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ABSTRACT: Inspired by the water-enhanced mechanical gradient character of the squid beak, we herein report a nanocomposite that mimics both the architecture and properties of this interesting natural material. Similar to the squid beak, we have developed nanocomposites where the degree of cross-linking is controlled along the length of the film. In this study, we utilized tunicate cellulose nanocrystals as the nanofiller that are functionalized with allyl moieties. Using photoinduced thiol-ene chemistry, we have been able to cross-link the CNC nanofiller. In the dry state where strong CNC interactions can occur, only a small mechanical contrast is observed between the cross-linked and uncross-linked samples. However, when the films are exposed to water, which "switches off" the noncovalent CNC interactions, a significant mechanical contrast is observed between the same films. For example, at 20 wt % CNC (in the dry film), an increase in wet modulus from 60 to 300 MPa (∼500% increase) is observed after photoirradiation. Furthermore, we show that the wet modulus can be controlled by altering the UV exposure time which allows access to mechanical gradient films.
Journal of the American Chemical Society 03/2013; · 9.91 Impact Factor
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ABSTRACT: Polymers that can easily be repaired after being damaged are attractive as this characteristic can improve the reliability, functionality, and lifetime of many products. In the last decade, researchers have thus developed new approaches to create stimuli-responsive polymer systems, which have the ability to autonomously heal or can be repaired upon exposure to an external stimulus. This review summarizes the current knowledge of optically healable or photo-healable polymers. The use of light as a stimulus for healing offers several attractive features, including the ability to deliver the stimulus locally, which opens up the possibility of healing the material under load, as well as the ability to tailor the wavelength of light to selectively address a specific component of the material, e.g. only the damaged parts. So far, two main classes of optically healable polymers have been explored, which are structurally dynamic polymers and mechanically activated reactive systems.
Chemical Society Reviews 03/2013; · 28.76 Impact Factor
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ABSTRACT: Low molecular weight supramolecular gels consist of small molecules (gelators) that in an appropriate solvent self-assemble into nano- or micro-scale network structures resulting in the formation of a gel. Most supramolecular gels consist of two parts, namely the solvent and the gelator. However, the concept of multi-component supramolecular gels, in which more than one compound is added to the solvent, offers a facile way (e.g. by changing the ratio of the different components) to tailor the properties of the gel. The simplest multi-component gels consist of two components added to the solvent and are the most widely studied to date. There are three general classes of such multi-component gels that have been investigated. The first class requires all the added components to access the gel; that is, no component forms a gel on its own. A second class uses two (or more) gelators which can either co-assemble or self-sort into distinct assemblies and the final class consists of one (or more) gelator and one (or more) non-gelling additive which can impact the assembly process of the gelator and therefore the gel's properties.
Chemical Society Reviews 06/2012; 41(18):6089-102. · 28.76 Impact Factor
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ABSTRACT: The synthesis of cadmium sulfide (CdS), zinc sulfide (ZnS), and lead sulfide (PbS) nanoparticle chains on cellulose nanocrystal
(CNC) templates can be accomplished by the reaction of the precursor salts. The use of a cationic surfactant, cetyltrimethylammonium
bromide (CTAB), was critical for the synthesis of well-defined semiconductor nanoparticle chains on the surface of the CNCs.
The semiconductor nanoparticle particle size and packing density on CNC surface could be controlled by the variation of the
precursor concentration and the pH of the salt solution.
Journal of Materials Science 04/2012; 46(17):5672-5679. · 2.02 Impact Factor
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ABSTRACT: A supramolecular polymer blend, formed via π-π interactions between a π-electron rich pyrenyl end-capped oligomer and a chain-folding oligomer containing pairs of π-electron poor naphthalene-diimide (NDI) units, has been reinforced with cellulose nanocrystals (CNCs) to afford a healable nanocomposite material. Nanocomposites with varying weight percentage of CNCs (from 1.25 to 20.0 wt %) within the healable supramolecular polymeric matrix have been prepared via solvent casting followed by compression molding, and their mechanical properties and healing behavior have been evaluated. It is found that homogeneously dispersed films can be formed with CNCs at less than 10 wt %. Above 10 wt % CNC heterogeneous nanocomposites were obtained. All the nanocomposites formed could be rehealed upon exposure to elevated temperatures although, for the homogeneous films, it was found that the healing rate was reduced with increasing CNC content. The best combination of healing efficiency and mechanical properties was obtained with the 7.5 wt % CNC nanocomposite which exhibited a tensile modulus enhanced by as much as a factor of 20 over the matrix material alone and could be fully rehealed at 85 °C within 30 min. Thus it is demonstrated that supramolecular nanocomposites can afford greatly enhanced mechanical properties relative to the unreinforced polymer, while still allowing efficient thermal healing.
Journal of the American Chemical Society 03/2012; 134(11):5362-8. · 9.91 Impact Factor
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ABSTRACT: Films exhibiting multiresponsive shape-memory properties have been accessed using covalently cross-linked metallo-supramolecular polymers. Low molecular weight poly(butadiene) was end-capped with 4-oxy-2,6-bis(N-methylbenzimidazolyl)pyridine (-OMebip) ligands that upon addition of metal salts spontaneously formed high molecular weight metallo-supramolecular polymers. The addition of a tetra-functional thiol along with a photoinitiator results in mechanically stable films via solution-casting. These films consist of a soft poly(butadiene) phase and a hard metal-ligand phase. Photo-cross-linking of the poly(butadiene) soft phase, via the thiol-ene reaction, upon exposure to relatively low intensity light, allows access to a diverse range of permanent shapes. Investigations into the temporary shape fixing and recovery of these materials were undertaken to determine the effects of cross-link density and the nature of the metal salts. The key component in fixing and releasing the temporary shape is the metal-ligand hard phase, and as such any stimulus that can disrupt this phase (light, heat, or chemicals) can be used to create the temporary shape and induce its recovery back to the permanent shape.
Journal of the American Chemical Society 08/2011; 133(32):12866-74. · 9.91 Impact Factor
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ABSTRACT: New biomimetic, stimuli-responsive mechanically adaptive nanocomposites, which change their mechanical properties upon exposure to water and display a water-activated shape-memory effect, were investigated. These materials were produced by introducing rigid cotton cellulose nanowhiskers (CNWs) into a rubbery polyurethane (PU) matrix. A series of materials with CNW concentrations of 2–20% v/v was produced by solution blending CNWs and the PU. Films were subsequently prepared by compression molding. The introduction of CNWs led to an increase of the tensile storage moduli (E′) in the dry nanocomposites. The level of reinforcement scaled with the CNW content and followed the Halpin–Kardos model below and the percolation model above the percolation limit of 7% v/v. Upon exposure to water, the materials with a CNW content above the percolation limit swelled slightly and showed a decrease of E′, for example from 1 GPa to 144 MPa in the case of the material with 20% v/v CNWs. This effect is the result of competitive hydrogen bonding between water and CNWs, which reduces the hydrogen bonding between the CNWs and weakens the CNW network that drives the reinforcement in the dry state. The mechanically adaptive behavior and a high elasticity of the wet materials are the basis for a shape-memory effect that uses water as the stimulus. Polarized Raman spectroscopy revealed that in the temporary shape, generated by stretching and drying water-swollen nanocomposites, the CNWs display a significant level of uniaxial orientation.
08/2011;
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ABSTRACT: Polymers with the ability to repair themselves after sustaining damage could extend the lifetimes of materials used in many applications. Most approaches to healable materials require heating the damaged area. Here we present metallosupramolecular polymers that can be mended through exposure to light. They consist of telechelic, rubbery, low-molecular-mass polymers with ligand end groups that are non-covalently linked through metal-ion binding. On exposure to ultraviolet light, the metal-ligand motifs are electronically excited and the absorbed energy is converted into heat. This causes temporary disengagement of the metal-ligand motifs and a concomitant reversible decrease in the polymers' molecular mass and viscosity, thereby allowing quick and efficient defect healing. Light can be applied locally to a damage site, so objects can in principle be healed under load. We anticipate that this approach to healable materials, based on supramolecular polymers and a light-heat conversion step, can be applied to a wide range of supramolecular materials that use different chemistries.
Nature 04/2011; 472(7343):334-7. · 36.28 Impact Factor
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ABSTRACT: The mechanically induced molecular deformation of cellulose nanowhiskers embedded in subpercolation concentration in an epoxy resin matrix was monitored through Raman spectroscopy. Cellulose nanowhiskers isolated by sulfuric acid hydrolysis from tunicates and by sulfuric acid hydrolysis and hydrochloric acid hydrolysis from cotton were used to study how the aspect ratio (ca. 76 for tunicate and 19 for cotton) and surface charges (38 and 85 mmol SO(4)(-)/kg for sulfuric acid hydrolysis of cotton and tunicate, respectively; no detectable surface charges for hydrochloric acid hydrolysis) originating from the isolation process influence stress transfer in such systems. Atomic force microscopy confirmed that uncharged cellulose nanowhiskers produced by hydrochloric acid hydrolysis have a much higher tendency to aggregate than the charged cotton or tunicate nanowhiskers. Each of these nanowhisker types was incorporated in a concentration of 0.7 vol % in a thermosetting epoxy resin matrix. Mechanically induced shifts of the Raman peak initially located at 1095 cm(-1) were used to express the level of deformation imparted to the nanowhiskers embedded in the resin. Much larger shifts of the diagnostic Raman band were observed for nanocomposites with tunicate nanowhiskers than for the corresponding samples comprising cotton nanowhiskers. In the case of nanocomposites comprising nanowhiskers produced by hydrochloric acid hydrolysis, no significant Raman band shift was observed. These results are indicative of different modes of stress transfer, which in turn appear to originate from the different sample morphologies.
Biomacromolecules 03/2011; 12(4):1363-9. · 5.48 Impact Factor
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CHIMIA International Journal for Chemistry 01/2011; 65(9):745. · 1.21 Impact Factor
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ABSTRACT: New materials that have the ability to reversibly adapt to their environment and possess a wide range of responses ranging from self-healing to mechanical work are continually emerging. These adaptive systems have the potential to revolutionize technologies such as sensors and actuators, as well as numerous biomedical applications. We will describe the emergence of a new trend in the design of adaptive materials that involves the use of reversible chemistry (both non-covalent and covalent) to programme a response that originates at the most fundamental (molecular) level. Materials that make use of this approach - structurally dynamic polymers - produce macroscopic responses from a change in the material's molecular architecture (that is, the rearrangement or reorganization of the polymer components, or polymeric aggregates). This design approach requires careful selection of the reversible/dynamic bond used in the construction of the material to control its environmental responsiveness.
Nature Material 01/2011; 10(1):14-27. · 32.84 Impact Factor
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12/2010;
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ABSTRACT: An elastomeric, healable, supramolecular polymer blend comprising a chain-folding polyimide and a telechelic polyurethane with pyrenyl end groups is compatibilized by aromatic pi-pi stacking between the pi-electron-deficient diimide groups and the pi-electron-rich pyrenyl units. This interpolymer interaction is the key to forming a tough, healable, elastomeric material. Variable-temperature FTIR analysis of the bulk material also conclusively demonstrates the presence of hydrogen bonding, which complements the pi-pi stacking interactions. Variable-temperature SAXS analysis shows that the healable polymeric blend has a nanophase-separated morphology and that the X-ray contrast between the two types of domain increases with increasing temperature, a feature that is repeatable over several heating and cooling cycles. A fractured sample of this material reproducibly regains more than 95% of the tensile modulus, 91% of the elongation to break, and 77% of the modulus of toughness of the pristine material.
Journal of the American Chemical Society 09/2010; 132(34):12051-8. · 9.91 Impact Factor
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ABSTRACT: An elastomeric, healable, supramolecular polymer blend comprising a chain-folding polyimide and a telechelic polyurethane with pyrenyl end groups is compatibilized by aromatic π−π stacking between the π-electron-deficient diimide groups and the π-electron-rich pyrenyl units. This interpolymer interaction is the key to forming a tough, healable, elastomeric material. Variable-temperature FTIR analysis of the bulk material also conclusively demonstrates the presence of hydrogen bonding, which complements the π−π stacking interactions. Variable-temperature SAXS analysis shows that the healable polymeric blend has a nanophase-separated morphology and that the X-ray contrast between the two types of domain increases with increasing temperature, a feature that is repeatable over several heating and cooling cycles. A fractured sample of this material reproducibly regains more than 95% of the tensile modulus, 91% of the elongation to break, and 77% of the modulus of toughness of the pristine material.
08/2010;
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ABSTRACT: The mechanism of gelation of 50/50 w/w mixtures of guanosine (G) and 2',3',5'-tri-O-acetylguanosine (TAcG) in aqueous 0.354 M KCl was investigated using a combination of static light scattering (SLS), polarized and depolarized dynamic light scattering (VV and VH DLS), small-angle neutron and X-ray scattering (SANS and SAXS), and viscometric experiments. SLS and viscometry show a dramatic increase in apparent molecular weight and hydrodynamic volume at 0.2 wt % and 0.3 wt %, respectively, indicating the critical concentration for self-association of G/TAcG quartets into columnar assemblies lies below 0.2 wt %. Above this concentration, SANS and SAXS generate complementary information on the structure of the individual columnar stacks. VV and VH DLS results indicate bimodal correlation functions, whose properties suggest, respectively, translational and rotational diffusion of a bimodal distribution of particles. The fast mode appears to originate from fibrillar agglomerates of G/TAcG columnar quartet assemblies, while the slow mode comes from microgel domains. Guinier plot analysis of the SLS data probes the internal structure of the microgel domains. Collectively, the results suggest that sol and microgel phases coexist below the macroscopic gel point, and that the sol phase contains individual columnar stacks of G/TAcG quartets and fibrillar aggregates formed via lateral aggregation of these columnar assemblies. With increasing concentration, the DLS data indicate a progressive increase in the volume fraction of microgel domains, which ultimately leads to macroscopic gelation. Prior observation of a transient network contribution to the gel rheology at low temperature is attributed to the presence of individual columnar stacks within the gel network.
Langmuir 04/2010; 26(12):10093-101. · 4.19 Impact Factor
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ABSTRACT: Quantitative insights into the stress-transfer mechanisms that determine the mechanical properties of tunicate cellulose whisker/poly(vinyl acetate) nanocomposites were gained by Raman spectroscopy. The extent of stress-transfer is influenced by local orientation (or anisotropy) of the whiskers, which in turn is governed by the processing conditions used to fabricate the nanocomposites. Solution-cast materials display no microscopic anisotropy, while samples that were cast and subsequently compression molded contain both isotropic regions as well as domains of locally oriented whiskers. Polarized optical microscopy showed these regions to have dimensions in the hundreds of mum. Polarized Raman spectroscopy of the 1095 cm(-1) Raman band, associated with C-O ring stretching of the cellulose backbone, was used to quantify the local orientation of the cellulose whiskers. Clear and discernible shifts of this Raman band upon uniaxial deformation of nanocomposite films were further used to determine the level of stress experienced by the cellulose whiskers, ultimately reflecting the levels of stress-transfer predominantly between the poly(vinyl acetate) matrix and the tunicate whiskers, but also between the whiskers within the network. In the isotropic regions, where whiskers form a percolating network, the observed Raman shift rate with respect to strain is smaller than in the regions where the whiskers are uniaxially orientated. The Raman shift is strongly affected by the presence of water, leading to a lack of stress-transfer when the samples are fully hydrated, which is clearly detected by the Raman technique. Heating of the nanocomposites above the glass transition temperature of the poly(vinyl acetate) matrix also reduces the stress experienced by the individual whiskers.
Biomacromolecules 02/2010; 11(3):762-8. · 5.48 Impact Factor
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ABSTRACT: A new series of biomimetic stimuli-responsive nanocomposites, which change their mechanical properties upon exposure to physiological conditions, was prepared and investigated. The materials were produced by introducing percolating networks of cellulose nanofibers or "whiskers" derived from tunicates into poly(vinyl acetate) (PVAc), poly(butyl methacrylate) (PBMA), and blends of these polymers, with the objective of determining how the hydrophobicity and glass-transition temperature (Tg) of the polymer matrix affect the water-induced mechanically dynamic behavior. Below the Tg (approximately 60-70 degrees C), the incorporation of whiskers (15.1-16.5% v/v) modestly increased the tensile storage moduli (E') of the neat polymers from 0.6 to 3.8 GPa (PBMA) and from 2 to 5.2 GPa (PVAc). The reinforcement was much more dramatic above Tg, where E' increased from 1.2 to 690 MPa (PVAc) and approximately 1 MPa to 1.1 GPa (PBMA). Upon exposure to physiological conditions (immersion in artificial cerebrospinal fluid, ACSF, at 37 degrees C) all materials displayed a decrease in E'. The most significant contrast was seen in PVAc; for example, the E' of a 16.5% v/v PVAc/whisker nanocomposite decreased from 5.2 GPa to 12.7 MPa. Only a modest modulus decrease was measured for PBMA/whisker nanocomposite; here the E' of a 15.1% v/v PBMA/whisker nanocomposite decreased from 3.8 to 1.2 GPa. A systematic investigation revealed that the magnitude of the mechanical contrast was related to the degree of swelling with ACSF, which was shown to increase with whisker content, temperature, and polarity of the matrix (PVAc>PBMA). The mechanical morphing of the new materials can be described in the framework of both the percolation and Halpin-Kardos models for nanocomposite reinforcement, and is the result of changing interactions among the nanoparticles and plasticization of the matrix upon swelling.
ACS Applied Materials & Interfaces 01/2010; 2(1):165-74. · 4.53 Impact Factor
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ABSTRACT: A novel supramolecular polymer system, in which the terminal pyrenyl groups of a polyamide intercalate into the chain-folds of a polyimide via electronically-complementary pi-pi stacking, shows both enhanced mechanical properties relative to those of its individual components and facile healing characteristics as a result of the thermoreversibility of non-covalent interactions.
Chemical Communications 11/2009; · 6.17 Impact Factor
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ABSTRACT: The past few decades have seen a significant growth in the field of supramolecular polymerizations, in which (reversible) noncovalent interactions (e.g., hydrogen bonding, metal−ligand coordination, π−π stacking, etc.) between (macro)monomeric units are utilized to build polymeric assemblies. These polymeric aggregates can exist in an equilibrium state between low and high molecular weight species, which in turn opens the door to a new matrix of properties. For example, such supramolecular polymers are potentially an interesting class of stimuli- or environmentally responsive, “smart” materials. Additionally, the establishment of an equilibrium during the assembly process imparts on the system the ability to “proofread” assemblies and, depending on the nature of the (macro)molecules, can allow efficient access to controlled, well-defined nanostructures. This Perspective will focus on the basic concepts of such supramolecular polymerizations, such as mechanism of assembly growth, and the effects of growth kinetics, phase segregation, and growth on the surface has on the assembly and properties of the resulting supramolecular polymers, highlighting these concepts with selected literature examples.
08/2009;
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Stuart J Rowan
Nature Chemistry 08/2009; 1(5):347-8. · 20.52 Impact Factor
