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Polyrotaxane (PR) has garnered increasing attention due to its unique structure and exceptional performance. In this study, a polypseudorotaxane (PPR) initiator was prepared through the self-assembly of bromine-capped Pluronic F68 and β-cyclodextrins (β-CD) in water. Polyrotaxane-containing triblock copolymers (PR copolymers) were successfully synthesized by atom transfer radical polymerization (ATRP) of butyl methacrylate (BMA) using the PPR initiator in the presence of Cu(I)Br/PMDETA. The structure of the PR copolymers was thoroughly characterized using infrared spectroscopy (IR), proton nuclear magnetic resonance (1H NMR), and gel permeation chromatography (GPC). The mobility of β-CD in the PR copolymers was demonstrated through dielectric measurements. Mechanical tests, including tensile strength assessments, thermal mechanical analysis, and dynamic mechanical analysis, confirmed the excellent mechanical properties and good processability of the PR copolymer, attributed to the PBMA blocks. Furthermore, the mechanical properties were found to be modulated by the motility of the threaded β-CDs. Consequently, the superior mechanical properties and the high mobility of the threaded β-CDs suggest promising potential for the as-prepared PR polymer in various advanced applications. [ABSTRACT FROM AUTHOR]

Bacterial infections, especially those from drug‐resistant strains, pose a significant threat to healing diabetic skin injuries, with current treatments being intricated and often unsatisfactory. Inspired by octopuses, a biomimetic material using α‐cyclodextrin (α‐CD) and polyethylene glycol (PEG) assembled with graphene oxide end‐capped polyrotaxanes (GO‐PR) is developed, where α‐CD mimics the flexible tentacles of an octopus. Further, α‐CD is cationically modified with polyethyleneimine (PEI) to resemble octopus suction cups, creating GO‐PRP, which effectively captures and adheres to bacteria. Importantly, to emulate an octopus's ink defense, GO‐PRP is used as a carrier for nitric oxide (NO), resulting in GO‐PRP/NONOate. Utilizing the photothermal conversion of GO, near‐infrared light exposure triggers rapid heating and NO release, providing efficient antibacterial activity and biofilm dispersion, significantly reducing inflammation in diabetic skin injuries in type I rats. During wound healing, sustained NO release promotes vascular endothelial growth factor production and blood vessel regeneration, enhancing collagen formation and shortening the healing time for diabetic skin infections. Thus, octopus‐inspired GO‐PRP/NONOate emerges as a novel biomaterial for treating drug‐resistant bacterial infections in diabetic wounds in the biomedical field. [ABSTRACT FROM AUTHOR]

Polyethylene Glycol (PEG)-based flexible phase change materials have broad and practical application value in thermal management of flexible electronic devices. Considering the typical application cases and safety of phase change materials (PCMs), in this work, we grafted molecular nanoparticles, POSS, with both hydrophobic and flame retardant functions to the surface of PLR sheets through amidation reaction. The successful grafting of POSS has been fully verified by Fourier-transform infrared spectroscopy, energy dispersive spectroscopy and surface contact angle. The formation of the cross-linked structure and the introduction of POSS make the phase change latent heat of the phase change material slightly decrease from 102.4 J g−1 to 94.4 J g−1, but there is still a high retention rate. It is worth pointing out that the PCMs have excellent shape stability and leakage resistance, cycle stability, and shape memory performance (Rf-99%, Rr-99%). The introduce of cross-linked structure and POSS significantly enhanced the Young’s modulus and tensile strength of the PCM. The surface POSS functionalization endowed the PCM with significantly enhanced hydrophobicity. Specifically, the contact angle of the material was significantly increased from 71° for PLR to 123° for POSS-PLR, and it also had enhanced fire safety with pHRR reduction by 18.4% and THR reduction by 19.1%.

An aqueous solution of chlorinated polyethylene glycol (Cl-PEG-Cl) and α-cyclodextrin (α-CD) was used to form inclusion complexes, which several α-CDs are threaded into the linear PEG chain and produced a so-called polypseudorotaxane (PPRx). By attaching 4-ethylaniline as the blocking agent to the chlorinated PEG chain ends, the complex will be stabilized, resulting in the formation of so-called polyrotaxane (PRx) (also known as molecular necklace). Finally, crosslinked αCD-based PRx with a tubular structure was formed via the condensation reactions between α-cyclodextrins and epichlorohydrin. Using concentrated NaOH solution, polymer chains were then removed from complexes, resulting in the so-called molecular tube (MT). This novel method led to the improvement in polyrotaxane conversion with less production steps and reduced materials overall costs. Resulting products in each section were characterized by 1H and 13C nuclear magnetic resonance spectroscopies (1H-NMR and 13C-NMR), from which complex inclusion ratio and length of the nanotubes were estimated. XRD was also used to confirm tubular structure of the inclusion complexes. [ABSTRACT FROM AUTHOR]

Although our knowledge and understanding of adsorptions in natural and artificial systems has increased dramatically during the past century, adsorption associated with nonporous polymers remains something of a mystery, hampering applications. Here we demonstrate a model system for adaptisorption of nonporous polymers, wherein dative B−N bonds and host‐guest binding units act as the kinetic and thermodynamic components, respectively. The coupling of these two components enables nonporous polymer crystals to adsorb molecules from solution and undergo recrystallization as thermodynamically favored crystals. Adaptisorption of nonporous polymer crystals not only extends the types of adsorption in which the sorbate molecules are integrated in a precise and orderly manner in the sorbent systems, but also provides a facile and accurate approach to the construction of polymeric materials with precise architectures and integrated functions. [ABSTRACT FROM AUTHOR]

The pulley structure has been widely employed to improve mechanical properties. Polyrotaxane‐based waterborne polyurethane (WPU) typically exhibits good tensile strength and Young's modulus. However, achieving outstanding self‐healability of polyrotaxane‐based WPU under mild conditions generally proves insufficient solely relying on host‐guest interactions. Herein, a strategy that constructs a triple synergy of host‐guest interaction, hydrogen bonds, and metal coordination bonds by sequentially introducing tannic acid (TA) and Fe3+ is proposed to prepare polyrotaxane‐based WPU with excellent mechanical performance and high self‐healable capability. Besides the reversible non‐covalent bonding contributing to intrinsic self‐healing, the unique sliding motion of WPU's molecule chain acts as a driving force, promoting efficient contact among reversible bonds. Notably, benefiting from the sliding motion of β‐cyclodextrin (β‐CD) along a chain, the dynamic reconstruction of hydrogen bonds and metal coordination bonds, the resulting supramolecular WPU exhibited a tensile strength of 46.05 MPa and a toughness of 130.30 MPa, with satisfactory self‐healing performance (tensile strength healing efficiency of more than 95%). This work enriches the self‐healing mechanism and expands the concepts for the design of resilient self‐healing environmentally friendly supramolecular WPU. [ABSTRACT FROM AUTHOR]

We previously reported that acid-degradable methylated β-cyclodextrins (Me-β-CDs)-threaded polyrotaxanes (Me-PRXs) can induce autophagic cell death through endoplasmic reticulum (ER) stress-related autophagy, even in apoptosis-resistant cells. Hence, Me-PRXs show great potential as anticancer therapeutics. In this study, peptide-supermolecule conjugates were designed to achieve the targeted delivery of Me-PRX to malignant tumors. Arg-Gly-Asp peptides are well-known binding motifs of integrin αvβ3, which is overexpressed on angiogenic sites and many malignant tumors. The tumor-targeted cyclic Arg-Gly-Asp (cRGD) peptide was orthogonally post-modified to Me-PRX via click chemistry. Surface plasmon resonance (SPR) results indicated that cRGD-Me-PRX strongly binds to integrin αvβ3, whereas non-targeted cyclic Arg-Ala-Glu (cRGE) peptide conjugated to Me-PRX (cRGE-Me-PRX) failed to interact with integrins αvβ3. In vitro, cRGD-Me-PRX demonstrated enhanced cellular internalization and antitumor activity in 4T1 cells than that of unmodified Me-PRX and non-targeted cRGE-Me-PRX, due to its ability to recognize integrin αvβ3. Furthermore, cRGD-Me-PRX accumulated effectively in tumors, leading to antitumor effects, and exhibited excellent biocompatibility and safety in vivo. Therefore, cRGD conjugation to enhance selectivity for integrin αvβ3-positive cancer cells is a promising design strategy for Me-PRXs in antitumor therapy. [ABSTRACT FROM AUTHOR]

Polymer‐based composites containing functional organic fillers with polyvinylidene fluoride (PVDF) as a matrix were prepared using a simple and short melt‐compounding method, and their mechanical properties were evaluated. Polyrotaxane and nanocellulose were used as functional organic fillers. A PVDF/organic filler composite with improved mechanical hardness was prepared, even when using a fluoropolymer that tends to separate phases from other components. The optimum conditions for improving in Young's modulus were estimated from the composites prepared by varying the organic filler content. As a result, the Young's modulus increased to 1548 MPa, maximum stress approached 50 MPa, and strain elongation was 20% at contents of polyrotaxane:nanocellulose = 0.6 wt%:0.3 wt%. Furthermore, the miscibility of both components was evaluated based on the change in the crystallization temperature of the composite, the PVDF matrix, and each organic filler. The partial miscibility and dispersion of the organic fillers in the fluoropolymer matrix are suggested to be responsible for improving the mechanical properties. Highlights: Unique composites containing nanocellulose and polyrotaxane were prepared.Organic fillers were introduced into a phase‐separable fluoropolymer matrix.Mechanical properties were improved by introduction of organic fillers.Nanocellulose seems to adsorb to the polymer chain ends of fluoropolymer.Polyrotaxane showed partial miscibility with fluoropolymer matrix. [ABSTRACT FROM AUTHOR]

Polyrotaxane (PR) has garnered increasing attention due to its unique structure and exceptional performance. In this study, a polypseudorotaxane (PPR) initiator was prepared through the self-assembly of bromine-capped Pluronic F68 and β-cyclodextrins (β-CD) in water. Polyrotaxane-containing triblock copolymers (PR copolymers) were successfully synthesized by atom transfer radical polymerization (ATRP) of butyl methacrylate (BMA) using the PPR initiator in the presence of Cu(I)Br/PMDETA. The structure of the PR copolymers was thoroughly characterized using infrared spectroscopy (IR), proton nuclear magnetic resonance (1H NMR), and gel permeation chromatography (GPC). The mobility of β-CD in the PR copolymers was demonstrated through dielectric measurements. Mechanical tests, including tensile strength assessments, thermal mechanical analysis, and dynamic mechanical analysis, confirmed the excellent mechanical properties and good processability of the PR copolymer, attributed to the PBMA blocks. Furthermore, the mechanical properties were found to be modulated by the motility of the threaded β-CDs. Consequently, the superior mechanical properties and the high mobility of the threaded β-CDs suggest promising potential for the as-prepared PR polymer in various advanced applications.

Phase change materials (PCMs) have received much attention regarding the thermal regulation of electronic devices. However, the main limitations of using organic PCMs are the low thermal conductivity and leakage during the phase change process. This work aims to improve these limitations to increase the thermal conductivity of the leakage‐proof PCM formed by a polyrotaxane that serves as a support material to encapsulate PEG. For this purpose, different contents of graphene nanoplatelets (GNP) are blended. To facilitate its postindustrial production and to meet ecological standards, the synthesis of this PCM is simple and only using water as a solvent. The PCMs can be thermally processed conveniently by a hot press. Furthermore, the PCMs achieve high enthalpy values (132.9–142.9 J g−1) due to the action of GNPs as thermally conductive fillers. The PCMs exhibited an increase of 60–257% in thermal conductivity values with higher GNP content, and show great shape stability and no leakage during phase change. These improvements solve the main problems of organic PCMs, thus making PLR‐PEG‐GNP‐based materials a good candidate for use as thermal energy storage materials in industrial applications as thermoregulators of solid‐state disks or realizing the "shaving peaks and filling valleys" effect for thermoelectric generators. [ABSTRACT FROM AUTHOR]

Herein, polymer-based composites containing polyrotaxane and nanocellulose as organic fillers and organo-modified carbon nanotubes as inorganic nanofillers in a polypropylene matrix were prepared. The two types of functional organic fillers were combined with polypropylene using a simple melt-compounding method and showed improved mechanical properties in the matrix polymer. A jet-black composite material was obtained by combining organo-modified carbon nanotubes and long-chain phosphonic acid as a modifier to the polypropylene matrix. In this case, the long-chain phosphonic acid modifier exhibited effects typical of filler dispersants. Polymer composites containing two types of functional organic fillers and organo-modified carbon nanotubes were prepared uniaxially. In the drawn composites, the carbon nanotubes showed a uniaxial orientation, dramatically improving the mechanical characteristics of the prepared materials. [ABSTRACT FROM AUTHOR]

The modification of vinyl groups on polyrotaxane derivatives, obtained with polyethylene glycol as the axial molecule and α-cyclodextrin as the cyclic molecule, allows the production of crosslinkers that react with various monomers, facilitating the formation of polymer networks. In contrast to conventional polymer crosslinked networks using typical crosslinking agents, polymer networks employing polyrotaxane crosslinking agents allow for mobile crosslinking points. Consequently, the resulting polymeric crosslinked network may exhibit increased toughness, as external stress is uniformly distributed throughout the polymeric network. This distribution helps to avoid excessive stress concentration in specific areas. To optimize the mechanical properties of polymer networks formed using polyrotaxane crosslinkers, we investigated the impact of the molecular weight of the axial molecules and the number of crosslinking points of the cyclic molecules in the polyrotaxane crosslinkers on the mechanical properties of the resulting polymer networks. Our results show that the fracture strain, fracture stress, and fracture energy of the resultant polymer networks increase with increasing molecular weight of polyethylene glycol. We also observed that the fracture stress and toughness of the polymer networks increased when there was less than one modified vinyl group on α-cyclodextrin, compared to the case with multiple vinyl groups.

Molecular gels, which are soft and flexible materials, are candidates for healthcare, cosmetic base, and electronic applications as new materials. In this study, a new polymeric organogelator bearing a polyrotaxane (PR) structure was developed and could induce the gelation of N′,N″-dimethylformamide (DMF), a known solvent for dissolving polymeric materials and salts. Furthermore, the resulting DMF molecular gels exhibited thixotropic properties, observed by the inversion method using vials, which are essential for gel spreading. The scanning electron microscopy of the xerogels suggested that the gel-forming ability and thixotropic property of gels were imparted by the network of the laminated aggregates of thin layer material similar to those of other gels made of clay materials. This thin layer material would be formed by the aggregation of polymeric organogelators. The dynamic viscoelasticity measurements of the obtained gels revealed the stability and pseudo-thixotropic behaviors of the obtained gels, as well as a specific concentration effect on the mechanical behavior of the gels attributed to the introduction of the PR structure. Additionally, the preparation of the polymer organogelator/polymer composites was investigated to improve the mechanical properties via the filler effect induced by the agglomerates of organogelator. Moreover, the tensile tests confirmed that the introduction of the gelator enhanced the mechanical properties of the composites. [ABSTRACT FROM AUTHOR]

New composite materials were prepared via cross-linking of polyethylene glycol/2-hydroxypropyl-β-cyclodextrins polyrotaxane (PEG/HPβCD) and polyisoprene/HPβCD semi-polyrotaxane (PI/HPβCD SR) with 1,6-hexamethylene diizocyanate (HMDI). Advanced instrumental methods (such WAXS (wide angle X-ray scattering), AFM (atomic force microscopy), SEM (scanning electron microscopy), and thermal and dynamic vapor sorption) were employed for the structural, morphological and thermal characterization of the resulting composite materials. The roughness parameters calculated using AFM indicate a smoother surface for the composite material with 10 wt% of PI/HPβCD SR, denoting that a homogeneous film was obtained. SEM analysis reveals porous morphologies for both composite materials and the pore sizes increase with the increasing concentration of PI/HPβCD SR in the matrix. Dynamic vapor sorption/desorption measurements and type IV isotherms confirmed the hydrophilic and porous materials, which are in agreement with SEM analysis. The composite with a higher PI/HPβCD SR concentration in the matrix showed increased thermal stability than that of the pure cross-linked material. This material was further tested as a sorbent for methylene blue (MB) dye removal from an aqueous solution. The adsorption capacity of the composite film was found to be 2.58 mg g−1 at 25 °C. [ABSTRACT FROM AUTHOR]

Preparing strong and flexible atelocollagen-based materials for biomedical applications is still a challenging task. To address this challenge, this study describes the synthesis and characterization of water-soluble polyrotaxanes (PRs) with different coverage ratios and molecular weights of axle polymers, and their potential applications for PR-reinforced atelocollagen threads (PRATs). A novel method was established for the syntheses of PRs with relatively low coverage ratio at the sub-gram scale, in which the aldehyde groups were employed as crosslinking sites for preparing the PRATs via reductive amination. The aldehyde groups were successfully quantified by 1H nuclear magnetic resonance spectroscopy using 1,1-dimethylhydrazine as an aldehyde marker. Fourier-transform infrared and thermogravimetric analysis measurements supported the characterization of the PRs. Interestingly, tensile testing demonstrated that coverage ratio affected the mechanical properties of the PRATs more strongly than molecular weight. The insights obtained in this study would facilitate the development of soft materials based on atelocollagens and PRs. [ABSTRACT FROM AUTHOR]

We previously reported that acid-degradable methylated β-cyclodextrins (Me-β-CDs)-threaded polyrotaxanes (Me-PRXs) can induce autophagic cell death through endoplasmic reticulum (ER) stress-related autophagy, even in apoptosis-resistant cells. Hence, Me-PRXs show great potential as anticancer therapeutics. In this study, peptide-supermolecule conjugates were designed to achieve the targeted delivery of Me-PRX to malignant tumors. Arg-Gly-Asp peptides are well-known binding motifs of integrin αvβ3, which is overexpressed on angiogenic sites and many malignant tumors. The tumor-targeted cyclic Arg-Gly-Asp (cRGD) peptide was orthogonally post-modified to Me-PRX via click chemistry. Surface plasmon resonance (SPR) results indicated that cRGD-Me-PRX strongly binds to integrin αvβ3, whereas non-targeted cyclic Arg-Ala-Glu (cRGE) peptide conjugated to Me-PRX (cRGE-Me-PRX) failed to interact with integrins αvβ3. In vitro, cRGD-Me-PRX demonstrated enhanced cellular internalization and antitumor activity in 4T1 cells than that of unmodified Me-PRX and non-targeted cRGE-Me-PRX, due to its ability to recognize integrin αvβ3. Furthermore, cRGD-Me-PRX accumulated effectively in tumors, leading to antitumor effects, and exhibited excellent biocompatibility and safety in vivo. Therefore, cRGD conjugation to enhance selectivity for integrin αvβ3-positive cancer cells is a promising design strategy for Me-PRXs in antitumor therapy.

Activation of autophagy represents a potential therapeutic strategy for the treatment of diseases that are caused by the accumulation of defective proteins and the formation of abnormal organelles. Methylated β-cyclodextrins-threaded polyrotaxane (Me-PRX), a supramolecular structured polymer, induces autophagy by interacting with the endoplasmic reticulum. We previously reported on the successful activation of mitochondria-targeted autophagy by delivering Me-RRX to mitochondria using a MITO-Porter, a mitochondria-targeted nanocarrier. The same level of autophagy induction was achieved at one-twentieth the dosage for the MITO-Porter (Me-PRX) compared to the naked Me-PRX. We report herein on the quantitative evaluation of the intracellular organelle localization of both naked Me-PRX and the MITO-Porter (Me-PRX). Mitochondria, endoplasmic reticulum and lysosomes were selected as target organelles because they would be involved in autophagy induction. In addition, organelle injury and cell viability assays were performed. The results showed that the naked Me-PRX and the MITO-Porter (Me-PRX) were localized in different intracellular organelles, and organelle injury was different, depending on the route of administration, indicating that different organelles contribute to autophagy induction. These findings indicate that the organelle to which the autophagy-inducing molecules are delivered plays an important role in the level of induction of autophagy. [ABSTRACT FROM AUTHOR]

The mechanical properties and miscibility of polymer‐based composites containing cellulose nanofiber (CNF) and polyrotaxane (p‐rtx) as organic fillers were studied in detail. CNF and p‐rtx were introduced as powders into a polypropylene (PP) matrix, and composites were prepared using a simple melt‐compounding method. The best mechanical properties were achieved when CNF and p‐rtx were loaded at a concentration of 0.6 wt%. The Young's modulus of the composite increased by 760 MPa compared with that of the PP matrix. In addition, the presence of mica in the composite promoted the epitaxial growth of PP along the (1 3 0) plane. The various shifts in the melting/crystallization temperatures of the composites prepared at different CNF:p‐rtx ratios confirmed the partial miscibility between the fillers and the matrix. The enhancement in the mechanical properties of the composite is believed to be due to the miscibility of the surfaces of aggregates of the organic fillers with PP and the uniform dispersion of the organic fillers in the matrix. [ABSTRACT FROM AUTHOR]

Polymeric systems that provide cationic charges or biocide‐release therapeutics are used to treat the bacteria‐infected wound. However, most antibacterial polymers based on topologies with restricted molecular dynamics still do not satisfy the clinical requirements due to their limited antibacterial efficacy at safe concentrations in vivo. Here a NO‐releasing topological supramolecular nanocarrier with rotatable and slidable molecular entities is reported to provide conformational freedom to promote the interactions between the carrier and the pathogenic microbes, hence greatly improving the antibacterial performance. With improved contacting‐killing and efficient delivery of NO biocide from the molecularly dynamic cationic ligand design, the NO‐loaded topological nanocarrier achieves excellent antibacterial and anti‐biofilm effects via destroying the bacterial membrane and DNA. MRSA‐infected rat model is also brought out to demonstrate its wound‐healing effect with neglectable toxicity in vivo. Introducing flexible molecular motions into therapeutic polymeric systems is a general design to enhance the healing of a range of diseases. [ABSTRACT FROM AUTHOR]

A solid slide‐ring supramolecular elastomer is constructed by free‐radical polymerization of 2‐(2‐methoxyethoxy)ethyl methacrylate, acrylate‐modified perylene diimides (PDI), and the polyrotaxane (PR) cross‐linker. Benefiting from reciprocating shuttle function of slide‐ring PR formed by acrylate‐modified α‐cyclodextrin threading on polyethylene glycol, the resultant supramolecular elastomer not only presents excellent tensile property, toughness, and fatigue resistance up to 100 cycles, but also gives reversible mechano‐induced fluorescence changes from red to orange luminescence due to a reversible conversion of PDI dimer to monomer upon mechanical stretching. After the dye molecule Nile blue is added as a fluorescent acceptor, the supramolecular elastomer exhibits highly reversible mechano‐induced regulation of energy transfer and can perform five cycles without optical fatigue. This bifunctional mechanochromic slide‐ring supramolecular elastomer, which not only possesses mechanically reversible motion of the slide‐ring cross‐linkers but also has the mechanochromic response of fluorophore, endows the intrinsic superiority of slide‐ring into fatigue resistant mechanoresponsive strain sensing materials. [ABSTRACT FROM AUTHOR]

Polyrotaxane (PR) is a supramolecular polymer in which an axial polymer extends through multiple cyclic molecules. Specifically, PR comprises polyethylene glycol, α‐cyclodextrin and adamantane as the axial polymer, cyclic molecule and terminal blocking group, respectively. PR is a useful stress relaxation material because the cyclic polymers can freely slide and rotate in cyclic motions on the axial polymer. In this study, 4,4′‐diphenylmethane bismaleimide (BMI)/2,2′‐diallylbisphenol A (DABPA) resin was blended with PR as a toughness modifier; the effect of PR on the cured properties of BMI/DABPA resin is reported and the properties are related to the phase structure of BMI/DABPA/PR alloy. The BMI/DABPA/PR alloy formed a microphase‐separated structure with PR particles dispersed in the BMI/DABPA resin matrix. Increasing PR concentration greatly improved the toughness, impact resistance and adhesiveness of the resin. The glass transition temperature also increased because the numerous hydroxyl groups of α‐cyclodextrins in PR formed intermolecular hydrogen bonds in the BMI/DABPA resin, forming a dense network structure. In contrast, owing to the small concentration ratio of PR to BMI/DABPA resin, the dielectric constant, dielectric loss tangent and water absorption were only slightly higher than those of the unmodified resin. © 2022 Society of Industrial Chemistry. [ABSTRACT FROM AUTHOR]

Abstract The development of chemo/photothermal nanotherapeutic systems with excellent photothermal performance, stable drug loading, tumor targeting and strong membrane penetration still remains a challenge. To address this problem, herein a rod-like nanocomposite system (AuNR@FA-PR/PEG) forming from folic acid (FA) terminated carboxylated cyclodextrin (CD) pseudopolyrotaxane (FA-PR) and polyethylene glycol (PEG) modifying gold nanorods (AuNR) was reported. Cisplatin (CDDP) was loaded in AuNR@FA-PR/PEG via coordination bonds to prepare a rod-like pH-responsive nanosystem (AuNR@FA-PR/PEG/CDDP) with chemotherapy/photothermal therapy. The rod-like morphology of AuNR@FA-PR/PEG was characterized by transmission electron microscope. In vitro drug release experiments showed the pH-responsive of AuNR@FA-PR/PEG/CDDP. In vivo real-time imaging assays proved AuNR@FA-PR/PEG/CDDP could rapidly enrich in the tumor area and stay for a long time because of folate targeting and their rod-like morphology. In vivo photothermal imaging assays showed AuNR@FA-PR/PEG/CDDP excellent photothermal performance, the average temperature of tumor region could reach 63.5 °C after 10 min irradiation. In vitro and in vivo experiments also demonstrated that the combined therapy of chemotherapy and photothermal therapy had an outstandingly synergistic effect and improved the therapeutic efficacy comparing with chemotherapy and photothermal therapy alone. Therefore, the prepared rod-like AuNR@FA-PR/PEG/CDDP will provide a new strategy for the effective treatment of cancer.

Doxorubicin (DOX)-conjugated acid-degradable polyrotaxanes (PRXs) were designed as supramolecular drug carriers capable of releasing drugs in acidic cellular environments. Acid-degradable PRXs composed of α-cyclodextrin (α-CD) as a cyclic molecule, poly(ethylene glycol) (PEG) as a polymer axis, and N-triphenylmethyl (N-Trt) groups as an acid-labile stopper molecules were synthesized and DOX was conjugated with the threaded α-CDs in the PRXs. Because the acid-induced cleavage of N-Trt groups in PRXs leads to PRX dissociation, the DOX-modified α-CDs were released under acidic conditions (pH 5.0). The cytotoxicity of DOX-conjugated PRXs in colon-26 cells revealed significant cell death for DOX-conjugated PRXs after 48 h of treatment. Confocal laser scanning microscopy (CLSM) analysis revealed that the fluorescence signals derived from DOX-conjugated PRXs were observed in cellular nuclei after 48 h, suggesting that the DOX-modified α-CDs were released and accumulated in cellular nuclei. These results confirmed that acid-degradable PRXs can be utilized as drug carriers capable of releasing drug-modified α-CDs in acidic lysosomes and eliciting cytotoxicity. Overall, acid-degradable PRXs represent a promising supramolecular framework for the delivery and intracellular release of drug-modified α-CDs, and PRX–drug conjugates are expected to contribute to the development of pH-responsive drug carriers for cancer therapy. [ABSTRACT FROM AUTHOR]

Cyclodextrins (CDs) are one of the most extensively studied cyclic-oligosaccharides due to their low toxicity, good biodegradability and biocompatibility, facile chemical modification, and unique inclusion capacity. However, problems such as poor pharmacokinetics, plasma membrane disruption, hemolytic effects and a lack of target specificity still exist for their applications as drug carriers. Recently, polymers have been introduced into CDs to combine the advantages of both biomaterials for the superior delivery of anticancer agents in cancer treatment. In this review, we summarize four types of CD-based polymeric carriers for the delivery of chemotherapeutics or gene agents for cancer therapy. These CD-based polymers were classified based on their structural properties. Most of the CD-based polymers were amphiphilic with the introduction of hydrophobic/hydrophilic segments and were able to form nanoassemblies. Anticancer drugs could be included in the cavity of CDs, encapsulated in the nanoparticles or conjugated on the CD-based polymers. In addition, the unique structures of CDs enable the functionalization of targeting agents and stimuli-responsive materials to realize the targeting and precise release of anticancer agents. In summary, CD-based polymers are attractive carriers for anticancer agents. [ABSTRACT FROM AUTHOR]

Silicon is expected to become the ideal anode material for the next generation of high energy density lithium battery because of its high theoretical capacity (4200 mAh g−1). However, for silicon electrodes, the initial coulombic efficiency (ICE) is low and the volume of the electrode changes by over 300% after lithiation. The capacity of the silicon electrode decreases rapidly during cycling, hindering the practical application. In this work, a slidable and highly ionic conductive flexible polymer binder with a specific single‐ion structure (abbreviated as SSIP) is presented in which polyrotaxane acts as a dynamic crosslinker. The ionic conducting network is expected to reduce the overall resistance, improve ICE and stabilize the electrode interface. Furthermore, the introduction of slidable polyrotaxane increases the reversible dynamics of the binder and improves the long‐term cycling stability and rate performance. The silicon anode based on SSIP provides a discharge capacity of ≈1650 mAh g−1 after 400 cycles at 0.5C with a high ICE of upto 92.0%. Additionally, the electrode still exhibits a high ICE of 87.5% with an ultra‐high Si loading of 3.84 mg cm−2 and maintains a satisfying areal capacity of 5.9 mAh cm−2 after 50 cycles, exhibiting the potential application of SSIP in silicon‐based anodes. [ABSTRACT FROM AUTHOR]

The low permeability of antifungal agents to fungal biofilms, which allows the continued survival of the fungus inside, is a key issue that makes fungal infections difficult to cure. Inspired by the unique dynamic molecule motion properties of the polyrotaxane (PR) nanomedicine, herein, a dynamic delivery system Clo@mPRP/NONOate was fabricated by co-loading nitric oxide (NO) and the antifungal drug clotrimazole (Clo) onto the α-cyclodextrin (α-CD) PR modified mesoporous polydopamine (mPDA) nanoparticles, in which pentaethylenehexamine (PEHA) was grafted to α-CDs. The cationic α-CDs endowed this dynamic NO/Clo codelivery system with the ability to effectively attach to fungal biofilms through electrostatic interaction, while the introduction of PRs with flexible molecule motion (slide and rotation of CDs) enhanced the permeability of nanoparticles to biofilms. Meanwhile, NO could effectively inhibit the formation of fungal hyphae, showing an dissipating effect on mature biofilms, and could be further combined with Clo to completely eradicate fungi inside the biofilms. In addition, the dynamic system Clo@mPRP/NONOate could efficiently and synergistically eliminate planktonic Candida albicans (C. albicans) in a safe and no toxic side effect manner, and effectively cured C. albicans -induced vaginal infection in mice. Therefore, this dynamic NO/Clo codelivery system provided an effective solution to the clinical treatment of C. albicans -induced vaginal infection, and the application prospect could even be extended to other microbial infectious diseases. A dynamic codelivery system based on cationized cyclodextrin polyrotaxane combining nitric oxide and antifungal drugs clotrimazole was prepared to deal with the issue of clinical fungal biofilm infection. This dynamic codelivery system could be attached to the Candida albicans biofilms and penetrate into biofilm via flexible molecular mobility to effectively eradicate the fungi. This dynamic codelivery system could synergistically and efficiently eliminate planktonic-state Candida albicans , but did not show significant cytotoxicity to normal somatic cells. [Display omitted] [ABSTRACT FROM AUTHOR]

The physical properties of cyclic polymers differ from those of linear polymers. To prepare cyclic polymers, the ends of a linear polymer must intramolecularly react. Cyclic polymers are typically synthesized at low concentration because intermolecular linkage is preferential to intramolecular linkage at high concentrations. Therefore, preparation of cyclic polymers at high concentrations is difficult. This study demonstrates a new approach to obtain cyclic polymers from highly concentrated polymer solutions using pseudo-polyrotaxanes (pPRxs). Cyclic polymers are prepared by penetrating a linear polymer into the cavity of a cyclic host to form pPRx and then the ends of the linear polymer are subsequently connected. Our approach allows the synthesis of cyclic polymers at concentration that do not allow conventional cyclic polymer synthesis. Specifically, although without pPRx, almost no cyclic polymers were obtained (<1%), with pPRx, the cyclic polymer was obtained as the main product (proportion of cyclic PEG 14%). [ABSTRACT FROM AUTHOR]

Abstract Polymeric systems that provide cationic charges or biocide‐release therapeutics are used to treat the bacteria‐infected wound. However, most antibacterial polymers based on topologies with restricted molecular dynamics still do not satisfy the clinical requirements due to their limited antibacterial efficacy at safe concentrations in vivo. Here a NO‐releasing topological supramolecular nanocarrier with rotatable and slidable molecular entities is reported to provide conformational freedom to promote the interactions between the carrier and the pathogenic microbes, hence greatly improving the antibacterial performance. With improved contacting‐killing and efficient delivery of NO biocide from the molecularly dynamic cationic ligand design, the NO‐loaded topological nanocarrier achieves excellent antibacterial and anti‐biofilm effects via destroying the bacterial membrane and DNA. MRSA‐infected rat model is also brought out to demonstrate its wound‐healing effect with neglectable toxicity in vivo. Introducing flexible molecular motions into therapeutic polymeric systems is a general design to enhance the healing of a range of diseases.

Abstract Silicon is expected to become the ideal anode material for the next generation of high energy density lithium battery because of its high theoretical capacity (4200 mAh g−1). However, for silicon electrodes, the initial coulombic efficiency (ICE) is low and the volume of the electrode changes by over 300% after lithiation. The capacity of the silicon electrode decreases rapidly during cycling, hindering the practical application. In this work, a slidable and highly ionic conductive flexible polymer binder with a specific single‐ion structure (abbreviated as SSIP) is presented in which polyrotaxane acts as a dynamic crosslinker. The ionic conducting network is expected to reduce the overall resistance, improve ICE and stabilize the electrode interface. Furthermore, the introduction of slidable polyrotaxane increases the reversible dynamics of the binder and improves the long‐term cycling stability and rate performance. The silicon anode based on SSIP provides a discharge capacity of ≈1650 mAh g−1 after 400 cycles at 0.5C with a high ICE of upto 92.0%. Additionally, the electrode still exhibits a high ICE of 87.5% with an ultra‐high Si loading of 3.84 mg cm−2 and maintains a satisfying areal capacity of 5.9 mAh cm−2 after 50 cycles, exhibiting the potential application of SSIP in silicon‐based anodes.

We prepared a series of highly porous Polyrotaxane/sodium alginate, and Polyrotaxane/Chitosan foam alloys according to a sustainable pathway by using water as the only solvent. The foam alloys were further used as supporter materials for poly (ethylene glycol) (PEG) encapsulation, to fabricate shape-stable bio-based phase change materials (PCMs). The pore morphology and the internal interface between PEG and foam alloys were characterized by scanning electron microscope (SEM). Due to the good compatibility between foam alloys and PEG, the PCM performed perfect anti-leakage properties. The introduction of sodium alginate or Chitosan ensures the shape stability of the PCMs during the phase transition. The PCMs performed good cycle stability and showed ultra-high latent heat (171.6 J g−1–189.5 J g−1). Finally, we compared the typical indicators of this work with those reported in the literature, and the comparison highlighted that the present PCMs have the significant advantages: high melting enthalpy, convenient preparation and outstanding sustainability. Notably, the work provided a sustainable idea for the design of anti-leakage and shape-stable PEG-based PCMs. • The PCMs have ultra-high latent heat and perfect form stability. • The PCM can be fabricated in sustainable process with high efficiency. • It expanded the application of Chitosan and sodium alginate. [ABSTRACT FROM AUTHOR]

Cyclodextrins (CDs) are essential in the pharmaceutical industry and have long been used as food and pharmaceutical additives. CD-based interlocked molecules, such as rotaxanes, polyrotaxanes, catenanes, and polycatenanes, have been synthesized and have attracted considerable attention in supramolecular chemistry. Among them, CD polyrotaxanes have been employed as slide-ring materials and biomaterials. CD polycatenanes are new materials; therefore, to date, no examples of applied research on CD polycatenanes have been reported. Consequently, we expect that applied research on CD polycatenanes will accelerate in the future. This review article summarizes the syntheses and structural analyses of CD polyrotaxanes and polycatenanes to facilitate their applications in the pharmaceutical industry. We believe that this review will promote further research on CD-based interlocked molecules. [Display omitted] [ABSTRACT FROM AUTHOR]

• Polyrotaxane formed from anthracene polymer & β-Cyclodextrine rings. • Improved solubility & processability via encapsulation for the polyrotaxane. • Amorphous morphology & better thermal stability. • Smoother & more homogeneous surface observed for the encapsulated polymer. • Encapsulation enhanced redox potential & suppressed aggregation induced quenching. In this study, we present the synthesis of a novel host-guest polyrotaxane (PR1) using a microwave-assisted threading approach. The polyrotaxane structure involves the encapsulation of an anthracene-based conjugated polymer (P1) within β-cyclodextrin (β-CD) cavities. The successful formation of PR1 and P1 was confirmed using various spectroscopic and thermal techniques. Optimized geometry and vibrational frequencies of the polymer P1 conducted using DFT calculations at the DFT/B3LYP/6–311+ G (d) level of theory showed good agreement with experimental results. Physicochemical and electrical properties of PR1 and the free polymer P1 revealed significant improvements resulting from the encapsulation process. Particularly, enhanced solubility in DMF and DMSO and processability, improved thermal stability, surface homogeneity, and smoothness in PR1 compared to the free polymer. Additionally, the encapsulation process led to an enhanced redox potential of PR1 in comparison to the free polymer. Interestingly, the photoluminescence of thin films of P1 was found to be quenched due to a phenomenon known as aggregation caused quenching (ACQ). However, the encapsulation of the polymer using β-CD rings reduced the formation of aggregates, effectively suppressing the ACQ process. This resulted in the recovery of photoluminescence. Notably, the charge carrier mobility of the encapsulated polymer was maintained at a similar order of magnitude. [Display omitted] [ABSTRACT FROM AUTHOR]

Molecular gels, which are soft and flexible materials, are candidates for healthcare, cosmetic base, and electronic applications as new materials. In this study, a new polymeric organogelator bearing a polyrotaxane (PR) structure was developed and could induce the gelation of N′,N″-dimethylformamide (DMF), a known solvent for dissolving polymeric materials and salts. Furthermore, the resulting DMF molecular gels exhibited thixotropic properties, observed by the inversion method using vials, which are essential for gel spreading. The scanning electron microscopy of the xerogels suggested that the gel-forming ability and thixotropic property of gels were imparted by the network of the laminated aggregates of thin layer material similar to those of other gels made of clay materials. This thin layer material would be formed by the aggregation of polymeric organogelators. The dynamic viscoelasticity measurements of the obtained gels revealed the stability and pseudo-thixotropic behaviors of the obtained gels, as well as a specific concentration effect on the mechanical behavior of the gels attributed to the introduction of the PR structure. Additionally, the preparation of the polymer organogelator/polymer composites was investigated to improve the mechanical properties via the filler effect induced by the agglomerates of organogelator. Moreover, the tensile tests confirmed that the introduction of the gelator enhanced the mechanical properties of the composites.

New composite materials were prepared via cross-linking of polyethylene glycol/2-hydroxypropyl-β-cyclodextrins polyrotaxane (PEG/HPβCD) and polyisoprene/HPβCD semi-polyrotaxane (PI/HPβCD SR) with 1,6-hexamethylene diizocyanate (HMDI). Advanced instrumental methods (such WAXS (wide angle X-ray scattering), AFM (atomic force microscopy), SEM (scanning electron microscopy), and thermal and dynamic vapor sorption) were employed for the structural, morphological and thermal characterization of the resulting composite materials. The roughness parameters calculated using AFM indicate a smoother surface for the composite material with 10 wt% of PI/HPβCD SR, denoting that a homogeneous film was obtained. SEM analysis reveals porous morphologies for both composite materials and the pore sizes increase with the increasing concentration of PI/HPβCD SR in the matrix. Dynamic vapor sorption/desorption measurements and type IV isotherms confirmed the hydrophilic and porous materials, which are in agreement with SEM analysis. The composite with a higher PI/HPβCD SR concentration in the matrix showed increased thermal stability than that of the pure cross-linked material. This material was further tested as a sorbent for methylene blue (MB) dye removal from an aqueous solution. The adsorption capacity of the composite film was found to be 2.58 mg g−1 at 25 °C.

Preparing strong and flexible atelocollagen-based materials for biomedical applications is still a challenging task. To address this challenge, this study describes the synthesis and characterization of water-soluble polyrotaxanes (PRs) with different coverage ratios and molecular weights of axle polymers, and their potential applications for PR-reinforced atelocollagen threads (PRATs). A novel method was established for the syntheses of PRs with relatively low coverage ratio at the sub-gram scale, in which the aldehyde groups were employed as crosslinking sites for preparing the PRATs via reductive amination. The aldehyde groups were successfully quantified by 1H nuclear magnetic resonance spectroscopy using 1,1-dimethylhydrazine as an aldehyde marker. Fourier-transform infrared and thermogravimetric analysis measurements supported the characterization of the PRs. Interestingly, tensile testing demonstrated that coverage ratio affected the mechanical properties of the PRATs more strongly than molecular weight. The insights obtained in this study would facilitate the development of soft materials based on atelocollagens and PRs.

To improve the therapeutic potential of β-cyclodextrin (β-CD)-threaded acid-degradable polyrotaxanes (β-CD PRXs) in cholesterol-related metabolic disorders, we investigated the effect of carboxylation of β-CD PRXs on intracellular uptake. In this study, we established a synthetic method for the modification of carboxylalkyl carbamates on β-CD PRXs without degradation and synthesized three series of carboxyalkyl carbamate group-modified β-CD PRXs with different alkyl spacer lengths. The modification of carboxymethyl carbamate (CMC), carboxyethyl carbamate (CEC), and carboxypropyl carbamate (CPC) on the β-CD PRXs slightly reduced the interaction of the PRXs with the lipid layer model compared with the modification of 2-(2-hydroxyethoxy)ethyl carbamate (HEE-PRX), which was used in our previous studies. However, all the carboxylated β-CD PRXs showed a significantly stronger interaction with a protein model compared with HEE-PRX. The carboxylated β-CD PRXs showed significantly high intracellular uptake, through macrophage scavenger receptor A (MSR-A)-mediated endocytosis, in MSR-A-positive RAW 264.7 cells compared with HEE-PRX. Interestingly, the carboxylated β-CD PRXs also showed significantly higher intracellular uptake even in MSR-A-negative cells compared with HEE-PRX. Carboxylated β-CD PRXs are considered to strongly interact with other membrane proteins, resulting in high intracellular uptake. The length of the alkyl spacer affected the intracellular uptake levels of carboxylated PRXs, however, this relationship was varied for different cell types. Furthermore, none of the carboxylated β-CD PRXs exhibited cytotoxicity in the RAW 264.7 and NIH/3T3 cells. Altogether, carboxylation of β-CD PRXs is a promising chemical modification approach for their therapeutic application because carboxylated β-CD PRXs exhibit high cellular internalization efficiency in MSR-A-negative cells and negligible toxicity.

Despite the high-energy densities, the safety problem of thermal runaway in lithium-ion batteries (LIBs) severely hinders their further application. Therefore, as an essential part of LIBs, the separator should ideally have good thermal stability at high temperatures. Here, a novel polyrotaxane (PR)-based gel polymer electrolyte (GPE) with good thermal stability is made by a simple solution casting method. The thermal shrinkage of the PR is less than 20% even heated at 200 °C; in contrast, the commercial Celgard 2400 separator undergoes dramatic deformation above 140 °C. The gel polymer electrolyte presents excellent compatibility in the cells of LiFePO4 and LiNi0.5Co0.2Mn0.3O2 cathode. The cell composed of Li/GPE/LiFePO4 presents good discharge performance and excellent stored performance. The cell composed of Li/GPE/LiNi0.5Mn0.3Co0.2O2 presents excellent capacity retention of 85.9% in 300 cycles while discharging at the 0.5 C rate. This GPE is promising to be applied to Li metal batteries with high safety and good cycle life. [ABSTRACT FROM AUTHOR]

The development of chemo/photothermal nanotherapeutic systems with excellent photothermal performance, stable drug loading, tumor targeting and strong membrane penetration still remains a challenge. To address this problem, herein a rod-like nanocomposite system (AuNR@FA-PR/PEG) forming from folic acid (FA) terminated carboxylated cyclodextrin (CD) pseudopolyrotaxane (FA-PR) and polyethylene glycol (PEG) modifying gold nanorods (AuNR) was reported. Cisplatin (CDDP) was loaded in AuNR@FA-PR/PEG via coordination bonds to prepare a rod-like pH-responsive nanosystem (AuNR@FA-PR/PEG/CDDP) with chemotherapy/photothermal therapy. The rod-like morphology of AuNR@FA-PR/PEG was characterized by transmission electron microscope. In vitro drug release experiments showed the pH-responsive of AuNR@FA-PR/PEG/CDDP. In vivo real-time imaging assays proved AuNR@FA-PR/PEG/CDDP could rapidly enrich in the tumor area and stay for a long time because of folate targeting and their rod-like morphology. In vivo photothermal imaging assays showed AuNR@FA-PR/PEG/CDDP excellent photothermal performance, the average temperature of tumor region could reach 63.5 °C after 10 min irradiation. In vitro and in vivo experiments also demonstrated that the combined therapy of chemotherapy and photothermal therapy had an outstandingly synergistic effect and improved the therapeutic efficacy comparing with chemotherapy and photothermal therapy alone. Therefore, the prepared rod-like AuNR@FA-PR/PEG/CDDP will provide a new strategy for the effective treatment of cancer. [ABSTRACT FROM AUTHOR]

Recently, the potential of β-cyclodextrin-thread acid-degradable polyrotaxane (AdPRX) has been emphasized as a therapeutic agent for cholesterol-related metabolic disorders. In this study, we investigated whether carboxymethyl carbamate-modified AdPRX (CMCAdPRX) can be used for adsorption to calcium phosphate to treat bone diseases. We first synthesized CMC-AdPRX and used it to coat the calcium phosphate plate. RAW264.7 cells were then differentiated into osteoclasts via a receptor activator of nuclear factor-κB ligand, and the number of osteoclasts and the area of absorption lacunae were determined. The number of tartrate-resistant acid phosphatase-positive multinucleated cells was reduced on the CMC-AdPRX-coated plate. The area of the absorption lacunae was smaller with CMC-AdPRX than with AdPRX, which was not carboxy-modified. Our results suggest that CMC-AdPRX can adsorb to calcium phosphate and act on differentiated osteoclasts to suppress their functional expression. [ABSTRACT FROM AUTHOR]

Despite hundreds of studies involving slide-ring gels derived from cyclodextrin (CD)-based polyrotaxanes (PRs), their covalent cross-linking kinetics are not well characterized. We employ chemorheology as a tool to measure the gelation kinetics of a model slide-ring organogel derived from α-cyclodextrin/poly (ethylene glycol) PRs cross-linked with hexamethylenediisocyanate (HMDI) in DMSO. The viscoelastic properties of the gels were monitored in situ by small-amplitude oscillatory shear (SAOS) rheology, enabling us to estimate the activation barrier and rate law for cross-linking while mapping experimental parameters to kinetics and mechanical properties. Gelation time, gel point, and final gel elasticity depend on cross-linker concentration, but polyrotaxane concentration only affects gelation time and elasticity (not gel point), while temperature only affects gelation time and gel point (not final elasticity). These measurements facilitate the rational design of slide-ring networks by simple parameter selection (temperature, cross-linker concentration, PR concentration, reaction time).

Activation of autophagy represents a potential therapeutic strategy for the treatment of diseases that are caused by the accumulation of defective proteins and the formation of abnormal organelles. Methylated β-cyclodextrins-threaded polyrotaxane (Me-PRX), a supramolecular structured polymer, induces autophagy by interacting with the endoplasmic reticulum. We previously reported on the successful activation of mitochondria-targeted autophagy by delivering Me-RRX to mitochondria using a MITO-Porter, a mitochondria-targeted nanocarrier. The same level of autophagy induction was achieved at one-twentieth the dosage for the MITO-Porter (Me-PRX) compared to the naked Me-PRX. We report herein on the quantitative evaluation of the intracellular organelle localization of both naked Me-PRX and the MITO-Porter (Me-PRX). Mitochondria, endoplasmic reticulum and lysosomes were selected as target organelles because they would be involved in autophagy induction. In addition, organelle injury and cell viability assays were performed. The results showed that the naked Me-PRX and the MITO-Porter (Me-PRX) were localized in different intracellular organelles, and organelle injury was different, depending on the route of administration, indicating that different organelles contribute to autophagy induction. These findings indicate that the organelle to which the autophagy-inducing molecules are delivered plays an important role in the level of induction of autophagy.

[Display omitted] • Flexible and thermally conductive composites of polyrotaxane (PR) and hBN fillers. • Plasma surface modification improved dispersibility of hBN fillers in composites. • Reducing coverage of PR produced flexible and tough composites with modified hBN. • Gent model revealed increased extension between cross-links even in composites. An effective method for fabricating flexible materials containing thermally conductive fillers, such as hexagonal boron nitride (hBN), utilizes plasma surface modification and polyrotaxane (PR) with movable cross-linking points. This study demonstrated that lowering the coverage rates of PR composites increased the mobility of the cross-linking points. Plasma surface modification improved the dispersion of hBN and enabled homogeneous deformation of the PR composites owing to movable cross-linking points. Studying the deformation with a model including a finite extension effect indicated that the sliding range in the low-covered PR composites was extended compared to that in the high-covered PR composites, resulting in a smaller Young's modulus, longer extension, and higher toughness. [ABSTRACT FROM AUTHOR]

Rotaxanes are an emerging class of molecules composed of two building blocks: macrocycles and threads. Rotaxanes, and their pseudorotaxane and polyrotaxane relatives, serve as prototypes for molecular-level switches and machines and as components in materials like elastic polymers and 3D printing inks. The rigidity and flexibility of these molecules is a characteristic feature of their design. However, the mechanical properties of the assembled rotaxane and its components are rarely examined directly, and the translation of these properties from molecules to bulk materials is understudied. In this Review, we consider the mechanical properties of rotaxanes by making use of concepts borrowed from physical organic chemistry. Rigid molecules have fewer accessible conformations with higher energy barriers while flexible molecules have more accessible conformations and lower energy barriers. The macrocycles and threads become rigidified when threaded together as rotaxanes in which the formation of intermolecular interactions and increased steric contacts collectively reduce the conformational space and raise barriers. Conversely, rotational and translational isomerism in rotaxanes adds novel modes of flexibility. We find that rigidification in rotaxanes is almost universal, but novel degrees of flexibility can be introduced. Both have roles to play in the function of rotaxanes.

Polyrotaxane (PR) is a supramolecular polymer, in which an axial polymer extends through multiple cyclic molecules. PR specifically comprises polyethylene glycol, α -cyclodextrin, and adamantane as the axial polymer, cyclic molecule, and terminal blocking group, respectively. It is a useful stress-relaxing material because the cyclic polymers can freely slide and rotate in cyclic motions on the axial polymer. In this study, epoxy resin (DGEBA) cured with phenolic resin (PN) was blended with PR, which has methacryl groups at the ends of side chains of the cyclic molecules, as a toughness modifier. The effect of the methacryl group polymerization catalyst (DCP) on the cured properties of epoxy resin was reported. PR was homogeneously dispersed in the DGEBA/PN resin matrix. Increasing the PR concentration significantly improved the toughness, impact resistance, and adhesive properties of the DGEBA/PN/PR alloy. Moreover, adding DCP resulted in an increase in the glass transition temperature due to the decreased molecular mobility of the network. This phenomenon was attributed to the synergistic effect of the formation of an interpenetrating polymer network, which is an entangled network of the curing reaction of the DGEBA/PN resin and polymerization of PR, and the intermolecular hydrogen bonds between carbonyl and hydroxyl groups of PR and hydroxyl groups of the DGEBA/PN resin. In contrast, the increased interfacial adhesion between PR and the DGEBA/PN did not result in significant improvement of flexural properties. [Display omitted] • Polyrotaxane (PR) is a supramolecular polymer that acts a stress-relaxing material. • IPN is formed as entangled network of curing epoxy resin and PR polymerization. • Intermolecular hydrogen bonds between epoxy resin and PR improve heat resistance. • Increasing PR concentration substantially improves the toughness of epoxy resin. [ABSTRACT FROM AUTHOR]

Doxorubicin (DOX)-conjugated acid-degradable polyrotaxanes (PRXs) were designed as supramolecular drug carriers capable of releasing drugs in acidic cellular environments. Acid-degradable PRXs composed of α-cyclodextrin (α-CD) as a cyclic molecule, poly(ethylene glycol) (PEG) as a polymer axis, and N-triphenylmethyl (N-Trt) groups as an acid-labile stopper molecules were synthesized and DOX was conjugated with the threaded α-CDs in the PRXs. Because the acid-induced cleavage of N-Trt groups in PRXs leads to PRX dissociation, the DOX-modified α-CDs were released under acidic conditions (pH 5.0). The cytotoxicity of DOX-conjugated PRXs in colon-26 cells revealed significant cell death for DOX-conjugated PRXs after 48 h of treatment. Confocal laser scanning microscopy (CLSM) analysis revealed that the fluorescence signals derived from DOX-conjugated PRXs were observed in cellular nuclei after 48 h, suggesting that the DOX-modified α-CDs were released and accumulated in cellular nuclei. These results confirmed that acid-degradable PRXs can be utilized as drug carriers capable of releasing drug-modified α-CDs in acidic lysosomes and eliciting cytotoxicity. Overall, acid-degradable PRXs represent a promising supramolecular framework for the delivery and intracellular release of drug-modified α-CDs, and PRX–drug conjugates are expected to contribute to the development of pH-responsive drug carriers for cancer therapy.

Cyclodextrins (CDs) are one of the most extensively studied cyclic-oligosaccharides due to their low toxicity, good biodegradability and biocompatibility, facile chemical modification, and unique inclusion capacity. However, problems such as poor pharmacokinetics, plasma membrane disruption, hemolytic effects and a lack of target specificity still exist for their applications as drug carriers. Recently, polymers have been introduced into CDs to combine the advantages of both biomaterials for the superior delivery of anticancer agents in cancer treatment. In this review, we summarize four types of CD-based polymeric carriers for the delivery of chemotherapeutics or gene agents for cancer therapy. These CD-based polymers were classified based on their structural properties. Most of the CD-based polymers were amphiphilic with the introduction of hydrophobic/hydrophilic segments and were able to form nanoassemblies. Anticancer drugs could be included in the cavity of CDs, encapsulated in the nanoparticles or conjugated on the CD-based polymers. In addition, the unique structures of CDs enable the functionalization of targeting agents and stimuli-responsive materials to realize the targeting and precise release of anticancer agents. In summary, CD-based polymers are attractive carriers for anticancer agents.

Poly(ethylene glycol) diamine 1,1'-disubstituted ferrocene was utilized as a size-com-plementary site to synthesize lower coverage pseudopolyrotaxanes (pPRs) from self-assemblies with β- and γ-cyclodextrins (CDs). After end-capping β-CD pPRs using N-(triphenylmethyl)glycine (Trt-Gly-OH), an exact β-CD [3]polyrotaxane (PR) was created. However, an unexpected γ-CD [2]PR and a predictive chain folded stranded γ-CD pPR were identified from end-capped γ-CD pPRs. After end-capping a β-CD pPR self-assembled from β-CDs with amine terminated PEG containing ferrocene as a site-complementary site using Trt-Gly-OH, an exact β-CD [3]PR is invariably created. However, an unexpected γ-CD [2]PR and a predictive chain folded stranded γ-CD pPR are identified from end-capping γ-CD pPRs with Trt-Gly-OH. [ABSTRACT FROM AUTHOR]