Table Of ContentAdvances in Polymer Science 268
Sebastian Seiffert Editor
Supramolecular
Polymer Networks
and Gels
268
Advances in Polymer Science
EditorialBoard:
A.Abe,Yokohama,Japan
A.-C.Albertsson,Stockholm,Sweden
G.W.Coates,Ithaca,NY,USA
J.Genzer,Raleigh,NC,USA
S.Kobayashi,Kyoto,Japan
K.-S.Lee,Daejeon,SouthKorea
L.Leibler,Paris,France
T.E.Long,Blacksburg,VA,USA
M.Mo¨ller,Aachen,Germany
O.Okay,Istanbul,Turkey
V.Percec,Philadelphia,PA,USA
B.Z.Tang,HongKong,China
E.M.Terentjev,Cambridge,UK
M.J.Vicent,Valencia,Spain
B.Voit,Dresden,Germany
U.Wiesner,Ithaca,NY,USA
X.Zhang,Beijing,China
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Sebastian Seiffert
Editor
Supramolecular Polymer
Networks and Gels
With contributions by
(cid:1) (cid:1) (cid:1)
M. Anthamatten M. Chau P.Y.W. Dankers
(cid:1) (cid:1) (cid:1) (cid:1)
B.W. Greenland W. Hayes E. Kumacheva P. Li
(cid:1) (cid:1) (cid:1) (cid:1) (cid:1)
R. Liu O. Okay A.C.H. Pape T. Rossow S. Seiffert
S.E. Sriskandha (cid:1) H. The´rien-Aubin
Editor
SebastianSeiffert
FreieUniversita¨tBerlin
InstituteofChemistryandBiochemistry
Berlin
Germany
ISSN0065-3195 ISSN1436-5030 (electronic)
AdvancesinPolymerScience
ISBN978-3-319-15403-9 ISBN978-3-319-15404-6 (eBook)
DOI10.1007/978-3-319-15404-6
LibraryofCongressControlNumber:2015936665
SpringerChamHeidelbergNewYorkDordrechtLondon
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Preface
Supramolecular polymer networks and gels consist of monomeric, oligomeric, or
polymeric building blocks transiently and dynamically interconnected by non-
covalent bonds. This mode of interconnection is responsible for the promising
potential of these materials to serve as adaptive, self-healing, and stimuli-respon-
sivecoatings,elastomers,andscaffoldsinboththelifeandmaterialssciences.To
make this truly useful, it is necessary to achieve systematic and comprehensive
understandingofthemolecular-scaleinteractionsandmacromolecular-scalestruc-
tures anddynamics ofthese networksandgels. Various efforts have been and are
beingmadetoachievesuchunderstandingandtodevelopadvancedfunctionalsoft
materials.Itisthereforeagoodtimetoreviewsomeoftheseactivities;thisvolume
aims to provide such a review. In the following chapters, several examples and
achievements of recent and current research activities are given. Anthamatten
reviews hydrogen-bonding interactions to form soft solid polymer-network struc-
turesandmaterials,includingglasses,melts,andelastomers.Okayaddsaperspec-
tive on the design, mechanics, and self-healing of hydrogels formed via
hydrophobic interactions, with a particular emphasis on the role of surfactant
micelles within the gels. The development of donor–acceptor – stacking interac-
tions that serve as transient crosslinks in self-healable supramolecular polymer
networks is discussed by Greenland and Hayes. Chau, Sriskandha, The´rien-
Aubin, and Kumacheva highlight recent progress in the field of nanofibrillar
supramolecular gels, discussing both synthetic and natural materials. Liu adds a
particular view on the potential of cellulose and cellulose derivatives for the
formation of chemical and physical gels and microgels, with a specific focus on
supramolecular interactions within them. Finally, Pape and Dankers provide a
reviewonsupramolecularhydrogelsofseveralkindsforuseinthefieldofregener-
ativemedicine.
Iwouldliketotakethechancetogreatlythankallthesecolleaguesforproviding
thesedeepandillustrativeinsightsintotheirworkandthatoftheirpeers.Ibelieve
v
vi Preface
thatthecollectionofcontributionspresentedinthisvolumetrulyarcsfromfunda-
mentalphysical-chemicalinvestigationtoadvanceddevelopmentanduseofsupra-
molecular polymer networks and gels, which I expect to further evolve as a
particularlypromisingandfascinatingclassofsoftmatterinthenearfuture.
Berlin SebastianSeiffert
April2015
Contents
SupramolecularPolymerNetworks:Preparation,Properties,
andPotential .................................................................... 1
TorstenRossowandSebastianSeiffert
HydrogenBondinginSupramolecularPolymerNetworks:Glasses,
Melts,andElastomers ........................................................ 47
MitchellAnthamatten
Self-HealingHydrogelsFormedviaHydrophobicInteractions .......... 101
OguzOkay
Donor–Acceptorp–pStackingInteractions:FromSmallMolecule
ComplexestoHealableSupramolecularPolymerNetworks ............. 143
WayneHayesandBarnabyW.Greenland
SupramolecularNanofibrillarPolymerHydrogels ........................ 167
MokitChau,ShivanthiEaswariSriskandha,He´lo¨ıseThe´rien-Aubin,
andEugeniaKumacheva
CelluloseGelsandMicrogels:Synthesis,Service,andSupramolecular
Interactions ................................................................... 209
PingpingLiandRuigangLiu
SupramolecularHydrogelsforRegenerativeMedicine ................... 253
A.C.H.PapeandPatriciaY.W.Dankers
Index .......................................................................... 281
vii
Supramolecular Polymer Networks:
Preparation, Properties, and Potential
TorstenRossowandSebastianSeiffert
Contents
1 SupramolecularInteractions................................................................. 2
2 SupramolecularPolymerNetworksandOrganogels........................................ 5
2.1 HydrogenBonding..................................................................... 5
2.2 MetalComplexation.................................................................... 12
2.3 DynamicsinSupramolecularPolymerNetworks..................................... 18
3 SupramolecularHydrogels................................................................... 20
3.1 HydrogenBonding..................................................................... 21
3.2 MetalComplexation.................................................................... 24
3.3 MacrocyclicInclusionComplexation................................................. 26
3.4 IonicInteractions....................................................................... 30
3.5 HydrophobicInteractions.............................................................. 32
4 Applications.................................................................................. 33
4.1 Self-Healing............................................................................ 33
4.2 ShapeMemory......................................................................... 34
4.3 DrugDelivery.......................................................................... 35
4.4 MicrogelsforCellEncapsulation...................................................... 36
5 ConclusionsandOutlook.................................................................... 38
References........................................................................................ 38
Abstract Supramolecular polymer networks consist of macromolecules
interconnected by transient, noncovalent bonds such as those through hydrogen
bonding, transition metal complexation, hydrophobic interaction, ionic attraction,
or π–π stacking. These networks form an extraordinarily useful class of soft,
stimuli-sensitive materials. Although they assemble to strong materials under
T.Rossow
InstituteofChemistryandBiochemistry,FreieUniversita¨tBerlin,Takustr.3,14195Berlin,
Germany
S.Seiffert(*)
InstituteofChemistryandBiochemistry,FreieUniversita¨tBerlin,Takustr.3,14195Berlin,
Germany
SoftMatterandFunctionalMaterials,Helmholtz-ZentrumBerlin,Hahn-Meitner-Platz1,
14109Berlin,Germany
e-mail:[email protected]
©SpringerInternationalPublishingSwitzerland2015 1
S.Seiffert(ed.),SupramolecularPolymerNetworksandGels,AdvancesinPolymer
Science268,DOI10.1007/978-3-319-15404-6_1
2 T.RossowandS.Seiffert
favorable conditions, they are easily disassembled under other conditions. This
ambivalentnaturerenderssupramolecularpolymernetworksusefulforapplications
in drug delivery, tissue engineering, self-healing, and shape-memory materials.
Theseapplicationsrequireadeepandcomprehensiveunderstandingofthephysical
chemistry of supramolecular networks, with a particular view to the complex
interplay between their structure, dynamics, and properties. Approaches that have
attemptedtoderivesuchknowledgeareoftenbasedoninvestigationsofsupramo-
lecular polymer networks in the melt or of supramolecular polymer networks
swollen in organic media. These approaches are reviewed in the first part of this
chapter. In the second part, we focus on the preparation and characterization of
supramolecularhydrogelsbasedonsyntheticandnaturalprecursorsandrevealtheir
utilityandpotentialinlifescienceapplications.
Keywords Supramolecular polymer gels (cid:129) Stimuli-responsive materials (cid:129)
Noncovalentinteractions(cid:129)Supramolecularnetworkdynamics(cid:129)Self-assembly
1 Supramolecular Interactions
“Supramolecular chemistry may be defined as ‘chemistry beyond the molecule’,
bearingontheorganizedentitiesofhighercomplexitythatresultfromtheassoci-
ationoftwoormorechemicalspeciesheldtogetherbyintermolecularforces.”This
definitionwasgivenbyLehnin1987[1]whenhereceivedtheNobelprizetogether
with C. J. Pedersen and D. J. Cram for their work on host–guestchemistry. Since
then,supramolecularchemistryhasgainedincreasingattentionanddevelopedinto
an important, broad, and active field of research [2–4]. Today, research on supra-
molecular chemistry can be subdivided into several categories: host–guest com-
plexes[5–7],self-assembledarchitectures[8,9],supramolecularpolymers[10–14],
supramoleculargels[15–18],andsupramolecularpolymernetworks[19,20].
The term “supramolecular polymer” refers to a polymer built of monomeric
units associated through directional noncovalent physical interactions. Supramo-
leculargelstypicallyconsistoflowmolecularweightprecursorsthatself-assemble
intothree-dimensionalnetworksthroughnoncovalentinteractions;thesematerials
are often brittle and hard to customize. In contrast, supramolecular polymer net-
worksconsistofcovalentlyjoinedmacromolecularbuildingblocks(polymers)that
are functionalized with motifs that can bind to each other through noncovalent
interactionssuchashydrogenbonding[21–23],transitionmetalcomplexation[11,
24,25],hydrophobicinteraction[26],ionicattraction[10],orπ–πstacking[27–29],
serving to assemble the polymer chains into a network. Noncovalent interactions
strongly vary in their strength, as shown in Fig. 1. As a result, supramolecular
polymer materials can be tuned to exhibit different mechanical properties by
customuseoftheseinteractionsforpolymercross-linking.
Supramolecularpolymernetworkscombinethecharacteristicsofchemicaland
physical networksand can betailored tospecific needs throughthe use ofmacro-
molecular building blocks. Although they form strong materials under favorable
