Cholesterol-substituted 3,4-ethylenedioxythiophene (EDOT-MA-cholesterol) and Poly(3,4-ethylenedioxythiophene) (PEDOT-MA-cholesterol)
| Author(s) | Wu, Yuhang | |
| Author(s) | Nagane, Samadhan S. | |
| Author(s) | Baugh, Quintin | |
| Author(s) | Lo, Chun-Yuan | |
| Author(s) | Chhatre, Shrirang S. | |
| Author(s) | Lee, Junghyun | |
| Author(s) | Sitarik, Peter | |
| Author(s) | Kayser, Laure V. | |
| Author(s) | Martin, David C. | |
| Date Accessioned | 2023-08-10T20:20:17Z | |
| Date Available | 2023-08-10T20:20:17Z | |
| Publication Date | 2023-05-23 | |
| Description | This article was originally published in Giant. The version of record is available at: https://doi.org/10.1016/j.giant.2023.100163. ©2023 The Author(s). Published by Elsevier Ltd. | |
| Abstract | Cholesterol is a rigid, crystalline, non-polar natural substance that exists in animal blood and cell membranes. Some of its derivatives are known to form ordered liquid crystalline mesophases under suitable conditions. In this work, we carefully examined the influence of cholesterol substitution on the characteristics of 3,4-ethylenedioxythiophene (EDOT-MA-cholesterol) and its corresponding polymer poly(3,4-ethylenedioxythiophene) (PEDOT-MA-cholesterol) synthesized by both chemical and electrochemical polymerization. We found evidence for an ordered lamellar (smectic-like) structure in the EDOT-MA-cholesterol monomer by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X-ray diffraction techniques. The ordered phase was observed to form on cooling from the isotropic melt at about 80 °C. Due to the insulating and bulky cholesterol side group on the EDOT monomer, we found that there was a maximum charge density for electrodeposition at ∼ 0.155 C.cm−2. A series of electrodepositions were performed from 0 to 0.155 C.cm−2 for probing the change of the charge transport with more charges used for the electrodeposition. We found that the impedance increased in the high-frequency range (above 104 Hz) and decreased in the low-frequency range (below 102 Hz). Three equivalent circuit models were proposed for fitting impedance data at different charge densities for a better understanding of the film growth process. The suppressed cyclic voltammogram (CV) of PEDOT-MA-cholesterol showed that the charge storage capability was essentially eliminated in the thickest films. The limited doping of the films was corroborated by their diminished electrochromic behavior, polaron-dominating absorption in UV-vis, overoxidized S 2p X-ray Photoelectron Spectroscopy (XPS) signal of electrodeposited films, and proton Nuclear Magnetic Resonance (1H NMR) of chemically polymerized samples. Dense film morphologies were confirmed by scanning electron microscopy (SEM). Grazing incident X-ray diffraction (GIWAXS) indicated the disrupted stacking of conjugated chains, which correlated with the decreased conductivity of the PEDOT-MA-cholesterol films. The measurement of the electrical conductivity gave a value of around 3.30 × 10−6 S.cm−1 which is about six orders of magnitude lower than has been seen in PEDOT (∼3 S.cm-1). Graphical abstract available at: https://doi.org/10.1016/j.giant.2023.100163 | |
| Sponsor | This research was supported in part by the National Science Foundation (Grant No. DMR-1808048), the Air Force Office of Scientific Research MSIT Program for Next Generation Nanosystems, and the University of Delaware. The authors appreciate the help offered by Dr. Jing Qu for X-ray diffraction-related characterization and Dr. Chin Chen Kuo for DSC and TGA. We would like to thank Dr. Chandran Sabanayagam for his assistance with AFM-related characterization. We would like to thank Dr. Yong Zhao for the help provided on morphological analysis and cross-section imaging. We acknowledge the Advanced Materials Characterization Lab for use of their X-ray diffraction facility, DSC, and TGA, Surface Analysis Facility for XPS, the W. M. Keck Center for Advanced Microscopy and Microanalysis for their SEM, and the Bio-imaging Center of the Delaware Biotechnology institute for their AFM (Delaware INBRE grant #P20 GM103446). DCM thanks Emily Barbato, Dillon Belser, Bret Snodderly, and Yang Yu from his Spring 2023 MSEG 467/667 course on Electronically and Ionically Active Organic Molecular and Polymer Materials for their constructive comments on this manuscript. Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: David C. Martin reports financial support was provided by National Science Foundation. David C. Martin reports financial support was provided by The University of Delaware. David C. Martin has patent Biofunctional Thiophene Monomers pending to The University of Delaware. | |
| Citation | Wu, Yuhang, Samadhan S. Nagane, Quintin Baugh, Chun-Yuan Lo, Shrirang S. Chhatre, Junghyun Lee, Peter Sitarik, Laure V. Kayser, and David C. Martin. “Cholesterol-Substituted 3,4-Ethylenedioxythiophene (EDOT-MA-Cholesterol) and Poly(3,4-Ethylenedioxythiophene) (PEDOT-MA-Cholesterol).” Giant 15 (2023): 100163. https://doi.org/10.1016/j.giant.2023.100163. | |
| ISSN | 2666-5425 | |
| URL | https://udspace.udel.edu/handle/19716/33063 | |
| Language | en_US | |
| Publisher | Giant | |
| dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | |
| Keywords | cholesterol-substituted EDOT | |
| Keywords | cholesterol-substituted PEDOT | |
| Keywords | ordered smectic-like structures | |
| Keywords | surface roughness | |
| Keywords | electrodeposition | |
| Keywords | charge transport | |
| Title | Cholesterol-substituted 3,4-ethylenedioxythiophene (EDOT-MA-cholesterol) and Poly(3,4-ethylenedioxythiophene) (PEDOT-MA-cholesterol) | |
| Type | Article |
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