Conducting polymers : bioinspired intelligent materials and devices

266 Pages·2015·16.672 MB·English

by  Toribio Fernandez Otero, Hans-Jorg Schneider, Mohsen Shahinpoor

Conducting Polymers
Bioinspired Intelligent Materials and Devices
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RSC Smart Materials
Series Editors:
Professor Hans-Jörg Schneider, Saarland University, Germany
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00 Professor Mohsen Shahinpoor, University of Maine, USA
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74 Titles in this Series:
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6 1: Janus Particle Synthesis, Self-Assembly and Applications
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7 2: Smart Materials for Drug Delivery: Volume 1
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7 3: Smart Materials for Drug Delivery: Volume 2
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39/ 4: Materials Design Inspired by Nature
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0.1 5: Responsive Photonic Nanostructures: Smart Nanoscale Optical
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oi: Materials
g | d 6: Magnetorheology: Advances and Applications
or 7: Functional Nanometer-Sized Clusters of Transition Metals: Synthesis,
c.
s.rs Properties and Applications
ub 8: Mechanochromic Fluorescent Materials: Phenomena, Materials and
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p:// Applications
htt 9: Cell Surface Engineering: Fabrication of Functional Nanoshells
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o 10: Biointerfaces: Where Material Meets Biology
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01 11: Semiconductor Nanowires: From Next-Generation Electronics to
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m 12: Supramolecular Materials for Opto-Electronics
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n 25 14: Chemoresponsive Materials: Stimulation by Chemical and Biological
o Signals
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P Chemical Approach Towards Material Science
17: Ionic Polymer Metal Composites (IPMCs): Smart Multi-Functional
Materials and Artificial Muscles, Volume 1
18: Ionic Polymer Metal Composites (IPMCs): Smart Multi-Functional
Materials and Artificial Muscles, Volume 2
19: Conducting Polymers: Bioinspired Intelligent Materials and Devices
How to obtain future titles on publication:
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Conducting Polymers
Bioinspired Intelligent Materials
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97 Toribio Fernández Otero
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03 Technical University of Cartagena, Spain
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0. Email: [email protected]
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org | RSC Smart Materials No. 19
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s.r Print ISBN: 978-1-78262-315-1
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on A catalogue record for this book is available from the British Library
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2 © Toribio Fernández Otero 2016
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5 Apart from fair dealing for the purposes of research for non-commercial purposes or for
n 2 private study, criticism or review, as permitted under the Copyright, Designs and Patents
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ed Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may
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blis not be reproduced, stored or transmitted, in any form or by any means, without the prior
u permission in writing of The Royal Society of Chemistry or the copyright owner, or in
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appropriate Reproduction Rights Organization outside the UK. Enquiries concerning
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Chemistry at the address printed on this page.
The RSC is not responsible for individual opinions expressed in this work.
The authors have sought to locate owners of all reproduced material not in their
own possession and trust that no copyrights have been inadvertently infringed.
Published by the Royal Society of Chemistry,
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Printed in the United Kingdom by CPI Group (UK) Ltd, Croydon, CR0 4YY, UK
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d The proximity paradox: human scientific models predicted the existence of
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or subatomic particles and astronomical structures beyond the borders of the
sc. known universe years before the construction of the required equipment for
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b their observation, but they cannot describe life and life functions that constitute
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n htt TF Otero
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37 Preface
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oi:1 Human scientific knowledge has advanced to different borders. One of these
g | d limits is shown around us and every day we observe it; in fact it takes part of
or ourselves. Life, life functions and malfunctions are outside of the descrip-
c.
s.rs tions or predictions of any scientific model.
ub Present physical models were able to predict the existence of subatomic
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p:// particles or astronomical structures beyond the borders of the explored uni-
htt verse long before we designed and constructed devices required for their
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o observation. But they cannot describe or predict health or illnesses that
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01 constitute our every experience. Life is chemistry. Biochemical reactions
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er include biopolymers and macromolecules as reactants. The reactions induce
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m conformational movements, but current chemical models do not include
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o quantification of any conformational, allosteric or structural reaction-driven
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5 changes.
on 2 Up until the 1980s, chemists did not have at their disposal dense reactive
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he gels that could mimic the intracellular matrix (ICM) of living cells, which
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bli constitutive polymeric chains may participate as reactants in chemical or
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P electrochemical reactions. From them, a plethora of different materials has
emerged, giving electroactive films in liquid electrolytes, including conduct-
ing polymers, redox polymers, fullerenes, carbon nanotubes, graphenes,
phthalocyanines and so on.
In this book the electrochemistry of conducting polymers as reactive gels
that mimic, in its simplest expression (reactive chains, reaction-driven con-
formational movements, ions and water), the composition of the ICM in liv-
ing cells is described.
Electrochemical reactions (oxidation or reduction) from the different fam-
ilies of conducting polymers (Chapter 4) drive conformational movements
of the constitutive polymeric chains and structural macroscopic changes
of the film, such as conformational relaxation, swelling, shrinking and
RSC Smart Materials No. 19
Conducting Polymers: Bioinspired Intelligent Materials and Devices
By Toribio Fernández Otero
© Toribio Fernández Otero 2016
Published by the Royal Society of Chemistry, www.rsc.org
vii
View Online
viii Preface
conformational compaction from different energetic states of trapped ions.
Chapter 6 describes how these reaction-driven structural changes that mimic
biochemical reactions are identified, controlled and quantified.
Such reactive gels can be used as material models of the ICM to obtain the
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0 empirical kinetics of the reaction. The new aspect, from a chemical kinetic
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F point of view, is the possibility of repeating the full, selected kinetic procedure
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4 using different shrunken or conformationally packed initial states. Surpris-
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2 ing results have been attained, such as the activation energy (E ), the reaction
6 a
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8 coefficient (k) and the reaction order being the three of them, which are func-
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8 tions of the initial energetic state of packed conformations. The kinetic mag-
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9/ nitudes include conformational and structural quantitative information: the
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10 chemical kinetics become structural chemical kinetics (Chapter 7).
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1 The electrochemically stimulated conformational relaxation (ESCR)
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d model and the consequential structural chemical kinetic (SCK) model here
org | presented describe the obtained empirical results. Variation of the chain
sc. conformational energy during a reaction reaches a quantitative magnitude.
bs.r The final structural equations for E , k and the reaction orders are adapted
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htt like enzymatic reactions, and allosteric and folding/misfolding effects.
on The faradaic ionic exchange shifts the gel composition by several orders
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1 of magnitude, as functional reactions do in organs. The values of any
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er composition-dependent properties of the material (volume, color, charge
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m storage, ionic storage, ionic conductivity and so on) will change under the
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5 5 is devoted to these composition-dependent properties, each mimicking a
n 2 biological function. Each of these biomimetic properties allows the devel-
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ed opment of a biomimetic device that works in a way driven by the reaction
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blis of the device’s constitutive material, as biological organs do. In this regard,
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decontaminating systems, artificial chemical synapses, chemo-ionic-
conformational memories, smart surfaces, electrochromic devices, organic
batteries, biosensors and mechanical sensors. However, the reaction shifts
the value of each of the composition-dependent properties simultaneously.
This fact opens an unexplored and unexpected scientific and technologi-
cal world of multi-tool devices, where several tools work simultaneously
in a physically uniform device driven by the same reaction. Chapter 9 is
devoted to the exploration of sensing motors, inspired by haptic muscles.
Haptic muscles and the brain give rise to proprioception. Based on electro-
chemical, polymeric and mechanical basic principles, a theoretical model
is presented describing artificial proprioception and the attained experi-
mental results.
A short review of some of the basic electrochemical cells and methods is
given (Chapter 2). Chapter 3 is devoted to the complex mechanism of the
electrochemical synthesis of conducting polymers whose control allows the
synthesis of tailored materials and may help new researchers to understand
the new concepts and principles presented here.
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Preface ix
Some final consideration and remarks related to reactions and structures,
materials and biological structural processes are collected in the final chap-
ter. Challenges in the quantification and prediction of biological reactions
and functions are presented, while the door is left open for a quantitative
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0 description of electro-chemo-conformational memories and brain memory.
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8- Toribio Fernández Otero
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37 Acknowledgements
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oi:1 I have received immeasurable support and encouragement from my parents
g | d and brothers, friends, and co-workers. I could never have completed this
or book without them. I thank God for sending them to support me on this
c.
s.rs journey. This acknowledgements section could never be complete without
ub expressing my sincere gratitude to these individuals.
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p:// I will always be in permanent debt to each and every one of my cultural cow-
htt herd (brañeiros y vaqueiros) brothers from the Cantabric Mountains Range
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o in the northern part of Spain, and in particular to those from my hometown,
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01 Palacios del Sil, where I spent my childhood. I am also in debt to my brañeiros
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er ancestors that kept this isolated and hardy but efficient civilization frozen in
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m time for centuries. They helped that eager boy to mature, while he enjoyed
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o plants, flowers, animals, water springs, rain, snow, sunny days, storms, stars,
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5 and the sky and land. Breathing fresh and clean air from the mountain tops
on 2 and listening every night to old stories around a fire helped me fall in love
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he with nature forever. That civilization of transhumance shepherds has dis-
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bli solved into the wind over the last 30 years but my childhood probably helped
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literature is just focused on a small fraction of the truth sought. We should
always be ready to think outside of the boxes that others have built.
Finding a way through a fog-filled forest under a severe storm is a difficult
task if you don’t have solid reference points. I was blessed when I found my
way to Don José Escudero, my primary school teacher. Had it not been for
him, I would never have become a researcher and would most likely have
spent my life as a coal miner, as many of my elementary school fellows did.
His incessant pressure on my parents and his help teaching me as a free
student for three years (exams were taken annually during a day in June at
the secondary school located 50 km from my town) gave me the possibility
to combine my student and shepherd duties. I was quite fortunate to find
RSC Smart Materials No. 19
Conducting Polymers: Bioinspired Intelligent Materials and Devices
By Toribio Fernández Otero
© Toribio Fernández Otero 2016
Published by the Royal Society of Chemistry, www.rsc.org
xi
View Online
xii Acknowledgements
some good teachers in my life, but Don José Escudero remains my master
and milestone.
Some days with grazing cows and goats were long when I was growing up.
The temptation to climb the surrounding mountains was invariably there
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1 and I learned that behind a mountain you will always find new mountains
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F and, in between them, you will find new forests, rivers, lakes and rocks.
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2 I am both scientifically and personally indebted to many people that I
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8 have met on my journey. Dr M. Sánchez Cruz from the Rocasolano Institute
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8 of the CSIC was my thesis supervisor, who revealed to me the fascinating
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10 for many years of the Journal of Electroanalytical Chemistry, encouraged me
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1 by correcting several of my first papers and giving me useful experimental
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d advice. Without the heartening effort of this personally involved editor, I may
org | not have pursued my career as a scientist. After finishing my Ph.D. I moved
sc. to the newly founded Faculty of Chemistry in San Sebastian (Basque Coun-
bs.r try), which was to become devoted to the development of polymer science
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p:// and polymer technologies. After several hard years organizing and delivering
htt teaching activities I started a new research group, with the help of tenacious
on students, with the aim of combining my electrochemical background with
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1 polymers. This was at the beginning of the 1980s, when the first papers from
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er the MacDiarmid, Diaz and Osada groups were published. By repeating the
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m experimental results from Prof. Diaz’s papers on electropolymerization and
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ov the electrochemical characterization of the generated films, this fascinating
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5 journey was initiated. Without Prof. MacDiarmid’s and Osada’s encouraging
n 2 comments, which they shared any time I had the chance to meet them (at
o
ed least once per year), I probably would have moved to another polymeric field.
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blis Since then, tens of Ph.D. and Masters students have devoted their time and
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is with all of them. Dr Melling has reviewed the original manuscript giving a
lot of useful advice and comments, thanks Dan.
Finally, I must be thankful for the deep economic crisis that has affected
Spain over the last five years: the number of students in my laboratory has
dropped to one. The upside of this is that I finally got the time to write this
book.
Without the unwavering emotional and spiritual support of my wife Ana,
my sons Miguel and Juan, and my daughters-in-law, I would never have
embarked on this journey, let alone complete it. Their constant support is
the cornerstone of my life and I can never thank them enough.