RESUMO
Reversible cross-links by non-covalent bonds have been widely used to produce supramolecular hydrogels that are both tough and functional. While various supramolecular hydrogels with several kinds of reversible cross-links have been designed for many years, a universal design that would allow control of mechanical and functional properties remains unavailable. The physical properties of reversible cross-links are usually quantified by thermodynamics, dynamics, and bond energies. Herein, we investigated the relationship between the molecular mobility and mechanical toughness of supramolecular hydrogels consisting of two kinetically distinct reversible cross-links via host-guest interactions. The molecular mobility was quantified as the second-order average relaxation time (ãτãw) of the reversible cross-links. We discovered that hydrogels combining fast (ãτãw = 1.8 or 18 s) and slowly (ãτãw = 6.6 × 103 or 9.5 × 103 s) reversible cross-links showed increased toughness compared to hydrogels with only one type of cross-link because relaxation processes in the former occurred with wide timescales.
RESUMO
Polyurethane (PU) materials with movable crosslinking were prepared by a typical two-step synthetic process using an acetylated γ-cyclodextrin (TAcγCD) diol compound. The soft segment of PU is polytetrahydrofuran (PTHF), and the hard segment consists of hexamethylene diisocyanate (HDI) and 1,3-propylene glycol (POD). The synthesized PU materials exhibited the typical mechanical characteristics of a movable crosslinking network, and the presence of hydrogen bonds from the urethane bonds resulted in a synergistic effect. Two kinds of noncovalent bond crosslinking increased the Young's modulus of the material without affecting its toughness. Fourier transform infrared spectroscopy and X-ray scattering measurements were performed to analyze the effect of introducing movable crosslinking on the internal hydrogen bond and the microphase separation structure of PU, and the results showed that the carbonyl groups on TAcγCD could form hydrogen bonds with the PU chains and that the introduction of movable crosslinking weakened the hydrogen bonds between the hard segments of PU. When stretched, the movable crosslinking of the PU materials suppressed the orientation of polymer chains (shish-kebab orientation) in the tensile direction. The mechanical properties of the movable crosslinked PU materials show promise for future application in the industrial field.
RESUMO
Hydrogels are biocompatible polymer networks; however, they have the disadvantage of having poor mechanical properties. Herein, the mechanical properties of host-guest hydrogels were increased by adding a filler and incorporating other noncovalent interactions. Cellulose was added as a filler to the hydrogels to afford a composite. Citric acid-modified cellulose (CAC) with many carboxyl groups was used instead of conventional cellulose. The preparation began with mixing an acrylamide-based αCD host polymer (p-αCD) and a dodecanoic acid guest polymer (p-AADA) to form supramolecular hydrogels (p-αCD/p-AADA). However, when CAC was directly added to p-αCD/p-AADA to form biocomposite hydrogels (p-αCD/p-AADA/CAC), it showed weaker mechanical properties than p-αCD/p-AADA itself. This was caused by the strong intramolecular hydrogen bonding (H-bonding) within the CAC, which prevented the CAC reinforcing p-αCD/p-AADA in p-αCD/p-AADA/CAC. Then, calcium chloride solution (CaCl2) was used to form calcium ion (Ca2+) complexes between the CAC and p-αCD/p-AADA. This approach successfully created supramolecular biocomposite hydrogels assisted by Ca2+ complexes (p-αCD/p-AADA/CAC/Ca2+) with improved mechanical properties relative to p-αCD/p-AADA hydrogels; the toughness was increased 6-fold, from 1 to 6 MJ/m3. The mechanical properties were improved because of the disruption of the intramolecular H-bonding within the CAC by Ca2+ and subsequent complex formation between the carboxyl groups of CAC and p-AADA. This mechanism is a new approach for improving the mechanical properties of hydrogels that can be broadly applied as biomaterials.
Assuntos
Hidrogéis , Polímeros , Materiais Biocompatíveis , Cálcio , CeluloseRESUMO
We prepared photoresponsive actuators as both hydrogels and dry gels consisting of 4-arm poly(ethylene glycol) (PEG) cross-linked by a [c2]daisy chain, which is a double-threaded [2]rotaxane dimer with α-cyclodextrin (αCD) and stilbene. The obtained gels showed fast and large deformation triggered by UV irradiation in both wet and dry states. The UV/vis spectroscopy results, NMR measurements and tensile tests on the gels revealed that the actuation is driven by photoisomerization of the stilbene unit in the [c2]daisy chain. The responsiveness of these gels depends on the molecular weight of the 4-arm PEG. These results suggest that αCD recognizes trans-stilbene prior to UV irradiation to maintain the length of the PEG chain in the polymer network and that photoisomerization allows αCD to leave the cis-stilbene moiety and move onto the PEG chain because the association constant of αCD with cis-stilbene is quite low. Thus, the sliding motion of the αCD unit shrinks the [c2]daisy chain, leading to the contraction of the gels. In both wet and dry states, these actuations are repeatable through reversible photoisomerization of the stilbene moiety using different wavelengths of UV-light irradiation and can be used to perform bending and lifting actions (for 15 times heavier weight compared to the dry gel).
RESUMO
Practical applications like very thin stress-strain sensors require high strength, stretchability, and conductivity, simultaneously. One of the approaches is improving the toughness of the stress-strain sensing materials. Polymeric materials with movable cross-links in which the polymer chain penetrates the cavity of cyclodextrin (CD) demonstrate enhanced strength and stretchability, simultaneously. We designed two approaches that utilize elastomer nanocomposites with movable cross-links and carbon filler (ketjenblack, KB). One approach is mixing SC (a single movable cross-network material), a linear polymer (poly(ethyl acrylate), PEA), and KB to obtain their composite. The electrical resistance increases proportionally with tensile strain, leading to the application of this composite as a stress-strain sensor. The responses of this material are stable for over 100 loading and unloading cycles. The other approach is a composite made with KB and a movable cross-network elastomer for knitting dissimilar polymers (KP), where movable cross-links connect the CD-modified polystyrene (PSCD) and PEA. The obtained composite acts as a highly sensitive stress-strain sensor that exhibits an exponential increase in resistance with increasing tensile strain due to the polymer dethreading from the CD rings. The designed preparations of highly repeatable or highly responsive stress-strain sensors with good mechanical properties can help broaden their application in electrical devices.
RESUMO
The introduction of non-covalent bonds is effective for achieving self-healing properties because they can be controlled reversibly. One approach to introduce these bonds into supramolecular materials is use of host-guest interactions. This feature article summarizes the development of supramolecular materials constructed by non-covalent cross-linking through several approaches, such as host-guest interactions between host polymers and guest polymers, 1 : 2-type host-guest interactions, and host-guest interactions from the polymerization of host-guest inclusion complexes. Host-guest interactions show self-healing functions while also enabling stimuli-responsiveness (redox, pH, and temperature). The self-healing function of supramolecular materials is achieved by stress dispersion arising from host-guest interactions when stress is applied. Reversible bonds based on host-guest interactions have tremendous potential to expand the variety of functional materials.
RESUMO
The host-guest interaction as noncovalent bonds can make polymeric materials tough and flexible based on the reversibility property, which is a promising approach to extend the lifetime of polymeric materials. Supramolecular materials with cyclodextrin and adamantane are prepared by mixing host polymers and guest polymers by planetary ball milling. The toughness of the supramolecular materials prepared by ball milling is approximately 2 to 5 times higher than that of supramolecular materials prepared by casting, which is the conventional method. The materials maintain their mechanical properties during repeated ball milling treatments. They are also applicable as self-healable bulk materials and coatings, and they retain the transparency of the substrate. Moreover, fractured pieces of the materials can be re-adhered within 10 min. Dynamic mechanical analysis, thermal property measurements, small-angle X-ray scattering, and microscopy observations reveal these behaviors in detail. Scars formed on the coating disappear within a few seconds at 60 °C. At the same time, the coating shows scratch resistance due to its good mechanical properties. The ball milling method mixes the host polymer and guest polymer at the nano level to achieve the self-healing and recycling properties.
RESUMO
High toughness with self-healing ability has become the ultimate goal in materials research. Herein, thermoplastic polyurethane (TPU) was linked via host-guest (HG) interactions to increase its mechanical properties and self-healing ability. TPU linked via HG interactions was prepared by the step-growth bulk polymerization of hexamethylene diisocyanate (HDI), tetraethylene glycol (TEG), and HG interactions between permethylated amino ßCD (PMeAmßCD) and adamantane amine (AdAm). TPU linked with 10 mol% of HG interactions (HG(10)) showed the highest rupture stress and fracture energy (GF) of 11 MPa and 25 MJ·m-3, which are almost 40-fold and 1500-fold, respectively, higher than those of non-functionalized TEG-based TPU (PU). Additionally, damaged HG(10) shows 87% recovery after heated for 7 min at 80 °C, and completely cut HG(10) shows 80% recovery after 60 min of reattachment at same temperature. The HG interactions in TPU are an important factor in stress dispersion, increasing both its mechanical and self-healing properties. The TPU linked via HG interactions has great promise for use in industrial materials in the near future.
RESUMO
Stimuli-responsive hydrogels have attracted attention as soft actuators that act similarly to muscles. In this work, hydrogel actuators controlled by host-guest interactions have been developed. The introduction of a 1:1 inclusion complex into a hydrogel is a popular design for achieving a change in cross-linking density. To realize faster and larger deformation properties, the introduction of a 1:2 inclusion complex is effective because the alteration in cross-linking density in a hydrogel with 1:2 complexes is larger than that in a hydrogel with 1:1 complexes. A redox-responsive hydrogel actuator cross-linked with 1:2 inclusion complexes is designed, where γ-cyclodextrin (γCD) and viologens modified with an alkyl chain derivative (VC11) were employed as the host and guest units, respectively. γCD includes two VC11 molecules in its cavity. The obtained γCD-VC11 hydrogel cross-linked with the 1:2 complex showed faster and larger deformation behaviour than the αCD-VC11 and the ßCD-VC11 hydrogels cross-linked with a 1:1 complex. The deformation ratio and response speed of the γCD-VC11 hydrogel, which forms a supramolecular cross-linking structure by stimuli, are 3 and 11 times larger, respectively, than those of our previous hydrogel consisting of a ßCD/ferrocene 1:1 inclusion complex.
RESUMO
Synthetic polymers, typically prepared by addition polymerization or stepwise polymerization, are used constantly in our daily lives. In recent years, polymer scientists have focused on more environmentally friendly synthetic methods such as mild reaction conditions and biodegradable condensation polymers, including polyesters and polyamides. However, challenges remain in finding greener methods for the synthesis of polymers. Although reactions carried out in water are more environmentally friendly than those in organic solvents, aqueous media can lead to the hydrolysis of condensation polymers. Furthermore, bulk polymerizations are difficult to control. In biological systems, enzymes synthesize most polymers (proteins, DNAs, RNAs, and polysaccharides) in aqueous environments or in condensed phases (membranes). Most enzymes, such as DNA polymerases, RNA polymerases, and ribosomes, form doughnutlike shapes, which encircle the growing polymer chain. As biopolymers form, the active sites and the substrate-combining sites are located at the end of the growing polymer chain and carefully control the polymerization. Therefore, a synthetic catalyst that could insert the monomers between the active site and binding site would create an ideal biomimetic polymerization system. In this Account, we describe cyclodextrins (CDs) as catalysts that can polymerize cyclic esters (lactones and lactides). CDs can initiate polymerizations of cyclic esters in bulk without solvents (even water) to give products in high yields. During our studies on the polymerization of lactones by CDs in bulk, we found that CDs function not only as initiators (catalysts) but also as supporting architectures similar to chaperone proteins. CDs encircle a linear polymer chain so that the chain assumes the proper conformation and avoids coagulation. The CDs can mimic the strategy that living systems use to prepare polymers. Thus, we can obtain polyesters tethered to CDs without employing additional solvents or cocatalysts. Although CD has many hydroxyl groups, only one secondary hydroxyl group attaches to the polyester chain. In addition, the polymerization is highly specific for monomer substrates. We believe that this is the first system in which the catalyst includes monomers initially and subsequently activates the included monomers. The catalyst then inserts the monomers between the binding site and the growing chain. Therefore, this system should provide a new environmentally friendly route to produce biodegradable functional polymers.
Assuntos
Ciclodextrinas/química , Lactonas/síntese química , Poliésteres/síntese química , Biodegradação Ambiental , Materiais Biomiméticos/química , Catálise , DNA/química , Solventes/químicaRESUMO
BETA-cyclodextrin (beta-CD)-based nanosphere 1 initiated the oligomerization of delta-valerolactone (delta-VL) on the surface of 1 to give oligo(delta-VL)-tethered beta-CD nanosphere 2 in bulk. Atomic force microscopy indicated that the molecular size of 2 is twice that of 1. The addition of alpha-CD to 2 leads to the formation of poly-pseudo-rotaxane on the surface of 2 to give a nanosphere with poly-pseudo-rotaxane (alpha-CD[symbol: see text]2). 2D-NOESY NMR experiments showed correlation peaks between the inner protons of alpha-CD and the oligo(delta-VL) chains in an aqueous solution, indicating that the oligo(delta-VL) chains are included in the alpha-CD cavity. Alpha-CD[symbol: see text]2 has a core of beta-CDs with poly-pseudo-rotaxanes on the surface. It should be noted that 2 did not show polymerization ability for delta-VL, but after the formation of poly-pseudo-rotaxanes, oligo(delta-VL) of alpha-CD[symbol: see text]2 repropagated upon the addition of delta-VL. Alpha-CD[symbol: see text]2 is significantly larger than nanospheres 1 and 2. Additionally, postpolymerization increases the size of alpha-CD[symbol: see text]2. These behaviors are reminiscent of the function of a spherical virus, which forms an ordered spherical structure and releases RNA chains from the capsid surface.
Assuntos
Ciclodextrinas/síntese química , Poloxâmero/síntese química , Rotaxanos/síntese química , Ciclodextrinas/química , Nanosferas , Tamanho da Partícula , Poloxâmero/química , Pironas/química , Rotaxanos/química , Propriedades de Superfície , Água/químicaRESUMO
Cinnamoyl alpha-cyclodextrin (alpha-CD) has been found to initiate polymerization of delta-valerolactone (delta-VL) to give a polymer in high yield. By the presence of the cinnamoyl group, hydrogen bond was formed between the carbonyl oxygen of delta-VL and the hydroxyl group of CD to activate the monomer, which was observed by FT-IR measurements. However, the cinnamoyl group at the C(3)- and C(6)-positions of alpha-CD did not affect the polymerization ability. Only that of the C(2)-position showed high polymerization activity. The polymerization activity could be switched by the photoisomerization of the cinnamoyl group attached to the rim of alpha-CD. Specific monomer recognition and polymerization in the active site of the alpha-CD cavity was changed by the photoisomerization.
Assuntos
Cinamatos/química , Polímeros/síntese química , Pironas/química , alfa-Ciclodextrinas/química , Catálise , Domínio Catalítico , Ésteres/síntese química , Ésteres/química , Ligação de Hidrogênio , Isomerismo , Fotoquímica , Polímeros/química , Espectroscopia de Infravermelho com Transformada de Fourier , Especificidade por SubstratoRESUMO
Molecular recognition is useful in creating functional supramolecular materials. Non-covalent bond formations, such as host-guest interactions, hydrogen bonding, and electrostatic interaction, are effective tools for introducing various functions and properties into materials. This review focuses on such macroscopic functions as selective molecular adhesion, self-healing, toughness, and the actuation of supramolecular polymeric materials-materials which have potential in pharmaceutical development. These functions have been achieved using reversible bonding between cyclodextrins (CDs; cyclic host molecules) and guest molecules. For example, macroscopic adhesions between host-modified hydrogels and guest-modified hydrogels have been investigated. CD-modified hydrogels were found to show selective adhesion to a guest hydrogel with an appropriate molecular size for the CD cavity, indicating that the host-guest complex formation between the gels led to the adhesive behavior. Surprisingly, polymeric materials having host-guest cross-linking points show both high toughness and flexibility, unlike conventional covalently cross-linked materials. These materials also exhibited self-healing properties, capable of repairing damage to the materials. Furthermore, the supramolecular materials demonstrated macroscopic rapid expansion and contraction driven by external stimuli under wet or semi-dry conditions, in which the supramolecular gels vary the cross-linking density between the polymers accordingly. Different topological gels are able to vary the length of the polymer chain between cross-linking points to show large deformation. Both types of actuators were found to exhibit externally stimulated flexing behaviors. This review summarizes recent advancements in the development of these supramolecular materials, which appear to be promising new components in pharmaceutical science.
Assuntos
Ciclodextrinas/química , Ciclodextrinas/síntese química , Desenho de Fármacos , Substâncias Macromoleculares/química , Substâncias Macromoleculares/síntese química , Fenômenos Químicos , Hidrogéis , Estrutura Molecular , Polímeros/químicaRESUMO
Supramolecular materials have received considerable attention due to their higher fracture energy and self-recovery capability compared to conventional chemically cross-linked materials. Herein, we focus on the mechanical properties and self-recovery behaviours of supramolecular polymeric elastomers swollen with ionic liquid. We also gained insight into the correlation between ionic liquid content and mechanical properties. These supramolecular polymers with ionic liquid can be easily prepared from bulk copolymerization of the host-guest complex (peracetylated cyclodextrin and adamantane derivatives) and alkyl acrylates and subsequent immersion in ionic liquid such as 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. The supramolecular polymeric elastomers showed a self-recovery ability, which the conventional chemically cross-linked elastomers with ionic liquid cannot achieve.
RESUMO
Poly-pseudo-rotaxanes CDs contains as a subset 1 (CDs; cyclodextrins, 1; poly(delta-valerolactone) having single beta-CD at the end of the polymer chain) initiate polymerization of delta-valerolactone (delta-VL) in the solid state when CDs (alpha-CD, beta-CD, and 2,6-di-O-methyl-beta-CD) are threaded onto the polymer chain. 1 without threaded CDs did not show any polymerization ability for delta-VL. An adamantane molecule (Ad) inhibited the polymerization ability of CDs contains as a subset 1 for delta-VL, indicating that beta-CD at the end of CDs contains as a subset 1 could not bind delta-VL because the beta-CD cavity was occupied by Ad. It should be noted that the insertion reaction and the polymerization took place inside the beta-CD cavity at the end of CDs contains as a subset 1 and that the formation of poly-pseudo-rotaxane is necessary for the initiation of delta-VL. The structures of beta-CD contains as a subset 1 and 1 were characterized by powder X-ray diffraction measurements and solid-state NMR spectroscopies. The polymer chain of beta-CD contains as a subset 1 was found to elongate in the solid state, whereas the polymer chain of 1 formed a random coil conformation. 1 was deactivated for the polymerization by blocking the active cavity of beta-CD with the polymer chain. CDs threaded onto 1 are immune to the initiation of delta-VL directly but have an essential role to fold the polymer chain in a proper way as an artificial chaperone.
Assuntos
Ciclodextrinas/química , Lactonas/química , Chaperonas Moleculares/química , Polímeros/química , Rotaxanos/química , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Difração de Raios XRESUMO
Cyclodextrins were found to initiate ring-opening polymerization of some cyclic esters selectively to give a polyester with a CD at the chain end.