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(Download PDF) Mechanochemistry in Materials 1St Edition Simon Online Ebook All Chapter PDF
(Download PDF) Mechanochemistry in Materials 1St Edition Simon Online Ebook All Chapter PDF
(Download PDF) Mechanochemistry in Materials 1St Edition Simon Online Ebook All Chapter PDF
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Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-FP001
Mechanochemistry in Materials
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Editor-in-chief:
Ben Zhong Tang, The Hong Kong University of Science and Technology,
Hong Kong, China
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-FP001
Series editors:
Alaa S. Abd-El-Aziz, University of Prince Edward Island, Canada
Stephen L. Craig, Duke University, USA
Jianhua Dong, National Natural Science Foundation of China, China
Toshio Masuda, Shanghai University, China
Christoph Weder, University of Fribourg, Switzerland
Applications
11: Phosphorus-Based Polymers: From Synthesis to Applications
12: Poly(lactic acid) Science and Technology: Processing, Properties,
Additives and Applications
13: Cationic Polymers in Regenerative Medicine
14: Electrospinning: Principles, Practice and Possibilities
15: Glycopolymer Code: Synthesis of Glycopolymers and their Applications
16: Hyperbranched Polymers: Macromolecules in-between Deterministic
Linear Chains and Dendrimer Structures
17: Polymer Photovoltaics: Materials, Physics, and Device Engineering
18: Electrical Memory Materials and Devices
19: Nitroxide Mediated Polymerization: From Fundamentals to
Applications in Materials Science
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Mechanochemistry in Materials
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-FP001
Edited by
Yoan C. Simon
University of Southern Mississippi, USA
Email: yoan.simon@usm.edu
and
Stephen L. Craig
Duke University, USA
Email: stephen.craig@duke.edu
.
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-FP001 View Online
A catalogue record for this book is available from the British Library
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Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-FP007
Preface
decades ago a mechanically “smart” material was one whose properties were
well suited to its intended use. Materials were designed to withstand a cer-
tain load or to allow a certain amount of deformation. The material had to
resist or comply. In the intervening years, the moniker of smart materials
came to refer to systems that are capable of responding in a predetermined
manner to a given stimulus. Examples of smart materials include pH-respon-
sive micelles for drug delivery, programmable shape-memory materials that
can twist and tie or even materials that can move left or right depending on
the polarization of incident light. It is now clear that mechanical response
can be used as a similar stimulus-response mechanism.
Growing up as kids, judo was a somewhat popular sport and while neither
of us practiced it one of the elementary tenets of that martial art is the utili-
zation of the force of one’s opponent to one’s own advantage. One can draw
an analogy between mechanochemistry and this creed. Indeed, after many
vii
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viii Preface
years of designing materials to fight the effect of mechanical action (which
thankfully we still do for certain structural components), it is now clear that
mechanical force can be used to one’s advantage. The present treatise looks
at the contribution from various researchers from around the world towards
that direction. The range of scientists from different backgrounds is nec-
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-FP007
Preface ix
conditions, the nature of the matrix and kinetics considerations pertaining
to the mechanophore.
Along these lines, it is interesting to evaluate the influence that other
chains can have on the overall mechanoresponsiveness, especially via the
introduction of directional non-covalent interactions. Chapter 5 goes over
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-FP007
Contents
2.1 I ntroduction 36
2.2 Creation of Reactive Species 37
2.2.1 Radicals 37
2.2.2 Carbon Cations 38
2.2.3 Reactive Organic Functional Groups 39
2.3 Catalyst Activation 42
xi
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xii Contents
2.4 Spectral Change 44
2.5 Production of Small Molecules 47
2.6 Other 48
2.7 Conclusions and Perspectives 49
References 50
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-FP011
3.1 Introduction 53
3.2 ond–Isomerization Reactions
B 55
3.3 Covalent Bond Scission Reactions 58
3.4 Conjugated Polymers 63
3.5 Chromophore Rearrangement 64
3.6 Photonic Polymers and Cholesteric
Liquid Crystals 67
3.7 Conclusion 69
Acknowledgements 70
References 70
4.1 Introduction 76
.
Contents xiii
5.2.1 C oil-to-stretch Transition and
Bead-rod Model 120
5.2.2 Intra-chain Non-covalent Interactions 121
5.2.3 Inter-chain Non-covalent Interactions 123
5.2.4 Non-covalent Interactions in the Bulk 125
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-FP011
References 148
xiv Contents
7.3 M odeling Force-controlled Entrainment of BZ Gels 173
7.3.1 Phase Dynamics Equations for
Mechanically Deformed BZ Gels 174
7.3.2 Entraining the Responsive BZ Gel 176
7.4 Self-oscillating Gels Coupled Through
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-FP011
Chapter 1
Mechanochemistry: Inspiration
from Biology
TAMUKA CHIDANGURO, WENGUI WENG and Yoan C. Simon*
1
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2 Chapter 1
Aristotle’s student, first recorded that grinding cinnabar in a copper mortar
using a brass pestle could reduce it to mercury.2 In the 19th century, Faraday
and Lea applied sliding and grinding to study the chemical reactions of solid
substances.3
In many other ways though, for the better part of its existence, humankind
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-00001
has tried to use materials that would minimize their alteration upon applica-
tion of force. For instance, Damascus steel, which dates back to 900 AD, was a
metal of choice for weaponry as it remarkably exhibited superplasticity along
with incredible levels of hardness. Interestingly, it is also one of the early
examples (though unwittingly) of nanotechnology and mechanochemistry
as carbon nanotubes as well as cementite nanowires were proven to form
during the forging and annealing of Indian wootz steel. It is indeed believed
that the combination of heat and mechanical action along with impurities
in the ore (including carburizing wood and leave additives) was responsible
for the catalyzing the process responsible for the formation of these nano-
structures and the characteristic wavy patterns.4 The quest for materials that
would best resist mechanical constraints has been a technological driving
force throughout the Anthropocene and the field of polymer science is no
exception to this pursuit. For example, worldwide many groups have been
looking at nanocomposites as a source of reinforcement of lightweight mate-
rials, with many of these solutions having made it to commercial products in
the fields of transportation, construction or even appliances.5
From Staudinger to Melville,6,7 mechanical force was studied early on and
the random scission often seen as a foe engendering undesirable chain scis-
sion and weakening or worse causing the rupture of polymeric materials.
.
However, in the early 2000s, a new idea emerged in the realm of polymer
science.8 Namely, it became apparent that one could utilize mechanical force
to one’s advantage rather than combating it. Sensing, repair or self-stiffening
were some of the many putative functionalities proposed in the context of mech-
anochemistry (which have been achieved today and are described in detail
in the following chapters). Interestingly and regardless of whether Nature
was a source of inspiration for some of the seminal work, it is worth noting
that these very functions are ubiquitous in biological systems. Like in many
other areas of the sciences, materials researchers recognized early on that
one could learn a tremendous amount of information from studying biolog-
ical materials and understanding how millennia of evolutions have shaped
the functionalities of biological systems. Consequently, the present chapter
focuses on the mechanochemical strategies developed by Nature to achieve
some of the aforementioned functions. It aims to familiarize materials sci-
entists (who may not always have the opportunity to investigate them) with
some of the biomechanics and biophysics reports that cover these intricate
(and sometimes not entirely understood) processes. This chapter was writ-
ten from a polymer scientist’s perspective and will therefore remain partial
and sometimes simplistic. This “editorial line” is substantiated by two main
reasons. First, the audience of this book is presumed to be mostly polymer
researchers and it would be illusory to condense the complexity of biological
mechanotransduction pathways and make it fully accessible in a few pages.
View Online
cal forces. Instead, one can draw overarching guiding principles upon which
to base his/her reflection and ultimately the design of biomimetic mecha-
notransducers. Interestingly, there are already several reports of materials
which are (wittingly or not) akin to biological systems and, whenever suit-
able, we will draw a parallel between artificial and biological systems.
4 Chapter 1
10
forces as well as out-of-equilibrium dynamics. While the former are readily
achievable and have been realized in the field of mechanochemistry (see Chap-
ter 5), the latter is harder to implement in synthetic systems as dissipative
structures are still a research curiosity. It is interesting to note that many of
the biological systems involved in mechanotransduction in cells are either in
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-00001
require long fabrication time and are consequently rather costly. Of concern
also when designing next-generation mechanoresponsive polymers is the
introduction of environmental cost in the equation of the design of said
materials. Much like Nature chose to use limited raw materials, it would make
sense in the long run to limit oneself to non-deleterious starting materials
and/or materials that can be easily recycled/reused or degraded.
Whenever possible, the best approach to ensure the success of biomimetic
strategies takes advantage of the synergistic combination of diverse expertise
(e.g. biophysicists, to synthetic chemists, material scientists, computational
chemists and bioengineers). It is only through the combination of these
know-hows that we will succeed in developing not only passively smart mate-
rials (i.e. that will be pre-programmed to respond by means of set transitions)
but also actively smart materials (i.e. whereby a feedback loop serves to mod-
ulate the response as proposed in Chapter 7 of this monograph).
16 Chapter 1
Published on 24 October 2017 on http://pubs.rsc.org | doi:10.1039/9781782623885-00001
.
Figure 1.8
Interaction between cell binding and mechanics as illustrated by the
spatial positioning of RGD and PHSRN loops in fibronectin. Forces in
the tens of pN are sufficient to modulate integrin specificity by altering
the distance between these two loops. Reproduced from ref. 38 with
permission from The Royal Society of Chemistry.
Work done by Discher et al. in their investigation of red blood cell (RBC)
protein, β-spectrin, also showed how mechanical forces can influence spe-
cific binding of a protein to cysteine residues.39 In RBCs, blood flow induces
stresses that can lead to deformation. The membrane of RBC is reinforced
by a cytoskeleton constituted in part of spectrin chains connected to F-ac-
tin through its cysteine residues (Figure 1.9).40 F-actin is an essential protein
instrumental in the deformation process. Spectrin’s α and β chains contain
20 and 15 cysteines, respectively. In the experiment, RBCs were reversibly
lysed and filled with a reactive cysteine-modified fluorophore before being
reformed and sealed (“ghost RBCs”). They were then exposed to a range
of conditions at varying temperatures, while some were sheared using a
microfluidic device. They were then relysed and the results showed that the
sheared RBCs had about 66% more fluorescent dye compared to the static
ones, suggesting that the folding hides specific domains.
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De Herstelde Gemeente, is er nog eene Luthersche Kerk (naamlijk
voor de uitgewekenen, of de Herstelden,) alhier gebouwd, ter plaatse
alwaar het Dolhuis gestaan heeft: ’t is een ruim gebouw, doch zonder
eenigen cieraad.
Het St. Pieters Gasthuis, dat zijnen naam ontleent van één der
Gasthuizen welken weleer hier ter stede waren, komt eerst in
aanmerking: het was in oude tijde de Kloosters der Oude en Nieuwe
Nonnen: alles wat hierin gevonden wordt is ongemeen aan het
oogmerk voldoende; het heeft zijne eigene bakkerij en brouwerij, ook is
er de stads Apotheek in geplaatst: even binnen de groote poort is een
Beiërt, alwaar de bedelaars en arme vreemdelingen drie nachten om
niet kunnen logeeren, ontvangende des avonds en morgens ook spijs
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Het Burger weeshuis, was weleer het St. Lucie klooster in 1580
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de Keizers kroon, het Burger weeshuis: dit huis is groot, aanzienlijk, en
ook zeer rijk.
Van het Dol- of Krankzinnig huis hebben wij reeds gesproken: (zie
boven Bladz. 10).
Het St. Joris hof, staande tegen de oude Waals Kerk: was eertijds het
Pauliniaanen klooster; ’t is nu een Proveniers huis, schoon ’t voorheen
ook voor Leprozen gediend hebbe.
Behalven alle de gemelde gebouwen vindt men hier ter stede nog eene
menigte hofjens en Godsdienstige gestichten, door bijzondere
persoonen van verscheidene Gezinten, met Godsdienstige oogmerken,
aangelegd: de voornaamsten zijn:
WERELDLIJKE GEBOUWEN.
Het zoude ons bestek te veel gevergd weezen, wilde men eene
beschrijving van het inwendige des gebouws van ons [17]vorderen, wij
kunnen er slechts iet weinigs van zeggen; de talrijke vertrekken,
welken er in zijn, zijn allen der bezichtiginge overwaardig; eenigen van
dezelven zijn vercierd met overheerelijke schilderstukken, en
beschilderingen van de voornaamste oude meesters; de
vroedschapskamer munt daarin boven alle anderen uit: op de
wapenkamer zijn ook veele bijzonderheden te zien, voornaamlijk van
oude wapenen, harnassen, enz.
Het Willige rasphuis voor vrouwlieden, dat weleer aan den Y-kant
stond, en ter weeringe van bedelaarij diende, niet alleen, maar ook ter
gevangenplaatse van vrouwen, wier gedrag opsluiting verdiende, en
wier naastbestaanden de kosten van een bijzonder Beterhuis niet
konden draagen, almede door den aanleg van het voornoemde
algemeene Werkhuis, ten onbruike geraakt zijnde, werd de grond
daarvan bebouwd, met het allen lof verdienende Kweekschool voor
de Zeevaart; eene instelling die Amsteldam eere aandoet, en ons ’t
ons voorgeschreven bekrompen bestek doet betreuren; want gaarne
weidden wij ten breedsten over het aanleggen van die lofwaardige
schoole uit.
KERKLIJKE REGEERING.
Ingevolge onze gewoonte in het reeds afgewerkt gedeelte van ons
uitgebreid plan, bepaalen wij ons hier ook weder alleenlijk tot de
Gereformeerde, of Heerschende kerk in Amsteldam: deeze gemeente
dan wordt bediend door 29 Predikanten, één van welken in de
Hoogduitsche taale moet prediken: de Gasthuiskerk had weleer haar
afzonderlijken Predikant; doch thans predikt deeze ook op zijn beurt in
de andere kerken, gelijk de overige Predikanten ook de Gasthuiskerk
op hunne beurt moeten waarneemen: de gewoone kerkenraad bestaat
voords uit gemelde Predikanten, een gelijk getal Ouderlingen, waarvan
jaarlijks de helft afgaan, gelijk ook van de Diaconen, die 42 in getal zijn,
en een afzonderlijk Collegie uitmaaken, doch van den grooten
kerkenraad ook leden zijn: den Diaconen zijn 12 Diaconessen
toegevoegd, [25]die voor al het vrouwlijke in dat groote ligchaam zorg
draagen; voorheen zond de Wethouderschap twee Gemagtigden in
den kerkenraad; doch sedert eenige jaaren vindt zulks geen plaats
meer: in gevalle van eene vacature onder de Predikanten, worden
Burgemeesteren om handopening tot het doen van een beroep
verzocht; na bekomen verlof, maakt de gewoone kerkenraad een
nominatie van drie, het zelfde doet het Collegie van Diaconen: deeze
dubbelde nominatie wordt in den grooten kerkenraad tot een drietal
gebragt, en daaruit wordt bij meerderheid van stemmen één verkozen,
op welke verkiezing vervolgends de goedkeuring van Burgemeesteren
verzocht wordt.
WERELDLIJKE REGEERING.