Low-Molecular-Mass Gels Responding To Ultrasounds

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Cite this: Chem. Soc. Rev., 2014,

43, 5346
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Low-molecular-mass gels responding to

ultrasound and mechanical stress: towards
self-healing materials
Xudong Yu,ab Liming Chen,a Mingming Zhanga and Tao Yi*a
In this review, we focus on the types of smart supramolecular gels whose self-assembly processes are
aected or even triggered by physical forces including sonication and mechanical stress (mechanical
force). The types of gels that are responsive to sonication and mechanical stress are examined and
summarised. The gels exhibit non-covalent interactions among the gelator molecules and show
dynamic and reversible properties controlled by the stimuli. Upon stimulation, the gelators cause
instant and in situ gelation of organic solvents or water with dierent modes and outcomes of selfassembly. On the other hand, sonication and mechanical stress, as external factors, can give rise to
dynamic changes in microscopic morphology, optical properties, etc. Certain thixotropic supramolecular gels exhibit perfect self-healing characteristics. The driving forces and the mechanism of
Received 7th February 2014
the self-assembly process and the responsive outcome of morphological and spectroscopic changes
DOI: 10.1039/c4cs00066h
are discussed. Those supramolecular gels responding to sonication and mechanical stress oer a wide
www.rsc.org/csr
range of applications in fields such as smart and adaptive materials, switches, drug control and release,
and tissue engineering.
1. Introduction
There has been an enormous increase in interest over the past
decades in the structures and properties of low-molecular-mass
organic gelators (LMOGs, molecules whose molar mass is o3000)
a
Department of Chemistry, and Concerted Innovation Center of Chemistry for

Energy Materials, Fudan University, 220 Handan Road, Shanghai 200433, China.
E-mail: yitao@fudan.edu.cn
b
College of Science, Hebei University of Science and Technology, Yuhua Road 70,
Shijiazhuang 050080, China
Xudong Yu
Xudong Yu completed his MS

degree at the Department of
Chemistry, Nankai University, in
2008 and subsequently obtained
his PhD degree in 2011 from the
Department of Chemistry, Fudan
University. Currently, he is
working in the College of Science,
Hebei University of Science and
Technology. His research interests
include supramolecular assembly of
cholesterol-based organogels and
molecular recognition.
5346 | Chem. Soc. Rev., 2014, 43, 5346--5371
and their organo-/hydrogels.13 These gelator molecules selfassemble in organic solvents or water through highly specific
non-covalent interactions, such as hydrogen bonding, hydrophobic interactions, polarpolar interactions, electrostatic interactions and pp stacking, that drive the one-dimensional growth
of the gelator molecules to produce nanoscale or microscale
structures in the form of fibres, strands and tapes. These extended
objects join together to form three-dimensional networks that
encapsulate the solvent and prevent flow.47 The use of these
interactions for the directed self-assembly of a given structure
Liming Chen received his BSc

degree in applied chemistry from
Fudan University, Shanghai,
China, in 2012. In the same
year he joined Professor Tao Yis
group as a PhD candidate.
Currently, he is working on the
early detection of cancer and
medical application of hydrogels.
Liming Chen
This journal is The Royal Society of Chemistry 2014
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requires knowledge of their strength and of their dependence on

distance and directionality. In the order of decreasing strength,
these interactions are as follows: (a) electrostatic interactions (ion
ion, iondipole and dipoledipole interactions) and coordinative
bonding (metalligand), (b) hydrogen bonding, (c) pp stacking
and (d) van der Waals forces. In addition, hydrophobic or
solvophobic effects, as well as the fine balance of the forces among
gelator molecules and solvent molecules, often play an important
role. Although a single interaction is generally much weaker than a
covalent bond, the cooperative action of many such interactions
may lead to a supramolecular framework that is thermodynamically and kinetically stable under a variety of conditions.8 LMOGs
constructed by a self-assembled approach are much more versatile,
with tuneable functionality, than those of polymer materials
because of their dynamic nature; therefore, it is envisioned that
molecularly defined, intelligent materials may be constructed by
using the supramolecular concept.914 In particular, such materials
susceptible to the effects of external stimuli are of interest and play
a crucial role as functional soft materials.1519
When an external stimulus acts on an LMOG, a change in the
chemical structure, molecular configuration or aggregation mode
of the gelator may occur depending on the type and strength of
the stimulus. Most of the common physical stimuli will not
change the chemical structure of the gelator but can modulate
the molecular configuration or the self-assembly process of the
gelator except light stimulus (Fig. 1). For example, moderate heat
is a typical physical stimulus extensively used to control gel
formation or construct gel-related switches. Sonication and
mechanical stress have recently been observed to be important
stimuli for gel-like soft materials. This type of stimulation may
trigger an imbalance in the self-assembly system toward an
intermediate state, which could be partly or wholly reverted to
the initial state by external or internal stimuli. It is reasonable to
conclude that gelation could occur with the aid of a physical force,
such as mechanical force or sonication.20,21 Even though a large
amount of studies have been dedicated to the molecular design,
synthesis and properties of LMOGs, few of them have focussed on
Mingming Zhang obtained his PhD

from the Laboratory of Advanced
Materials of Fudan University. His
PhD study was carried out under
the guidance of Prof. Tao Yi and
his research mainly focused on
the development of stimulus
responsive supramolecular soft
materials. He is currently a postdoctoral fellow at the Racah
Institute of Physics, Hebrew
University of Jerusalem.
Mingming Zhang
Fig. 1
The types of physical stimuli and their eect on gel formation.
the physical force driving gelation. In this account, we mainly

highlight so-called physical-stimulus-driven/-responsive LMOGs,
whose self-assembly process and functionality can be controlled
by physical stimuli without the change of chemical identity of
gelator molecules, which are used extensively to construct selfhealing materials with reversibility.
Ultrasound waves are a kind of high frequency mechanical
waves that require a physical medium in order to support their
propagation.22 When ultrasound waves propagate in mediums
such as liquid or liquidpowder suspension, cavitation which
could create extreme physical and chemical conditions usually
occurs.23 This cavitation effect may provide high energy to
induce certain chemical and physical changes, which have long
been studied in, for example, chemical reactions, such as
the degradation of halohydrocarbons,24 polymerisation reactions,25 oxidationreduction reactions,26 and with respect to
reaction selectivity.27 Very recently, Christopher W. Bielawski
et al. demonstrated that ultrasound could affect the previously
Tao Yi received her BSc (1987),

MS (1990) and PhD degrees
(1998) from Peking University.
She was a JSPS postdoctoral
fellow at Kyoto University from
1999 to 2001. She worked in
Paris University (XI) as a red
position researcher of CNRS
from 2003 to 2004. She is now
a full professor in the Department of Chemistry, Fudan
University. Her research interests
focus on stimulus responsive
Tao Yi
supramolecular soft matter and
its application in bio-imaging and drug delivery systems. She has
authored about 120 peer reviewed publications.
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elusive retroclick reaction, transforming triazoles into their azide

and alkyne precursors.28 Ultrasound has also been widely used in
the field of medical care, in vivo imaging and food and cosmetic
industries. In materials chemistry, ultrasound is used to break
and disperse particles. However, it is amazing and intriguing that
ultrasound, as an external stimulus, has been observed to promote gel formation.20,29 Ultrasound may be suitable for stimulating gelation in a dynamic manner with a high energy barrier.
Sonication-induced gelation is a rapid crystallisation process that
yields fibre-like aggregates in a metastable system. Traditional gel
formation often requires a heatingcooling process. By contrast,
sonication-activated gel formation can occur instantly at room
temperature, which makes these gels highly attractive in realworld applications. In this context, the history and evolution of
ultrasound-assisted gels, as well as the gelation mechanism
thereof, have been explored and discussed.
In addition to ultrasound, physical shearing stress, as a weaker
and purely mechanical force, can also aect gel properties at microor macro-levels. Most LMOGs are converted to a sol or sol-like state
when agitated by mechanical stress, and the gel state can be
recovered after a heatingcooling treatment. Notably, some LMOGs
referred to as thixotropic gels, as third-generation self-healing
materials, have the ability to regain their consistency in situ by
internal stimuli after the removal of the external stress.30 Due to the
dynamic bonding in the corresponding supramolecular systems,
these thixotropic gels have become increasingly appealing as they
could be developed into autonomously, intrinsically healing materials that would theoretically be capable of repeatedly healing the
same damage site.9,11,31 The self-healing process in supramolecular
systems is a form of biomimicry and of great significance for
industry, fracture and fatigue, biomaterials and smart materials.32,33
Herein, we examine several types of thixotropic gel systems, their
self-healing mechanisms, as well as their extended applications.
Apart from the above-mentioned stimuli, there are also other
types of physical stimuli, such as electrostatic interactions, magnetism and pressure. However, these stimuli have received little
attention from researchers in the field of LMOGs. Therefore, in
this account, we mainly focus on physical organogels controlled by
sonication and mechanical stress. These physical stimuli do not
introduce any new species into an organogel system for tuning or
switching gel properties, including morphology and surface
wettability, colour, emission and chirality. Moreover, the changes
or switches triggered by these physical stimuli are always reversible.
The following text is divided into four parts: types of gels
that respond to ultrasound and mechanical stress, gelation
mechanisms controlled by ultrasound and mechanical stress,
the application of smart organogels sensitive to ultrasound and
mechanical stress, and summary and prospects.
2. Types of LMOGs responsive to

ultrasound and mechanical stress
The presently reported physical-stimulus-responsive organogels
generally exhibit multiple non-covalent intermolecular interactions,
including metalligand interactions, dipolar forces, hydrogen
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bonding, pp interactions and hydrophobic interactions. The

delicate balance between these interactions plays an important
role not only in the formation of nano/micro architectures but
also in the resulting stimulus-responsive character. Therefore,
small structural variations in a gelator will result in quite
different gelation properties. In fact, it is still a great challenge
to design a gelator that can precisely respond to a physical
stimulus, particularly a mechanical force. Many physicalstimulus-responsive organogelators have been discovered accidentally and have been further modified and developed by
organic synthesis, resulting in systematic synthesis procedures
such as those detailed in the following.
2.1
Metallogels
Metallogelators are generally composed of a coordination polyhedron of a metal ion that can provide a rigid framework with
functionality and other non-covalent interactions such as hydrogen bonding and pp interactions to form a flexible bond to metal
ions. Physical forces are not sufficiently strong to break the metal
ligand interaction but can tune the flexible linker to affect the
aggregation mode of the gelators. The first example of gel formation induced by ultrasound was reported by Naota et al. for a
dinuclear Pd complex.34 The sol state of anti-1a (n = 5) in various
solutions such as CCl4, acetone, 1,4-dioxane, ethyl acetate and
toluene could be converted to an opaque gel state when treated
with sonication for 310 s due to the transformation of intramolecular pp stacking into intermolecular pp stacking (Fig. 2).
The resulting sonogel was reverted to a sol upon heating at above
Tg (sol-to-gel transition temperature) and subsequently cooling to
room temperature. However, the syn-1 and optically pure anti-1
could not gel any solvent under sonication. This behaviour indicated that heterochiral aggregation (RSRS. . .) may have occurred in
the gel state. In another study, palladium complex 2a2c containing a peptide as a linker was designed.35 This complex could gelate
esters or chlorobenzene with the aid of sonication by a switchable
solgel transition. Kinetic studies suggested that the gelation
process was composed of two steps: a sonication-triggered initial
step and a spontaneous propagation step. Without sonication,
intramolecular H-bonding involving the chloro ligand 2a prevents
the formation of a dipeptide by intermolecular H-bonding. Ultrasound irradiation releases this self-locked structure and promotes
the formation of semi-stable initial aggregates, and these initial
domains undergo spontaneous b-sheet aggregation with excess
unaggregated complexes. The sonication time is an important
factor affecting the fibre order of such gels. Increasing the duration
of sonication increases the concentration of the active domain,
leading to accelerated gelation rates and the formation of higherorder nanostructures with heat-resistant properties.
By replacing the palladium ion of 1 with platinum, the
precise control of phosphorescent emission was achieved by
ultrasound-induced gelation of organic liquids (anti-3a, n = 5,
Fig. 2B).36 Nonemissive solutions of racemic, shortlinked anti3a and optically pure, long-linked anti-3c (n = 7) in organic
liquids are transformed immediately into stable phosphorescent gels upon brief irradiation with ultrasound. Emission from
the gels can be controlled by adjusting the sonication time,
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Fig. 2 (A) Chemical structures of 13; (B) emission colour change between solution and sonogel of ()-anti-3a (n = 4) in cyclohexane (1.5 10
with different sonication time. (Reprinted with permission from ref. 36. Copyright 2011, American Chemical Society.)
linker length and optical activity of the complexes. Spectroscopic

and structural analyses indicate that structure-dependent homoand heterochiral aggregations and ultrasound control of the
aggregate morphology are key factors for emission enhancement.
Two organometallic terpyridyl platinum gelators containing
hydrophobic cholesterol with or without large steric hindrance
were synthesised and characterised by our group (Fig. 3).37 The
complex with three bulky tert-butyl groups (4) can form a stable
gel in several types of solvents such as ethyl acetate, toluene
and n-propanol when triggered by sonication at 40 1C with a
slow sol-to-gel transition lasting over 40 min. The sonogel in
n-propanol of 4 displayed dierent colours (from yellow to red)
and luminescence enhancement for the precipitate obtained by
a heatingcooling process. The morphology, as well as the
surface wettability, of 4 can also be reversibly adjusted by
sonication and heating. Mechanistic studies indicated that
sonication may transform the molecular conformation of 4,
M)
via a thermally dynamic process, from a conformation with the

1,8-naphthalimide perpendicular to tBu3tpy to a conformation
of the complex with the 1,8-naphthalimide ring coplanar to
tBu3tpy, which induces the ionic dipolar and hydrophobic
interactions required for gelation and thus can switch the
optical properties of the complex in the aggregated state. Both
anti-3 and 4 showed suitable configurations for adjusting the
photophysical properties of the gel system by physical stimuli
such as sonication. With a similar structure, the complex 5a5d
showed thixotropic properties.38 For example, shaking the gel
of 5d (10 mg mL 1 in cyclohexane obtained by a heating
cooling process) with a vibrator for 5 min would disturb the
gel completely, a state that would persist for half an hour, and
the gel would then reform.
Another multi-responsive metallogelator, 6, containing
ferrocene, carbonyl amide and a cholesterol group as a neutral
complex was reported by Fangs group.39 The metallogelator
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Fig. 3
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Chemical structures of 46.
could gel cyclohexane at concentrations as low as 0.09 wt%,

placing the gelator in the category of supra-gelator. By a
shakingrest process, a gelsolgel transformation was observed.
However, the gel responded to sonication negatively. When the
gel was treated with sonication, a viscous suspension rather than
a gel was formed.
Thixotropic properties have also been observed for other
metallogels with dierent metal ions such as Zn2+ and
Cu+/Cu2+. A. M. Jamiesons group reported the first type of
metallogel containing Zn2+ (7), which was responsive toward
multiple stimuli, such as shakingrest, sonication and chemostimulus (Fig. 4).40 The addition of Zn(ClO4)2 along with a
small percentage of lanthanide ions could polymerise the
monomers through metalligand interactions, thus resulting
in dynamic self-assembly and gel formation in acetonitrile.
The spherulitic structured gel is fragile and very sensitive to
mechanical perturbation, resulting in thixotropic behaviour
that is highly dependent on formation history. When the gel
state is recovered after shearing, the globular particles are
broken into progressively smaller particles as the amount of
mechanical stress is increased. Gels formed by sonication
irradiation exhibit the highest strength due to the increase
5350 | Chem. Soc. Rev., 2014, 43, 5346--5371
in the strength of interparticle interactions afforded by an

increased number of surface contacts. The responsive nature
of these gels can be tailored by the metal ion salts used to form
the gels. These metallo-supramolecular gels offer a facile route
to multi-responsive organicinorganic hybrid materials,
whose properties can be tuned by appropriate manipulation
of metal ion combinations and taking into account the role of
possible counterion and solvent coordination.
Generally, most gels exhibit thixotropic properties in aprotic
solvents, such as toluene, benzene, cyclohexane and DMSO,
because of the competing interaction between the gelator and
solvent molecules. Recently, Leonard R. MacGillivray reported
the Cu+/Cu2+-based metallogel 8 along with a variety of counter
anions that could gel in water and polar organic solvents such
as acetonitrile, nitromethane and methanol.41 The hydrogel is
thixotropic, composed of nanoscale metalorganic particles
(NMOPs) and exhibits a high surface area, which likely
accounts for the gelation of the polar aqueous medium. The
hydrogel was converted into a sol when subjected to shaking;
then, after resting for 34 h, it reformed into a new gel.
Interestingly, the hydrogel could be formed easily when the
metalorganic particle powder was exposed to water vapour.
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Fig. 4 (A) Chemical structure of 7; (B) the typical multi-stimuli responsive behavior of gel 7 + Zn2+ (11 wt% in acetonitrile); (C) Cu+/Cu2+ based metallogel 8.
(Reprinted with permission from ref. 40. Copyright 2006, American Chemical Society.)
2.2
Cholesterol-based organogels
Cholesterol derivatives are very important gelators in supramolecular chemistry.42 The first rational synthesis of cholesterolbased LMOGs was proposed by RG Weiss and coworkers.43,44
They showed that molecular systems comprising an aromatic (A)
moiety connected to a steroidal (S) group through a functionalised link (L) could display eective gelation ability. Some of
these gelators are sensitive to sonication or mechanical force.
The first sonication-triggered solgel conversion in ALS systems
was reported by our group.45 Compounds 910 with different
acyl amino linkages and different hydrogen bonding sites have
been designed and synthesized (Fig. 5). Compound 9a failed to
Fig. 5
gelate any tested solvent due to the lack of intermolecular

hydrogen bonding, whereas 9b formed gels in alcohols exclusively upon ultrasound irradiation; other external stimuli such as
quick heating or cooling did not initiate aggregation. However,
10 could form stable gels in a variety of solvents via a slow
heatingcooling process or upon ultrasound irradiation for only
a few seconds (0.16 W cm 2, 40 kHz). The different stimuli
yielded different self-assembled morphologies, from the large
multiporous vesicle morphology of gels formed via traditional
heatingcooling treatment (T-gels) to the smooth surface of
sonogels (S-gels). Repaired by heat as an external stimulus, the
sonogel could be reverted to the initial state. The effects of
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sonocrystallisation and sonogelation were further discussed with

respect to the compounds 10a10c, which showed structural
changes in the alkyl diamine group. It was clear that the
locations of hydrogen bonds (by different alkyl chain lengths)
showed a strong effect on the solubility and gelling properties of
these compounds. A careful thermodynamic balance among the
main driving forces for self-assembly, hydrogen bonding and
hydrophobic and pp interactions, was rationalised in terms of
the solubility and cooperative self-assembly of molecular-scale
building blocks induced by sonication and thermal processes.46
In another study, a chiral amino acid was introduced into the
linker in 11a and 11b.47 The result showed that the position of
L-alanine in the linker affected intermolecular hydrogen bonding
and molecular polarity, thus resulting in different gelation
properties. The precipitate-to-gel transition of the gelator 11a
and the gel-to-gel transition of the gelator 11b, with the aid of
ultrasound, were monitored and studied. Both processes were
highly dependent on temperature. Compared with the solgel
transition, the direct and instant gel-to-gel transitions are more
convenient for controlled release, functional expression and
engineering applications.
The first thixotropic cholesterol-based organogel CNC (12a)
was reported by Weiss et al. (Fig. 6).48,49 The thixotropy of the
gel is highly dependent on morphology. The gelation abilities
of 12a and 12b are quite dierent, although they are structurally very similar. The spherulitic aggregates of 12a, composed
of highly branched, small fibres in n-alkane at an incubation
Review Article
temperature o28 1C or concentrations above 1.5 wt%, are

thixotropic and are transformed into more stable fibrils after
several cycles of repeated self-healing. In contrast, the fibre gel
network of 12b in ethyl acetate undergoes irreversible phase
separation upon mechanical agitation. The double bond at C5
forces the B-ring of the steroid part of 12b to adopt a boat
conformation, which aects the overall shape of the molecule
and thus its aggregation behaviour.
ALS2LS2 systems have attracted great attention in recent
years due to their thixotropic behaviour. Thixotropic properties
have been observed in most cholesterol-based derivatives with
an ALS2 structure. The gelator 13 prepared by our group could
form a transparent gel in toluene and an opaque gel in isopropanol, both of which exhibited thixotropic properties.50 When
treated with external mechanical stress, gel 13 (0.861.70 wt%)
in toluene lost most of its viscosity and transformed into a sol;
after resting for at least 20 minutes at room temperature, the gel
could be recovered. The self-healing process that occurred after
the gel-to-sol transition, which was induced by mechanical stress,
could be repeated many times. The thixotropy of the gel in toluene
strongly depended on concentration: below 0.86 wt%, a viscous
liquid was observed; in contrast, above 1.70 wt%, the gel could not
be destroyed simply by shaking by hand. It is interesting to note
that the gelation also occurred by a simple shakingresting
process in a solventsolid system at room temperature without
a heatingcooling process, which was referred to as agitationinduced gelation. The self-healing process of compound 13 in
Fig. 6 (A) Chemical structures of 1213; (B) AFM images of gel 13 in its original, broken and repaired state (scale bar, 2.5 mm). (Reprinted with permission
from ref. 50. Copyright 2012, Royal Society of Chemistry.)
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toluene was manifested as the destruction and regeneration of

nanoscale structures. Shaking by hand destroyed the cross-linked
nanoring structures with diameters ranging from 150 to 300 nm
into biased arcs, thus resulting in a gelsol transition. After
20 min, the repaired gel displayed more distinct and larger ring
structures with diameters ranging from 400 to 600 nm (Fig. 6B).
3D and phase AFM images also provided information regarding
this breakingrepair behaviour, which revealed that the morphology was repaired in diverging directions and that mass flow
transport also occurred from thicker walls to damaged areas. This
gel network was also sensitive to sonication. The ultrasoundinduced gel-to-gel transition process was monitored by AFM and
SEM images and it was shown that the original ring structure was
destroyed as expected, and smaller nanorings with pores measuring approximately 930 nm emerged from the original shells
simultaneously.
Fangs group intensively studied the eect of chiral residues
on the gel formation and thixotropic properties of LS2 (1417)
and ALS2 systems (1819) (Fig. 7). In those gelators, D/L-alanine
and D/L-cholesterol residues as well as the structure of the
spacer were used to tune the gelation behaviour.51 The results
show that gelators containing D-cholesterol residues (14b, 15b)
are more efficient gelators than their analogues with opposite
chirality (14a, 15a). For compounds with longer spacers (16, 17),
Chem Soc Rev
however, those containing L-alanine residues (16a, 17a) are

superior to the corresponding ones with D-alanine residues
(16b, 17b). As expected, these gels are thixotropic, as revealed
by rheological studies, and the mechanical properties of the
gels can be adjusted either by altering the spacer length or by
changing the gelator concentration. Surprisingly, 17a could
form a gel in triethylamine, butyl acetate, n-alkane (710 carbons)
or commercial oils spontaneously at room temperature within
10 min, indicating thixotropic properties. 18b and 18c can gel
several solvents spontaneously at room temperature. These gels
possess thixotropic properties and exhibit the selective gelation of
solvents from their mixtures with water.52 The gelation behaviour
can also be adjusted by modifying the spatial structure of the
linker with a benzene ring. Compounds 19ac can gel in a wide
variety of organic solvents. Specifically, 19a is a supergelator for
DMSO (CGC = 0.04% w/v). The 19aDMSO gel possesses excellent
mechanical strength and very smart thixotropic properties.53
On replacing the aromatic group with a Calix[4]arene group
in an ALS2 system, gelator 20 did not exhibit gelation in any pure
solvent (Fig. 8).54 However, it could gel (2.5% w/v) in solvents of
n-decane and acetonitrile mixed in a ratio of 1 : 1. The mechanical strength of the gel could be adjusted by varying the concentration of the gel and composition of the mixed solvents. These
gels possess smart and fully reversible thixotropic properties.
Fig. 7 Chemical structures of 1419.
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In another work, a chiral phenylalanine residue was incorporated into the linker instead of the ethyl diamine. The authors
observed that mechanical agitation or sonication could reduce
the duration of the gelation process of 21b from 30 h by a
typical heatingcooling process to 12 min. Moreover, the
strength of gel was also enhanced.55
2.3
Organogels containing p units and phenyl alkyl ethers
Similar to cholesterol groups, phenyl alkyl ethers with long

alkyl chains (n 4 8) can yield hydrophobic interactions and
therefore are widely used in the design of gelators. The reported
phenyl alkyl ether-based thixotropic gels are generally composed
of two or more phenyl alkyl ether residues. The first example of a
phenyl alkyl ester-based thixotropic gel was reported by Virgil
Fig. 9
Percec.56 The ester-based cylindrical dendrimers developed by

Percec could gel in various organic solvents with a wide range
of polarities (Fig. 9). 3,4-Substituted apical branching units on the
benzyl group in compounds 22a22e provided efficient thixotropic gelators in cyclohexane or toluene, whereas the 3,5-substituted
units did not show excellent gel properties. It was reported that
porous columnar mesophases provide a means by which to
prepare thixotropic gels, and the existence of weaker interactions
along the lateral direction and the column stratum versus hydrogen bonding along the length of the column was determined to
play an important role in the formation of porous columnar
mesophases and thixotropic gels.
The dendritic organogel 23 represents the first multimechanically responsive organogel constructed only by p units
Chemical structures of 22(ae).
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Fig. 10 The chemical structure of 23 and its multi-responsive behavior.
without hydrogen bonding (Fig. 10).57 The compound was

demonstrated to be a very ecient organogelator that could
gel more than 15 types of organic solvents after sonication for
15 min. Notably, the gelator could gel in tetrachloromethane
with a CGC of 0.05 wt%, placing the gelator in the category of
supergelators. In most of the solvents, the gel displayed thixotropic properties. For example, nanofibres with the bundle
structure of gel 23 were separated when subjected to vortexing.
The regenerated fibres were thicker than those of the fresh gel
after resting for approximately 24 hours. With the addition of
an azobenzene group, the gel could also undergo a reversible
gel-to-sol transition triggered by UV- and visible-light irradiation, which made the gel multi-stimuli responsive.
The self-healing properties of thixotropic gels (with an organogelator as the host) also rely heavily on concentration, and the
guest species is regarded as a junction for the rapid repair of the
destroyed assembly. For example, a naphthalenediimide-based
gelator tailed with phenyl alkyl ether (24) was reported by
P. Mukhopadhyay (Fig. 11). This gelator could form a stable,
thixotropic and transparent gel in cyclohexane.58 By changing
the concentration, the recovery time of the solgel process
could be tuned over a wide range, from a few seconds to
days. Rheological experiments suggested that the recovered
gel was weaker than the fresh gel (representing 72% of the
original amount). For the regeneration of injured nerve fibres
triggered by cAMP and neurotrophins, the authors employed
electron-rich 1,3- or 1,6-dihydroxynaphthalenes as adhesives
to regenerate the gel fibres positively via donoracceptor interactions, thus achieving the stimulus-induced regeneration
and self-healing of artificial tissues. This work intensively

studied the self-healing process under the effects of internal
and external factors and also provided a new model for
mimicking nerve fibre regeneration.
Another exciting example was reported by Shinkai and
coworkers.59 Gels 25a25d, composed of dianthracene units,
were prepared from a parent 2-substituted anthracenecarboxylic acid moiety by light irradiation (Fig. 12). The gelation
properties of the irradiated products are strongly dependent on
the conformation of the molecules. The photodimers dominated by the head-to-tail orientation form a thixotropic gel
(25a, b), whereas the system composed of mostly head-tohead photodimers (25c, d) appears as a fluid. The thixotropic
properties of compounds 25ab were exhibited in solvents
such as decalin, n-hexane and methylcyclohexane. The gel
formation is highly dependent on temperature. From 20 to
5 1C, the compounds were not observed to gel in any solvent
tested, even after a week; in contrast, at 20 1C, a transparent
gel could be formed within an hour, which indicated that
temperature played an important role in the formation of onedimensional aggregates. Notably, the gelation occurs even by
mixing the solvent and gelator at room temperature. Furthermore, fullerenes such as C60 or C70, as molecular adhesives,
were used to enhance the thixotropy of the gels; the process
was accompanied by the reversible integration and disintegration of the hostguest interaction upon mechanical agitation.
C70 appears to be a superior guest in terms of property
enhancement because its size better fits the concave-shaped
host (Fig. 12B).
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Fig. 12 (A) Chemical structures of 25(ad); (B) the thixotropic properties of organogel 25 with and without fullerenes. (Reprinted with permission from
ref. 59. Copyright 2012, American Chemical Society.)
2.4 Responsive organogels containing amino acids,

amides or urea
Hydrogen bonding is the most important noncovalent interaction in gel formation. Amides and urea are the most
5356 | Chem. Soc. Rev., 2014, 43, 5346--5371
commonly used proton donors and acceptors in LMOG systems. These hydrogen bonding units always cooperate with
other groups such as cholesterol or conjugated groups to
promote gelation. In this context, responsive gel networks
containing amino acid, amide and urea groups as the key
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components will be discussed as examples to demonstrate the

importance of complementary hydrogen bonding for the formation of self-assembly networks and the resulting stimuliresponsive behaviour.
2.4.1 Amino acid based gelators. A number of amino
acid based building blocks have been used to fabricate functional supramolecular architectures because of the chiralitymagnifying eect that occurs between the single-molecule and
macroscopic levels.6066 Moreover, amino acids, which are
generally used as linkers or as functional groups, represent
one of the best candidates for biological applications and can
supply facile hydrogen bonding modes in supramolecular gels.
The simple N-acylated amino acid 26 can form a turbid gel at
CGCs of approximately 6 wt% in octanol and 2 wt% in propylene glycol (Fig. 13).67 Ultrasound stimulation is used during
the early stages of gelation to promote not only the gelation
process but also the formation of homogeneous 3D interconnected fibre networks. This effect is particularly significant
for gelling systems with gelator concentrations near or below
the CGC. For example, the cooling of a hot solution of 3 wt%
26octanol under quiescent conditions was observed to result
in a nongelled liquid, which was stored for two more days
under ambient conditions. However, after sonication for approximately 1 min, gelation occurred rapidly to form a stable gel
within a few hours, and the CGC was reduced from B6 to
B2 wt% for octanol. Furthermore, the elasticity of the sonogel
of 26octanol was proved to be approximately two orders of
magnitude higher than that of the sample not subjected to
sonication. Moreover, when a heatingcooling treatment was
applied to the ultrasound-induced gel sample, the nongelled
Fig. 13
Chem Soc Rev
liquid was obtained again. This result implies that the gelling
state and the corresponding fibre network structure benefit
from the effect of ultrasound irradiation.
In addition to 26, most amino acid based sonogels are
composed of p systems such as phenyl, naphthyl and dipyridyl
groups. For example, the dispersion of particles of the peptide
compound 27 in alkanes or in the mixture of polar solvents
such as water/methanol (with the ratio of 1 : 4) can undergo a
precipitategel transition when treated with ultrasound at 20 1C
for 14 min.68 Interestingly, the compound can selectively gel
alkanes in wateralkane mixtures when exposed to ultrasound
without heating at room temperature, which might be more
meaningful for potential applications of the gel in industry, for
example, in the collection of petroleum from water.
Sonication not only decreases the CGC of the gelation
process but in some cases can also expand the range of
applicable gelation solvents to a large extent. The terminally
protected tripeptide 28 was observed to form a very weak gel
only in 1,2-dichlorobenzene by a typical heatingcooling process.69 However, by applying sonication for over 40 s, the
tripeptide could gel in many organic solvents, such as hexane,
cyclohexane, petrol, benzene, toluene, xylene and ethanol.
Some peptide-based gelators can not only gelate organic
solvents but can also form hydrogels in water under ultrasonic
treatment, which makes the gels more applicable in the field of
drug delivery. For example, the L-glutamic acid-based compound NBGE 29 reported by M. H. Liu could form stable gels
composed of a nanofibre network by the solgel and precipitate
gel processes in hexane, toluene and even water when treated
with ultrasound, displaying multiple transitions among different
Chemical structures of 2630 containing a peptide.
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phases triggered by sonication and heating.70 Heinz-Bernhard

Kraatz and co-workers recently investigated the sonicationinduced gelation properties and coiled fibrous architectures in
a short peptide of Boc-L-Phe-L-Lys(Z)-OMe (30).71 The peptide
displayed instant gelation in aliphatic and achromatic hydrocarbons starting from a suspension state within 10 s when
subjected to sonication. Additionally, the sonogel of the
dipeptide was also observed to exhibit thixotropic and selfhealing characteristics, as well as thermal chiroptical switching behaviour.
As one example of cyclopeptides, compound 31 with an
exposed NH2 group dissolves only in highly polar solvents
(Fig. 14), and gelation has been observed in some of these
solvents at low concentrations (usually in the range 0.52.0 wt%)
at room temperature.72 In fact, the preparation of 31 in DMF led
Fig. 14
Fig. 15
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invariably to instant gelation at a very low concentration

(0.3 wt%). Although 31 precipitates from water under ambient
conditions, ultrasound irradiation promotes the formation of a
weak gel instead of precipitation during the cooling process.
This hydrogel and precipitate returned to the soluble phase
upon heating, and this cycle could be repeated many times.
These results demonstrate that ultrasound induces and accelerates efficient primary nucleation that favours fibrillar aggregation. It should be noted that hydrogelation occurred even at
56 1C under sonication at a concentration of 1.5 wt%. The
N-acylated derivatives 32a32g lack the capacity to gel in DMF
and DMSO, even at relatively high concentrations.
In the molecular design of peptide-based organogelators,
the pendant groups of the peptides highly aect the gel properties. K. Das et al. observed that peptide-appended bolaamphiphiles 33a and 33b were capable of forming stable,
transparent, self-supporting hydrogels upon sonication at room
temperature at a final pH of 5.4, whereas bolaamphiphile 33c
was unable to form a gel under similar conditions (Fig. 15).73
These gelation experiments reveal that 33a is a more ecient
gelator than 33b upon sonication. After only 15 s of sonication,
33a forms a hydrogel instantaneously, whereas compound 33b
requires 1 h to gel. All of these hydrogels are exceptionally
stable over a wide range of pH levels (pH 48) for more than
3 months at room temperature. The polypeptide 34 could gel
in mixed solvents of THF/water (1 : 1) after sonication for
1030 min, exhibiting a fibrillar morphology.74 In particular, when
incubated at 60 1C, the gel underwent a reversible and in situ fibre
vesicle transition tuned by heat and sonication stimuli. It was
concluded that the lysine residue played an important role in the
gelation from a molecular structure point of view.
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Compared with the number of reports dedicated to sonogels, there are fewer reports about peptide-based thixotropic
organogels. As a typical example, the peptide compound
Nap-GFFYGGKOGEOGKOGSO (35) reported by Z. M. Yang
could self-assemble into a hydrogel by heatingcooling cycles
at a concentration above 0.8 wt% (Fig. 16).75 The gel was
thixotropic and could be converted to a viscous solution by
vortexing, shaking or pipetting; the viscous solution could then
be reverted to a gel after sitting at room temperature for a
certain period of time. This thixotropic property of gels formed
by 35 can facilitate cell harvesting post-culture. Further work
has shown that the hydrogel surface can slow down the spread
of EBs and the proliferation of murine ES cells compared with
that of gelatin. Moreover, the hydrogel can selectively improve
flk1 expression in different ES cells.
Gelator 36 is an unusual example of a peptide
dithienylcyclopentene-based gelator that shows multi-responsive
characteristics.76 36 forms an opaque gel in THF, acetone and
acetonitrile, in which the formation of anti-parallel b-sheets of the
biomimetic tetrapeptides is deemed to be the key driving force for
gelation. The organogel is responsive to various external stimuli,
including temperature, light, chemicals and mechanical force. In
the presence of catechol, the gel strength is enhanced, but the gel
retains thixotropic properties.
2.4.2 Urea-based organogels. It was demonstrated more
than five decades ago that urea-type hydrogen bonds were
capable of stabilising the assemblies of gelators. The selfassociation of urea involving two hydrogen bonds is much
stronger than that of amides or urethanes, thus decreasing the
solubility of the materials resulting in gelation or even precipitates. A family of ureido amphiphiles and bolaamphiphiles
derived from chiral aminopolyols (namely D-glucamine and
N-methyl-D-glucamine, 37a37d) have been observed to be excellent hydrogelators (Fig. 17).77 Such amphiphiles can be generated
from readily available unprotected aminosugars and hydrophobic isocyanates by one-step procedures in aqueous media.
These gelators can form hydrogels at room temperature after

sonication at low concentrations (1.03.0 wt%). It is noteworthy
that some derivatives (37b37d) also form lyotropic liquid
crystals with lamellar or hexagonal morphologies.
Some urea-based compounds have poor solubility and precipitate from solvents by the typical heatingcooling process. In
cases in which the direct transformation of these compounds
from precipitate to gel triggered by sonication at room temperature hardly occurs due to the strong interaction between
gelator molecules, heat, as a favourable secondary stimulus,
can be used in conjunction with sonication to produce sonogels. For example, compound 38 reported by Dou C. et al. was
dissolved in dimethylformamide (DMF) and dimethylsulfoxide
(DMSO) at elevated temperatures (Fig. 18).78 Upon slowly
cooling the hot solution to room temperature for over 15 min,
a large amount of ordinary precipitate was generated. To obtain
gels, the hot solution was stimulated by sonication in a water
bath at 25 1C for 10 s, and this process successfully prevented a
solprecipitate transition. However, during this process, the
temperature difference played an important role in determining the gelation and physical properties of the gel, which is
similar to the phenomenon observed in the sonogel process of
11a and 11b.
With a reasonable design, sonogels obtained by sonication
can also respond to other stimuli resulting in phase changes
and can then be reversed by a second stimulus without heat. A
suspension of tris-urea compound 39a could gel in organic
solvents, including acetone, MeOH, THF and diethyl phthalate,
after brief sonication.79 These gels were observed to be stable
for several months. Addition of Bu4N+X (but not that of
Bu4N+BF4 ) caused a gelsol transition. In another study, the
Lewis acid BF3OEt2 or ZnBr2, acting as a positive stimulus,
could re-gel the corresponding sol upon ultrasound treatment.
Thus, this gel was regarded as a smart switch stimulated
cooperatively by salt and ultrasound. Similar transitions have
also been achieved for 39b.80
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Fig. 17
Chemical structures of 37(ad).
Fig. 18
The cooperative eect of chemical input and sonication has

also been observed for the modified nucleoside organogel 40
containing a urea linker.81 By a heatingcooling process, a weak
and unstable hydrogel formed in water. After the hydrogel was
aged for approximately 12 h, water was expelled from the gel
network, and the gel transformed into an amorphous solid.
Following brief sonication for approximately 1 min, the precipitate could be reformed into a new and stable hydrogel. It
was proved that the OH radical produced by sonication in water
could oxidise 40 to a radical species, which exhibited a better
5360 | Chem. Soc. Rev., 2014, 43, 5346--5371
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balance between hydrophilic and hydrophobic interactions for

stabilising the gel state. Furthermore, after the removal of
ultrasound irradiation, the unstable radical species could be
gradually reverted to the original form.
The first urea-based thixotropic organogel, 41, was reported
by B. L. Feringa et al. (Fig. 18).82 41 could form gels in DMSO
by shaking or stirring at concentrations ranging from 20 to
40 mg mL 1, whereas in the lower concentration range of 10 to
20 mg mL 1, a gel could only be obtained by sonication. It
should be noted that this process was a sol-to-gel transition
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triggered by shaking or stirring, which was dierent from the

schemes reported by our group50 or Y. Fang,53 in which preexisting fibrils are broken by mechanical force. The room
temperature gels formed by mechanical stress usually exhibited
a lower Tg o 45 1C; therefore, it was concluded that the precipitateto-gel transition induced by shaking may be composed of
precipitate-to-sol and sol-to-gel transitions rather than a direct
precipitate-to-gel transition. The mechanism is such that
mechanically breaking fibrils would yield significantly more
fibril fragments as nucleation points. These fragments would
grow again rapidly into fibrils of sucient size and aggregate to
form a fibrous gel network.
2.5 Other types of organogels responsive to ultrasound and
mechanical stress
In addition to the above-mentioned gelator moieties, which are
classic and extensively used to construct organogels, there are
also many other types of organogelators discovered by serendipity that can respond to sonication or mechanical force. As a
typical example, Weiss et al. reported a series of organogelators
based on hydroxystearic acid (HSA) and stearic acid (SA) without any p units (Fig. 19).83 Some of these organogels recover
their viscoelasticity very rapidly after being destroyed by shear.
For example, gels of 42a in silicone oil (2 wt%) can recover
approximately 90% of their original viscoelasticity within 10 s
after the cessation of destructive shear, and several other gels,
Chem Soc Rev
including HAS, 42b, 43d and 43f, show reduced recovery of

viscoelasticity but are equally fast in doing so.
Due to the competition of multiple noncovalent interactions
between gelators and gelatorsolvent systems, LMOGs always
exhibit weak mechanical behaviour. Recently, multiple complementary hydrogen bonding motifs or cooperative multiple
noncovalent interactions have been observed for achieving
strong binding in organic solvents or water. These strong yet
reversible noncovalent interactions lead to thermodynamically
controlled supramolecular polymerisation, thus resulting in
self-supporting gels that can be moulded into different shapes
without cracking. As smart and adaptable materials, these gels
also show outstanding self-healing properties. For example,
Araki et al. reported the first nucleoside derived supragelator
containing alkylsilyl (48, Fig. 20), which could be used to
construct a flexible, self-supporting film from an ethyl acetate
solution (5% wt/wt).84
The sugar-based organogels 49a and 49b reported by A.
Vidyasagar and co-workers are also examples of selfsupporting gels that can gel in hydrocarbon solvents at concentrations as low as 0.2 wt% (Fig. 21).85 These alkane gels
show high gelsol transition temperatures indicative of the
high strength of the gels, which could be moulded into any
self-supporting geometrical shape. These gels also showed
remarkable self-healing properties. When a block of gel was
cut into two pieces and then joined together, the pieces merged
Fig. 20 Chemical structure of compound 48 and the image of the self-supported gel film. (Reprinted with permission from ref. 84. Copyright 2004,
Wiley-VCH Verlag GmbH & Co. KGaA.)
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Fig. 21
into a continuous block due to a dynamic equilibrium between

free dissolved gelators and self-assembled gelators (fibres) in
the gel. Such movement of free gelator molecules across the
interface allowed for the growth of fibres across the fusion
interface or the connection of broken fibres across the interface, thus facilitating the self-healing process. These gels also
displayed remarkably high transparency in the visible region
and weak transmittance in the ultraviolet region. Based on this
result, the gel may be placed in paraffin oil and moulded into
different optical components, such as lenses, prisms, gel plates
and tubes.
2.6
Two-component organogels
Two-component systems often display multiple functions in

surface patterns, optical properties, multi-response, etc. The
properties and functionality of these two-component systems
can be more precisely tuned and controlled in an intelligent
mode. However, in a two-component system, phase separation
is inevitable because of the competition between congeneric
molecules and heterogeneous components. As a result, the selfassembly of congeneric molecules themselves rather than heterogeneous components may be generated in two-component systems.
As an intense high-frequency compressional wave, ultrasound
may cleave and tune inter- or intramolecular interactions,
including hydrogen bonding, p-stacking and hydrophobic
interactions, in the self-assembly process of gel formation;
thus, ultrasound treatment may promote intermolecular interactions between heterogeneous molecules to produce a new
homogeneous gel system that has the functions of two components combined in one system. To form such a system, hydrogen bonding, electrostatic, coordination as well as p-stacking
interactions have been used to induce hostguest interactions
in organogels. A few typical examples are presented in the
following.
Fig. 22
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The smallest hostguest robust hydrogels formed by multiple hydrogen bond interactions among the rigid melamine (50)
and uric acid (51) were reported by J. W. Steed (Fig. 22).86
Neither of these compounds is soluble in water, but when
subjected to sonication and shaking over a period of approximately 5 minutes, the compounds could gel in water in a ratio
of 1 : 1 at concentrations of 0.8 wt% and above. Theoretical
calculations and 13C MAS-NMR and PXRD data revealed that
the rigid and planar assembly formed by strong pp stacking
and infinite hydrogen bonding assisted the gel formation.
It is reasonable to expect that ultrasound could be favourable in strengthening the hydrogen bonding among congenic molecules. Recently, we reported the ultrasound-assisted
co-aggregation of a gel (52) and a micro-crystal (53) system featuring an amino acid and imidazole-based derivative.87 Circular
dichroism (CD), XRD, IR data and optimised molecular geometry
calculations indicated that sonication weakened the intermolecular interaction between congeneric molecules of 52, thus
providing the opportunity for the naked COOH from 52 to bind
with the N-imidazole of 53 by hydrogen bonding. The sonicationtriggered co-aggregation was thermally stable and could not be
destroyed by repeated heatingcooling cycles. In a further study,
fibres with multicolour emission were obtained by tuning the
ratio of 52 to 53. The two-component sonogels are sensitive to
acid and metal ions, with the morphology transformed from that
of a fibre structure to that of vesicles. Moreover, both the gel
state and the morphology can be reversed by further addition of
alkali.
By virtue of a characteristic structure with a hydrophilic
exterior surface and a hydrophobic interior cavity, which can
accommodate a wide range of molecules as guests, cyclodextrins (CDs) have been widely used as hosts in supramolecular chemistry for fabricating various nanostructures.88,89
Among the varieties of guest molecules used, those containing
an adamantane group (AD) have been extensively used because
of the high-complexation ability between AD and CD, especially
b-CD.90,91 To investigate the aggregation properties of the
hostguest complex, we designed and synthesised a gelator
containing an AD group (54), whose gelation behaviour can be
controlled by sonication (Fig. 23).92 It is surprising that the selfassembly process of 54 can also be tuned by hostguest interactions via addition of b-CD under sonication. A structural
evolution from nanoribbons to ordered nanothreads was
observed by manipulation of the self-assembly between this
adamantine-based gelator and b-CD.93
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Fig. 23 (A) The structure of 54; the morphology of the DMF gel of (B) 54 and (C) 54 + b-CD triggered by sonication. (Reprinted with permission from
ref. 93. Copyright 2013, Royal Society of Chemistry.)
The two-component gels formed by hostguest interaction

can also be thixotropic. Recently, Liu and coworkers reported
two-component hydrogels composed of bolaamphiphilic L-histidine
(55) and benzene dicarboxylic acids (OPA, IPA or TPA) with the
capacity for noncovalent polymer formation after a traditional
heatingcooling process (Fig. 24). The structure of the dicarboxylic acids was proved to be an important factor for the
different behaviours of the gels. Hydrogels formed using
OPA55 and IPA55 showed thixotropic properties. When the
gels were shaken by hand, the hydrogels could transform into
sols without any phase separation, and the sols could again
transform into gels after being rested at room temperature for
several hours. However, thixotropy cannot be achieved by
TPA55 due to the linear molecular packing and ordered
hydrogen bonds among complexes in the compound.94
Using electrostatic interaction to construct hostguest functional organogels is also an effective way to obtain multiresponsive two-component gels. For example, Shinkai et al.
reported an oligothiophene-based organogelator 56 that could
gel in mixed solvents of EtOH and CH3Cl with a volume ratio of
1 : 1 and exhibited thixotropic behaviour.95 The addition of
1,2-bisammonium ethylene compounds as the guests of 56 could
shorten the recovery time after being mechanically broken and
made the gel more transparent without phase separation
because the hostguest interactions served as junction points.
The recovery time could be tuned by the concentration of the
guest (from 10 mg L 1 to 1.2 g L 1) from minutes to days. The
most interesting result obtained was the chiral memory switching displayed by the hostguest interaction. By a heating
cooling process, a gel with R,R-1,2-bisammonium cyclohexane
or S,S-1,2-bisammonium cyclohexane showed remarkable
induced CD spectra. By a shakingrest process, the recovered

gel was CD-silent; then, after a further heatingcooling cycle,
the CD signal could be recovered.
In a thixotropic gel system, emission can also be triggered
by mechanical force, just as in sonogels. Recently, Thomas
Baumgartner et al. reported an interesting mechanically driven
transition in emission colour controlled by heat and mechanical
force.96 In a homogeneous gel system, the electrostatic repulsion
prevented strong intermolecular interactions between 57 and 58
(57 as the emission donor, 58 as the acceptor, in a ratio of
100 : 1), thus leading to less energy transfer and the blue emission of 57; after shaking, changes in intramolecular conformation and phase separation decreased the intermolecular distance
between 57 and 58, resulting in an ecient energy transfer
process and thus orange emission. By further treating with heat,
the blue emission and gel state could be restored.
3. Mechanism of gelation controlled

by ultrasound and mechanical stress
As indicated in the examples described above, it is intriguing
that physical stimuli such as sonication and shearing stress do
not always serve as inhibitors of the gelation process; the
stimuli can also be favourable for gelation events. Unlike gels
controlled by chemical stimuli, whose structure is more predictable, most gel systems and their amazing physical properties, which are sensitive to physical stimuli, have been
discovered by serendipity. However, with the aid of techniques
such as X-ray diraction (XRD), small angle X-ray scattering
(SAXS), NMR, SEM, TEM, confocal laser scanning microscopy,
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Fig. 24
circular dichroism (CD) and absorption and fluorescent

spectroscopy, general rules that can guide us in designing
and studying new molecular systems have been developed that
make gelation predicable. These rules are associated with the
intrinsic nature of gelation and the corresponding response
processes.
3.1 Eect of ultrasound and mechanical stress expressed at
the molecular level of gelators
From the above results, it is indicated that the mechanical force
and moderate sonication generally do not change or destroy the
chemical structure of a molecule in gel tissues.9,23 Sonication
serves two functions in the gelation process. First, sonication
can transform intramolecular interactions into intermolecular
interactions to assist the gelation process in case that the
5364 | Chem. Soc. Rev., 2014, 43, 5346--5371
energy dierence between formation of the two kinds of interactions is in a certain range.3436,45,46 The instant solgel
transition afforded by ultrasound is often attributed to the
conversion of the mode of molecular hydrogen bonding or pp
bonding from intramolecular interaction to intermolecular
interaction. By applying a heatingcooling process, a gel can
reform into the original sol; thus, the process can be regarded
as a switch in the structure and rheology tuned by heat and
ultrasound. For example, the solgel transition of compound
anti-1 is triggered by structural transformation from self-locked
pp stacking to inter-locked pp stacking.34 The intramolecular
hydrogen bonding between the vicinal NH and Cl in Pd-based
peptide gelator 2a/2b can be disrupted when subjected to
ultrasound.35 As a result, aggregates of the molecules can be
reorganised by intermolecular hydrogen bonding to form a
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belt-like network with a b-sheet structure to trap solvent molecules

and thereby form a gel. In an ALS system such as 10b, we have also
observed a conformational transition from intramolecular hydrogen bonding between the CQO bond of naphthalic anhydride
and NH (ethyl imide) to intermolecular hydrogen bonding
accompanied by vesiclefibre morphological changes.45
The other function that sonication may serve is the optimisation of the sequence or strength of intermolecular interactions in systems featuring multiple noncovalent interactions
to promote gelation.46,47 Therefore, a supramolecular system
with multiple hydrogen bonding interactions is prone to be a
sonication-sensitive organogel. For example, with the aid of
sonication, compound 59 can form weak opaque gels in a
mixed solvent composed of CH2Cl2CH3OH or CH3Cl3CH3OH.
This finding indicates that there is a transition from dimeric
capsules to a cross-linked hydrogen bonding mode among
molecules that was favourable for gelation (Fig. 25).97 In some
cases, to optimise intermolecular interactions, sonication may
also trigger the transition of molecular conformations to a
dynamic mode. Complex 4 is a typical example in which
a sonication-induced transformation of the conformation from
a perpendicular mode to a coplanar mode of 1,8-naphthalimide
and the tBu3tpy ring has been suggested.37 Sonication may thus
become an effective method for generating two-component
multi-functional gel systems or other nano/micro materials
such as in the co-aggregate state of 52 + 53, with the transformation of hydrogen bonds among congeneric molecules into
interactions among heterogeneous components. In summary,
conformational changes in molecules toward intramolecular or
intermolecular interactions can be adjusted via sonication,
which makes the gelation process or gels themselves more
tuneable, easier to implement and intelligent systems for further
potential applications.
3.2 Eect of ultrasound and mechanical stress expressed as
macro aggregation of self-assemblies
The macroscopic eects of ultrasound and mechanical stress on gel
systems can provisionally be divided into four types: (a) sol-to-gel; (b)
gel-to-gel; (c) precipitate-to-gel; and (d) gel-to-sol transformations.
Chem Soc Rev
The sol-to-gel transformation is generally caused by a molecular

transformation of intramolecular interactions into intermolecular interactions by a stimulus, as previously discussed.
The other three situations or transformations are more complicated. It should be noted that among most sonicationresponsive or thixotropic gels, morphological transformation
plays an important role in determining macro state changes.
For example, in the sonication-induced direct gel-to-gel process
of compound 11b in CH3CN, the sonication triggered the
transformation of a coreshell structure into nanospheres,
and the nanospheres regenerated in cross-linked nanofibres
were then observed by a confocal laser microscope (CLSM).47
The observation of a micro-phase transformation from a gel to
a partial gel and then back to a gel is in accordance with this
result. However, XRD experiments did not provide any data
contradicting the conformation change. In toluene, sonication
displayed a cutting effect on the morphology; fibres measuring
100 nm in width were cut into spindly fibres measuring
2040 nm in width. A similar effect was observed for compound
13a in toluene; specifically, 2D pattern changes in which large
cross-linked rings were transformed into smaller rings under
sonication were observed. In all of these processes, destruction
and regeneration coexist; thus, the gel state is retained throughout the entire processes.
The sonication-triggered precipitate-to-gel transition is similar to the gel-to-gel transition, with the entangled fibrillar
structure as the terminal state in most cases. For example,
separated spherulites were obtained from precipitation particles
of a nongelled sample of 3 wt% 26octanol.67 Each spherulite
showed a porous structure formed by fibre arrays in which the
fibre arms grew radially from the centre. In contrast, homogeneous 3D interconnected fibre networks were obtained from
the ultrasound-induced gel phase. In such networks, nanometresized branched fibres can extend from one network to the
adjacent one via mutual interpenetration and entanglement.
The precipitate of 11a in CH3CN also undergoes a precipitateto-gel transition under sonication over a temperature range of
5070 1C, accompanied by a morphological transition from
irregular nanomicelles to entangled fibres.
Fig. 25 Possibility of the tris(urea) 59 related to the transformation between dimeric capsules and supramolecular gels by sonication. (Reprinted with
permission from ref. 97. Copyright 2012, Royal Society of Chemistry.)
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Fig. 26 SEM images of compound 54 from ethanol (2.4 wt%): (a) precipitate from a heatingcooling process; (b) partial gel after sonication for 5 min; (c)
S-gel after sonication for 10 min; scale bars for a, b and c are 5, 5 and 1 mm, respectively. (Reprinted with permission from ref. 92. Copyright 2012, Royal
Society of Chemistry.)
Amazingly, sonication-triggered morphological changes in

gel formation are mostly reversible. When a sonogel is heated
to form a sol and then cooled, the initial state before sonication
can be repaired by heat stimulus without fatigue. Therefore, switches in morphology or phase, even surfaces, can be
easily obtained by sonication and heat. For example, Yao and
co-workers reported a direct morphological switch between
vesicles in solution and fibres in a sonogel based on polypeptide organogelator 34.74 This morphological transition was
reversible and repeatable without obvious fatigue eects and
was accompanied by a switch in macroscopic properties between
those of a transparent solution and those of an opaque gel. A
reversible conversion between vesicles and three-dimensional
gel networks by self-assembly in response to heating and sonication over a certain concentration range was also observed in our
ALS structure (54). We were able to use this special property to
transform the ethanol sol of 54 into a gel state or vesicles over a
concentration range of 1.74.4 wt% by sonication or a heating
cooling process (Fig. 26).92
Generally, simple mechanical stress generated by shaking or
shear stress cannot aect molecular conformation; therefore,
the destruction and self-healing process in a thixotropic gel is
highly dependent on the transformation of aggregates and the
spontaneous balance between the aggregates and solvent molecules. Fibrillar or porous networks are inclined to trap solvent
molecules to support a gel state. When the primary junctions
are destroyed, the gel transforms into a disordered aggregation
or other phase state such as a sol, precipitate or partial gel. The
transformation from a spherical structure to fibres has been
observed in self-healing processes after the removal of the
external source of stress. For example, the dense packing of
NMOPs (nanoscale metalorganic particles) measuring approximately 50300 nm in diameter was observed to support the gel
structure of 8 + CuX.41 When exposed to shaking, the gel
accumulation was separated with the destruction of the secondary structure; then, after removing the stress, the spherical
particles were cross-linked into nanofibres within 612 weeks
(Fig. 27). The conversion was completed after approximately
one year. For this slow transition, an intermediate pearlnecklace-like structure was clearly observed. Recently, Shinkai
et al. also reported a similar morphological evolution of
isolated disc-like aggregates into one-dimensional crosslinked assemblies. It is interesting that in many sonogels or
5366 | Chem. Soc. Rev., 2014, 43, 5346--5371
Fig. 27 TEM micrographs of a hydrogel 41: (a) fresh gel upon standing
(44 h), (b) sol after shaking (5 min), (c) transition of NMOPs of reformed gel
into pearl-necklace structures (in red) (36 weeks), (d) pearl-necklace
nanostructures (red rectangle) and 1D nanobundles (red arrow) (612 weeks),
(e) nanobundles and nanospheres (612 weeks), and (f) nanobundles in aged
gels (about a year). (Reprinted with permission from ref. 41. Copyright 2011,
American Chemical Society.)
thixotropic gels, a fibrillar structure or fibril network is the

terminal state.
By shaking and resting, transformations in phase and
morphology, and even chirality, can be obtained in thixotropic
gels by internal stimuli. Such materials are regarded as thirdgeneration self-healing materials. However, as self-healing soft
materials, the repaired structure of thixotropic gels is reasonably altered in some respect compared with the original structure. This phenomenon may be compared to the self-healing of
natural materials such as skin and bone, whose recovered state
shows a slight variation from the original, indicating some
degree of destruction. In some thixotropic gel systems, the
transition from a gel to a sol then to a self-healed gel is not
always infinite due to the dynamic evolution of the instable
structures. For example, the organogel of CNC 12b in an alkane
solvent demonstrated the importance of morphology in determining the thixotropic properties.48 At a gelation temperature
r28 1C, the gel formed with highly branched, small fibres in
spherulitic aggregates, which was thixotropic. After several
cycles, the system exhibited fatigue, and the structure was
increasingly fibre-like. In contrast, at a temperature 428 1C,
only long fibres were observed, and self-healing could not occur.
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Review Article
The self-healing ability was ultimately attributed to the constant

growth of spherulitic aggregates into fibres throughout the
entire evolution process.
4. Application of LMOGs responding

to ultrasound and mechanical stress
In addition to the physical and gelation properties of LMOGs,
as well as the mechanisms that are important for designing and
studying new organogelators, the extensive applications of
these organogels are also of great importance. Physically responsive organogels have found applications in many fields, such as
wettability switches, hybrid materials and pollutant removal.
4.1
Surface switches constructed by sonogels
Wettability, which is usually determined by multiple factors

such as chemical composition and the micro- or nanostructure
on surfaces, is one of the most important properties of solid
surfaces and has attracted increasing attention in recent years
for biomimetic applications and self-cleaning materials. The
surface morphology of physically responsive gels can be transformed on the micro- or macroscale due to molecular transformation, molecular aggregation mode, etc., when subjected to
external stimulation, thus resulting in the transformation of
Fig. 28 SEM images of the xerogel of T-gel (a), S-gel (b), R-gel (c) of 10a
from p-xylene (15 mg mL 1) and the photographs of the water droplet on
glass slices, spin-coated with the T-gel (d), S-gel (e), and R-gel (f).
(Reprinted with permission from ref. 84. Copyright 2004, Wiley-VCH
Verlag GmbH & Co. KGaA.)
Chem Soc Rev
the surface of xerogels. The first inspiring example of controllable surface wettability adjusted by sonication in an organogel
system was reported by our group.45,46 After a heatingcooling
process, a xerogel film of 10a showed a superhydrophobic
surface with a vesicle morphology (composed of a fibrous
network with pores on the surface) (Fig. 28). After being treated
with sonication, the sonication-induced S-xerogel had a surface
with a water contact angle (CA) of 104.41; then, at applying a
heatingcooling process to the S-gel, the contact angle could be
recovered. However, with a similar conformation transformation from a spherulitic structure to a fibre network stimulated
by sonication, the opposite result was obtained for sonogel 4:
the precipitate generated by a heatingcooling process had a
more hydrophilic surface with an average CA of 951, whereas
the gel formed by ultrasound exhibited a hydrophobic surface
(CA = 1441).
4.2
Hybrid functional materials constructed by sonogels
One of the most important properties of responsive gels is the

facile tuneability of the structure of the gelators responsible
for the observed properties. To obtain complex functional
materials, one strategy is to generate new composites by the
assembly of gels with other systems.98103 David Bardelang and
coworkers incorporated QDs (quantum dots) into an organogel
network via ultrasound for the first time.104106 Morphological
studies suggested that large QDs were incorporated into the
surfaces of gel fibres, whereas the gelation properties and the
fluorescence of the QDs were not significantly affected. Moreover, a hybrid gel or xerogel with TEMPO-bound QDs could
sense the decomposition product of azobisisobutyronitrile
(AIBN) with apparent changes in fluorescence.
Our group also prepared a hybrid gel featuring peptidebased derivatives (60, Fig. 29A) and up-conversion nanophosphors (UCNPs) that could exhibit multi-colour emission
when excited by near-infrared light.107 UCNPs (NaYF4) were
successfully transformed into a self-assembled LMOG network
through physical interactions in a polar solvent via sonication.
As a result, the UCNPs are dispersed in a gel matrix, and the
individually dispersed UCNPs acted as physical cross-links
between the supramolecular fibres, thereby reinforcing the gel
structure (Fig. 29B). This new strategy for producing UCNPpeptide
hybrid multi-colour gels allows the UCNPs to retain their nanophosphor properties in the gel state. These UCNP nano-composite
Fig. 29 (A) Chemical structures of 60a and 60b. (B) Self-assembly of 60b + UCNPs and fluorescent images of 60b + UCNP gels in n-hexanol ([60b] =
2.3 10 2 M, 1.5 wt% of UCNPs); images from left to right: 60b + UCNPs-Red, 60b + [UCNPs-Red/UCNPs-Green (1/1 wt)], 60b + UCNPs-Green, 60b +
[UCNPs-Green/UCNPs-Blue (1/1 wt)], 60b + UCNPs-Blue, 60b + [UCNPs-Blue/UCNPs-Red (1/1 wt)] (lex = 980 nm). (Reprinted with permission from
ref. 107. Copyright 2009, Royal Society of Chemistry.)
Chem. Soc. Rev., 2014, 43, 5346--5371 | 5367
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Chem Soc Rev
gels may fulfil the requirements for colour displays and NIR light
absorption materials for generating power or may be modified to
function as biological labels.
4.3
Thixotropic gels for oil collection and pollutant removal
Notably, the phase-selective gelation between water and oil

triggered by mechanical force at room temperature indicates
the feasibility of removing oil or pollutants from water sources.108
The first example of phase-selective gelation was demonstrated
by Bhattacharya and Krishnan-Ghosh with amino acid amphiphiles.109 Molecular gelators based on closed-chain and open-chain
sugars have been studied recently, which exhibit phaseselective gelation and can gel oil in the presence of water
at room temperature.110,111 After the phase-selective gelation
of the oil in these mixtures, both the oil and gelator can be
recovered and reused.
Thixotropic gels can also be used for pollutant removal. For
example, the compound N-lauroyl-L-glutamic-a,g-dibutylamide
can gel in many organic solvents and exhibit thixotropic properties. By combining the gelator and an appropriate extractant,
such as thiophene for mercury chelators or 4-(2-pyridylazo)resorcinol (PAR) for nickel ions, with an organic hydrocarbon
solvent to form a thixotropic gel, a solidliquid system for
extraction was constructed in a previous study. Experimental
results revealed that the system required only 10 min of
shaking to extract metal from water with high selectivity.112
4.4
Rheology switching in thixotropic gels
The control of the rheological properties of fluids during selfhealing processes is of practical importance for industrial applications, biomaterials and smart systems.20,21,50 Switches in rheology
may control the motion of fluid molecules toward damaged areas
to realise self-healing. Some thixotropic organogels are very
sensitive to mechanical stress and show switchable rheological
properties. These gels hold potential applications in, for example,
art cleaning and protection113 and blood and cell conservation.114
5. Conclusions and outlook

In conclusion, the history, types, mechanisms, as well as
applications of ultrasound and mechanical stress driven/
responsive organogels were examined and summarised in this
review. These gels show distinct gelation properties such as
in situ and instant gelation, phase-selective gelation and selfhealing properties. The structures of the molecules in these
compounds greatly determine the resulting gelation properties.
Alkane chain length, the position of chirality units, substitution
groups, peptide sequences as well as the hydrogen bonding
mode or hydrogen bond numbers can all cause the responsive
properties of gels to vary. The reported cholesterol-based organogels with the structure of an ALS2 system are often both
sonication-responsive and thixotropic and exhibit gelation properties at room temperature; phenyl alkane ester-based organogelators exhibit properties similar to those of cholesterol-based
organogelators; metallogels often exhibit reversible and facile gel
5368 | Chem. Soc. Rev., 2014, 43, 5346--5371
Review Article
colour or emission control due to the adjustment of pp interactions; and amide-based organogels, including peptide-based
organogels, exhibit low toxicity, which makes the gels more
injectable and practical in the field of drug delivery.
The gelation and stimulus-responsive mechanisms of the
aforementioned gels have been thoroughly studied and analysed. The physically driven gelation process depends on many
factors, such as the structural adjustment of gelator molecules,
solvent eects, concentration, temperature, sonication and shear
stress. A tiny change in these factors greatly impacts the gelation
properties of gels due to the precise balance between the
molecular assembly of gelator molecules, solventgelator interactions and the applied external stimulus. It has been determined that conformational changes in molecular structure may
occur either in sonogels or in thixotropic gels during the solgel
phase-transition process; however, it is still difficult to study
these changes using the present techniques without crystallisation data. Sonication- or shear-stress-induced dissociation or the
cross-linking effect on aggregates of gelators often results in
fibrillisation phenomena, which offer schemes for moulding
fibres into living tissues. Therefore, the study of dynamic assemblies stimulated by mechanical stimuli in supramolecular gel
tissues holds great significance in the field of biomimetics.
The extensive applications of organogels are of great importance in the design and study of new organogelators, helping us to
address open issues such as characterising gels and determining
practical applications for gels. In reality, most LMOGs are far from
finding applications due to the poor robustness of non-covalent
systems. However, some gels with outstanding mechanical and
optical properties would be more useful for practical application,
and great eorts have been undertaken in this field by several
researchers. The reversible control of organogel properties by the
application of heat and mechanical stimuli is often accompanied
by transformations in phase, morphological structure and rheological and spectroscopic properties, which make these gels suitable
for application in the field of drug delivery, switchable devices,
adaptive materials and self-healing materials, among others.
Acknowledgements
The authors acknowledge financial support from the National
Basic Research Program of China (2013CB733700), the China
National Funds for Distinguished Young Scientists (21125104),
the National Natural Science Foundation of China (51373039,
91022021, and 21301047), the Program for Innovative Research
Team in University (IRT1117), the Program of Shanghai Subject
Chief Scientist (12XD1405900), and the Shanghai Leading Academic Discipline Project (B108).
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Low-Molecular-Mass Gels Responding To Ultrasounds

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