Efficient Synthesis of Cyclic Poly(ethylene glycol)s under High Concentration Conditions by the Assistance of Pseudopolyrotaxane with Cyclodextrin Derivatives.

An efficient synthesis of cyclic polymers (CPs) is in high demand due to their unique properties. However, polymer cyclization generally occurs at low concentrations (0.1 g/L), and the synthesis of CPs at high concentrations remains a challenge. Herein an efficient cyclization of poly(ethylene glycol) (Mn = 2000 g/mol, 4000 g/mol) (PEG-2k, PEG-4k) in high concentration (80 g/L) is realized by the assistance of pseudopolyrotaxane (pPRx). Water-soluble pPRx with a U-like-shape inclusion motif is prepared by mixing the 2-hydroxypropyl-γ-cyclodextrin (HPγCD) and PEG with (E)-3,4,5-trimethoxycinnamate (TCA-PEG-2k, TCA-PEG-4k). Subsequent irradiation of the pPRx solution (10-80 g/L) by UV light gives cyclic polymers through the intramolecular [2 + 2] photocycloaddition of the cinnamoyl moieties. The photoreaction of TCA-PEG-2k in the pPRx system gives cyclic monomers (C-1mer) as major products with a yield of 66% at 80 g/L. Additionally, the cyclization of TCA-PEG-4k also gives C-1mer as major products with a yield of 45% at a concentration of 80 g/L.

Supramolecular complex formation of polysulfide polymers and cyclodextrins.

We report the first preparation of a supramolecular polysulfide polymer, which is a polyrotaxane containing sulfur-styrene copolymer and methylated α-cyclodextrins (TMαCDs) as linear and cyclic molecules, respectively (SPRx). Compared to the sulfur-styrene copolymer prepared by a copolymerization method typically used to synthesize polysulfide polymers, the environmental and thermal stabilities of SPRx are significantly improved because the polysulfide polymer is covered with TMαCD.

Control of microenvironment around enzymes by hydrogels.

We prepared enzyme-immobilized hydrogels and investigated the effects of the cross-linking density and polymer properties on their oxidation reaction rate. The oxidation rate of enzyme-immobilized hydrogels increased as the cross-linking density in the hydrogels increased. In addition, we controlled the oxidation rate using hydrogels exhibiting an appropriate interaction with a decoy molecule in the hydrogel.

A palladium-catalyst stabilized in the chiral environment of a monoclonal antibody in water.

We report the first preparation of a monoclonal antibody (mAb) that can immobilize a palladium (Pd)-complex. The allylic amination reaction using a supramolecular catalyst consisting of the Pd-complex and mAb selectively gives the (R)-enantiomer product with an enantiomeric excess (ee) of 98 ± 2%. This is in sharp contrast to the reaction catalyzed by a conventional Pd-catalyst (ee < 2%).

Redox-responsive supramolecular polymeric networks having double-threaded inclusion complexes.

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.

Mechanical properties of supramolecular polymeric materials cross-linked by donor-acceptor interactions.

We prepared polymeric materials cross-linked by donor-acceptor (DA) interactions between pyrene (Py) and trinitrobenzene (TNB) on the same polymer side chain. Although a mixture of a Py polymer and a TNB polymer did not form an elastomer, a polymer bearing DA units on the same polymer chain formed an elastomer. The fracture energy of the elastomer was higher than that of the covalently cross-linked elastomer.

Mechanical and self-recovery properties of supramolecular ionic liquid elastomers based on host-guest interactions and correlation with ionic liquid content.

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.

Control of the threading ratio of cyclic molecules in polyrotaxanes consisting of poly(ethylene glycol) and α-cyclodextrins.

We demonstrated a feasible method for providing polyrotaxanes (PRxs) with a controlled threading ratio of cyclic molecules and chain length of linear polymers by extending the linear polymers in the pseudo-PRx. This method gave PRxs with a lower threading ratio and a higher mobility of cyclic molecules compared to usual methods used previously with a high threading ratio. In addition, our PRx improved the thermal stability of the linear polymers in PRx despite the low threading ratio.

Thermal ring-opening polymerization of an unsymmetrical silicon-bridged [1]ferrocenophane in coordination nanochannels.

Thermal ring-opening polymerization of the unsymmetrically substituted [1]ferrocenophane was performed in one-dimensional nanochannels of porous coordination polymers (PCPs). In contrast to conventional thermal polymerization in bulk, formation of cyclic polymer was inhibited in the channels. In addition, the tacticity of the resulting polymer was dependent on the pore size of PCPs.

Preparation of Porous Polysaccharides Templated by Coordination Polymer with Three-Dimensional Nanochannels.

Polymerization of monosaccharide monomers usually suffers from the production of polysaccharides with ill-defined structures because of the uncontrolled random reactions among many reactive hydroxyl groups on saccharide monomers. In particular, rational synthesis of polysaccharides with porosity approximating molecular dimensions is still in its infancy, despite their usefulness as drug carriers. Here, we disclose an efficient synthetic methodology for the preparation of polysaccharides with controllable mesoporosity in the structure, utilizing [Cu3(benzene-1,3,5-tricarboxylate)]n (HKUST-1; 1) as templates. Cationic ring-opening polymerization of 1,6-anhydro glucose was performed in nanochannels of 1, followed by removal of the host frameworks, giving polysaccharide particles as replicas of the original molds. Nitrogen adsorption measurement revealed that the obtained polysaccharide particles contained high mesoporosity in the structure, which could be controlled systematically depending on the polymerization conditions. Because of the large specific surface area, tunable porosity and particle size, we could also demonstrate the capabilities of our polysaccharides for loading and releasing of a drug molecule and protein.

The controlled synthesis of polyglucose in one-dimensional coordination nanochannels.

We demonstrate a feasible method for the preparation of polyglucose (PGlc) with controlled structures, where the polymerization of glucose monomers was performed using one-dimensional nanochannels of [La(1,3,5-benzenetrisbenzoate)(H2O)]n (1). Cationic ring-opening polymerization of 1,6-anhydro-ß-D-glucose (levoglucosan) using 1 gave a quasi-linear PGlc, which contrasts highly with the results obtained from conventional polymerizations in bulk and solution. The regulated structure of PGlc prepared using the PCP led to a remarkable improvement in the processability and thermal stability of PGlc, which is useful in applications as a bioplastic.

Manual control of catalytic reactions: Reactions by an apoenzyme gel and a cofactor gel.

Enzymes play a vital role in catalysing almost all chemical reactions that occur in biological systems. Some enzymes must form complexes with non-protein molecules called cofactors to express catalytic activities. Although the control of catalytic reactions via apoenzyme-cofactor complexes has attracted significant attention, the reports have been limited to the microscale. Here, we report a system to express catalytic activity by adhesion of an apoenzyme gel and a cofactor gel. The apoenzyme and cofactor gels act as catalysts when they form a gel assembly, but they lose catalytic ability upon manual dissociation. We successfully construct a system with switchable catalytic activity via adhesion and separation of the apoenzyme gel with the cofactor gel. We expect that this methodology can be applied to regulate the functional activities of enzymes that bear cofactors in their active sites, such as the oxygen transport of haemoglobin or myoglobin and the electron transport of cytochromes.

A macroscopic reaction: direct covalent bond formation between materials using a Suzuki-Miyaura cross-coupling reaction.

Cross-coupling reactions are important to form C-C covalent bonds using metal catalysts. Although many different cross-coupling reactions have been developed and applied to synthesize complex molecules or polymers (macromolecules), if cross-coupling reactions are realized in the macroscopic real world, the scope of materials should be dramatically broadened. Here, Suzuki-Miyaura coupling reactions are realized between macroscopic objects. When acrylamide gel modified with an iodophenyl group (I-gel) reacts with a gel possessing a phenylboronic group (PB-gel) using a palladium catalyst, the gels bond to form a single object. This concept can also be adapted for bonding between soft and hard materials. I-gel or PB-gel selectively bonds to the glass substrates whose surfaces are modified with an electrophile or nucleophile, respectively.

Supramolecular adhesives to hard surfaces: adhesion between host hydrogels and guest glass substrates through molecular recognition.

Supramolecular materials based on host-guest interactions should exhibit high selectivity and external stimuli-responsiveness. Among various stimuli, redox and photo stimuli are useful for its wide application. An external stimuli-responsive adhesive system between CD host-gels (CD gels) and guest molecules modified glass substrates (guest Sub) is focused. Here, the selective adhesion between host gels and guest substrates where adhesion depends on molecular complementarity is reported. Initially, it is thought that adhesion of a gel material onto a hard material might be difficult unless many guest molecules modified linear polymers immobilize on the surface of hard materials. However, reversible adhesion of the CD gels is observed by dissociating and re-forming inclusion complex in response to redox and photo stimuli.

Photoswitchable gel assembly based on molecular recognition.

The formation of effective and precise linkages in bottom-up or top-down processes is important for the development of self-assembled materials. Self-assembly through molecular recognition events is a powerful tool for producing functionalized materials. Photoresponsive molecular recognition systems can permit the creation of photoregulated self-assembled macroscopic objects. Here we demonstrate that macroscopic gel assembly can be highly regulated through photoisomerization of an azobenzene moiety that interacts differently with two host molecules. A photoregulated gel assembly system is developed using polyacrylamide-based hydrogels functionalized with azobenzene (guest) or cyclodextrin (host) moieties. Reversible adhesion and dissociation of the host gel from the guest gel may be controlled by photoirradiation. The differential affinities of α-cyclodextrin or ß-cyclodextrin for the trans-azobenzene and cis-azobenzene are employed in the construction of a photoswitchable gel assembly system.

pH-responsive movement of cucurbit[7]uril in a diblock polypseudorotaxane containing dimethyl beta-cyclodextrin and cucurbit[7]uril.

[Structure: see text] A polypseudorotaxane consisting of cucurbit[7]uril (CB[7])/N,N'-(3-phenylenebis(methylene)dipropargylamine (PMPA), [2]pseudorotaxane, and 2,6-O-dimethyl beta-cyclodextrin (DM-beta-CD)/alpha,omega-bisazidopropylene glycol 400 [2]pseudorotaxane was synthesized using the "click" reaction. The polypseudorotaxane structure was maintained in aqueous solution over a wide range of pH values with the DM-beta-CD units contributing to increased solubilization of the polypseudorotaxane without dethreading. The pH-responsive movement of the CB[7] units in the polypseudorotaxane was also observed.