588d

Polymeric catenanes synthesized via “click” chemistry and atom transfer radical coupling
journal, January 2015

  • Bunha, Ajaykumar; Cao, Peng-Fei; Mangadlao, Joey
  • Chemical Communications, Vol. 51, Issue 35
  • DOI: 10.1039/C5CC00373C

Catenated Poly(ε-caprolactone) and Poly( l -lactide) via Ring-Expansion Strategy
journal, June 2015


Synthesis, separation and characterization of knotted ring polymers
journal, January 2012


Imaging of Catenated, Figure-of-Eight, and Trefoil Knot Polymer Rings
journal, July 2009


Open Problems in Chemical Topology
journal, October 2008


Influence of a knot on the strength of a polymer strand
journal, May 1999

  • Saitta, A. Marco; Soper, Paul D.; Wasserman, E.
  • Nature, Vol. 399, Issue 6731
  • DOI: 10.1038/19935

Self-assembling knots of controlled topology by designing the geometry of patchy templates
journal, March 2015

  • Polles, Guido; Marenduzzo, Davide; Orlandini, Enzo
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7423

How Local Flexibility Affects Knot Positioning in Ring Polymers
journal, June 2016


A Trefoil Knotted Polymer Produced through Ring Expansion
journal, February 2015

  • Cao, Peng-Fei; Mangadlao, Joey; Advincula, Rigoberto
  • Angewandte Chemie International Edition, Vol. 54, Issue 17
  • DOI: 10.1002/anie.201411623

Surface Chemistry of Biodegradable Polymers for Drug Delivery Systems
journal, November 2005

  • Ha, Chang-Sik; Gardella, Joseph A.
  • Chemical Reviews, Vol. 105, Issue 11
  • DOI: 10.1021/cr040419y

Modulating the guest encapsulation and release properties of multi-arm star polyethylenimine- block -poly(ε-caprolactone)
journal, October 2009

  • Cao, Peng-Fei; Xiang, Rui; Liu, Xun-Yong
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 47, Issue 19
  • DOI: 10.1002/pola.23568

Degradation and Controlled Release Behavior of ε-Caprolactone Copolymers in Biodegradable Antifouling Coatings
journal, March 2006

  • Faÿ, Fabienne; Linossier, Isabelle; Langlois, Valérie
  • Biomacromolecules, Vol. 7, Issue 3
  • DOI: 10.1021/bm0509669

Dual Functional Nanocarrier for Cellular Imaging and Drug Delivery in Cancer Cells Based on π-Conjugated Core and Biodegradable Polymer Arms
journal, February 2016

  • Kulkarni, Bhagyashree; Surnar, Bapurao; Jayakannan, Manickam
  • Biomacromolecules, Vol. 17, Issue 3
  • DOI: 10.1021/acs.biomac.5b01654

Recent Developments in Ring Opening Polymerization of Lactones for Biomedical Applications
journal, November 2003

  • Albertsson, Ann-Christine; Varma, Indra K.
  • Biomacromolecules, Vol. 4, Issue 6
  • DOI: 10.1021/bm034247a

Compatibilized Polymer Blends Based on PDLLA and PCL for Application in Bioartificial Liver
journal, May 2008

  • Calandrelli, Luigi; Calarco, Anna; Laurienzo, Paola
  • Biomacromolecules, Vol. 9, Issue 6
  • DOI: 10.1021/bm7013087

Electrospun Nanofibrous P(DLLA–CL) Balloons as Calcium Phosphate Cement Filled Containers for Bone Repair: in Vitro and in Vivo Studies
journal, August 2015

  • Liu, Xunwei; Wei, Daixu; Zhong, Jian
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 33
  • DOI: 10.1021/acsami.5b04868

Random Copolymerization of ε-Caprolactone and Lactides Promoted by Pyrrolylpyridylamido Aluminum Complexes
journal, October 2012

  • Li, Gang; Lamberti, Marina; Pappalardo, Daniela
  • Macromolecules, Vol. 45, Issue 21
  • DOI: 10.1021/ma3019848

Biodegradable polymers with variable architectures via ring-expansion polymerization
journal, January 2004

  • Kricheldorf, Hans R.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 42, Issue 19
  • DOI: 10.1002/pola.20261

Active-Metal Template Synthesis of a Molecular Trefoil Knot
journal, September 2011

  • Barran, Perdita E.; Cole, Harriet L.; Goldup, Stephen M.
  • Angewandte Chemie International Edition, Vol. 50, Issue 51
  • DOI: 10.1002/anie.201105012

Strategies and Tactics for the Metal-Directed Synthesis of Rotaxanes, Knots, Catenanes, and Higher Order Links
journal, September 2011

  • Beves, Jonathon E.; Blight, Barry A.; Campbell, Christopher J.
  • Angewandte Chemie International Edition, Vol. 50, Issue 40
  • DOI: 10.1002/anie.201007963

Polymer catenanes via a supramolecularly templated ATRP initiator
journal, January 2011

  • Bunha, Ajaykumar; Tria, Maria Celeste; Advincula, Rigoberto
  • Chemical Communications, Vol. 47, Issue 32
  • DOI: 10.1039/c1cc13162a

Cyclic Polymers by Kinetically Controlled Step-Growth Polymerization
journal, April 2003

  • Kricheldorf, Hans R.; Schwarz, Gert
  • Macromolecular Rapid Communications, Vol. 24, Issue 56
  • DOI: 10.1002/marc.200390063

Zwitterionic Polymerization: A Kinetic Strategy for the Controlled Synthesis of Cyclic Polylactide
journal, March 2009

  • Jeong, Wonhee; Shin, Eun Ji; Culkin, Darcy A.
  • Journal of the American Chemical Society, Vol. 131, Issue 13
  • DOI: 10.1021/ja809617v

Zwitterionic Copolymerization: Synthesis of Cyclic Gradient Copolymers
journal, May 2011

  • Shin, Eun Ji; Brown, Hayley A.; Gonzalez, Silvia
  • Angewandte Chemie International Edition, Vol. 50, Issue 28
  • DOI: 10.1002/anie.201101853

Dicopper(I) Trefoil Knots:  Topological and Structural Effects on the Demetalation Rates and Mechanism
journal, May 1997

  • Meyer, Michel; Albrecht-Gary, Anne-Marie; Dietrich-Buchecker, Christiane O.
  • Journal of the American Chemical Society, Vol. 119, Issue 20
  • DOI: 10.1021/ja963737q

Synthesis of Macrocyclic Poly(ɛ-caprolactone) by Intramolecular Cross-Linking of Unsaturated End Groups of Chains Precyclic by the Initiation
journal, March 2006

  • Li, Haiying; Debuigne, Antoine; Jérome, Robert
  • Angewandte Chemie International Edition, Vol. 45, Issue 14
  • DOI: 10.1002/anie.200503961

Amphiphilic Sun-Shaped Polymers by Grafting Macrocyclic Copolyesters with PEO
journal, February 2008

  • Li, Haiying; Jérôme, Robert; Lecomte, Philippe
  • Macromolecules, Vol. 41, Issue 3
  • DOI: 10.1021/ma070282o

    Works referencing / citing this record:

    Polymer Nanosheet Containing Star-Like Copolymers: A Novel Scalable Controlled Release System
    journal, April 2018


    Continuous Flow Fabrication of Block Copolymer–Grafted Silica Micro‐Particles in Environmentally Friendly Water/Ethanol Media
    journal, October 2018

    • Ye, Piaoran; Cao, Peng‐Fei; Chen, Qiyi
    • Macromolecular Materials and Engineering, Vol. 304, Issue 2
    • DOI: 10.1002/mame.201800451

    Discovering privileged topologies of molecular knots with self-assembling models
    journal, August 2018