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Chemistry

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

Published: September 26th, 2016

DOI:

10.3791/54503

1Biological and Environmental Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), 2Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, 3Department of Organic and Polymeric Materials, Tokyo Institute of Technology

A protocol for the synthesis and characterization of diffusive motion of cyclic polymers at the single molecule level is presented.

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used for the synthesis of the cyclic poly(tetrahydrofuran) (poly(THF)). The diffusive motion of individual cyclic polymer chains in a melt state is visualized using single molecule fluorescence imaging by incorporating a fluorophore unit in the cyclic chains. The diffusive motion of the chains is quantitatively characterized by means of a combination of mean-squared displacement (MSD) analysis and a cumulative distribution function (CDF) analysis. The cyclic polymer exhibits multiple-mode diffusion which is distinct from its linear counterpart. The results demonstrate that the diffusional heterogeneity of polymers that is often hidden behind ensemble averaging can be revealed by the efficient synthesis of the cyclic polymers using the ESA-CF process and the quantitative analysis of the diffusive motion at the single molecule level using the MSD and CDF analyses.

Cyclic polymers are unique in that they do not have chain ends. They often exhibit unusual behaviors which is distinct from their linear counterpart, including increased thermal stability of polymer micelles by a linear-to-cyclic conversion,1,2 and spatial organization of DNA in bacterial cells by a loop formation.3 Topological interactions between the cyclic chains are believed to be the critical factor for such unusual behaviors.4,5 Therefore, characterizing the motion and relaxation of cyclic polymers under entangled conditions has been an important research topic in polymer science for decades.6

This work was supported by a Grant-in-Aid for Scientific Research No. 22750122 (S.H.), No. 26288099 (T.Y.), and No. 23350050 (Y.T.) of the Japan Society for the Promotion of Science. S.H. is grateful for The Kurata Memorial Hitachi Science and Technology Foundation. The research reported in this publication was supported by the King Abdullah University of Science and Technology (S.H.).

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Name Company Catalog Number Comments
Materials
THF Godo
Wakosil C-300 Wako Pure Chemical Industries
Acetone Godo
Toluene Godo
n-Hexane Godo
CHCl3 Kanto Chemical
Bio-Beads S-X1 Bio-Rad
Methyl triflate Nacalai Tesque
Triflic anhydride Nacalai Tesque
Potassium Hydroxide Wako Pure Chemical Industries
Ethanol Wako Pure Chemical Industries
Poly(tetrahydrofuran) Aldrich
Chloroform Wako Pure Chemical Industries
Immersion oil Cargille Type 37 / Type A
Equipment
2-Neck 100-mL round-bottom flask
Flask
Beaker
Funnel
Filter paper Whatman
Reflux condenser
Syringe
Water bath
Magnetic stirrer
Rotary evaporator
Microscope cover slips (24 x 24 mm, No. 1) Matsunami Glass CO22241
Staining jar AS ONE Corporation 1-7934-01
Ultrasonic cleaner VWR International  142-0047
Inverted microscope Olympus IX71
Ar-Kr ion laser Coherent Innova 70C
Berek compensator Newport 5540
Excitation filter Semrock LL01-488-12.5
Dichloric mirror Omega optical 500DRLP
Emission filter Semrock BLP01-488R-25
Lens and mirror Thorlabs
EM-CCD camera Andor Technology iXon
Objective lens (x100, N.A. = 1.3) Olympus UPLFLN 100XOP
Objective heater Bioptechs
Preparative GPC Japan Analytical Industry LC-908

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