SYNTHESIS AND CHARACTERIZATION OF POLYROTAXANES MADE FROM α-CDs THREADED ONTO TRIBLOCK COPOLYMERS WITH PEG AS A CENTRAL AXLE AND FLANKED BY TWO LOW MOLECULAR WEIGHT POLYSTYRENES AS OUTER STOPPERS

A study has been conducted on the synthesis and characterization of a kind of novel polyrotaxanes comprisingα- cyclodextrins (α-CDs) threaded on triblock eopolymers with poly(ethylene glycol) (PEG) as a central axle and flanked by two low molecular weight polystyrenes as outer stoppers.Styrene was allowed to telomerize with polypseudorotaxanes as chain transfer agents made from the self-assembly of a distal thiol-capped PEG with a varying amount ofα-CDs in the presence of a redox initiation system at 40~C i...

Self-assembly Polyrotaxanes Nanoparticles as Carriers for Anticancer Drug Methotrexate Delivery

α-Cyclodextrin/poly(ethylene glycol)(α-CD/PEG) polyrotaxane nanoparticles were prepared via a self-assembly method. Anticancer drug methotrexate(MTX) was loaded in the nanoparticles. The interaction between MTX and polyrotaxane was investigated. The formation, morphology, drug release and in vitro anticancer activity of the MTX loaded polyrotaxane nanoparticles were studied. The results show that the MTX could be efficiently absorbed on the nanoparticles, and hydrogen bonds were formed between MTX andα-CDs. The typical channel-type stacking assembly style of polyrotaxane nanoparticles was changed after MTX was loaded. The mean diameter of drug loaded polyrotaxane nanoparticles were around 200 nm and the drug loading content was as high as about 20%. Drug release profiles show that most of the loaded MTX was released within 8 hours and the cumulated release rate was as high as 98%. The blank polyrotaxane nanoparticles were nontoxicity to cells. The in vitro anticancer activity of the MTX loaded polyrotaxane nanoparticles was higher than that of free MTX.

Glutathione as the End Capper for Cyclodextrin/PEG Polyrotaxanes

A facile one-pot synthesis of α-cyclodextrin-based polyrotaxane （PR） in aqueous solution is reported, where the peptide glutathione was used as the end-capping agent and the thiol-ene Michael addition was used as the end-capping reaction. Both polyrotaxanes with low threading ratio and high threading ratio were successfully obtained. In contrast to the conventionally used multiple-step synthesis methods and hydrophobic end cappers, this one-pot aqueous synthesis as well as the biocompatibility of the end-capping agent could result in a much more biocompatible PR to be used as biomaterials.

Supramolecular Micelles and Reverse Micelles Based on Cyclodextrin Polyrotaxanes

A new supramolecular self-assembly approach to construct micelles and reverse micelles was reported.Double-hydrophilic block copolymers poly(ethylene oxide)-b-poly(N-isopropylacrylamide) (PEO-b-PNIPAAm) was synthesized via atom transfer radical polymerization (ATRP) using PEO macroinitiator.Because of the lower critical solution temperature (LCST) phase behavior of PNIPAAm,PEO-b-PNIPAAm block copolymers self-assembled to form PNIPAAm-core micelles at 40 ℃.The PNIPAAm-core micelles were disassembled to unimers when the temperature was decreased to 25 ℃.But the addition of α-cyclodextrins (α-CDs) could induce the formation of PNIPAAm-shell micelles because of the 'channel-type' crystallities induced by PEO/α-CDs polyrotaxanes.The assembly and disassembly procedure of micelles and reverse micelles were investigated by dynamic light scattering (DLS),X-ray diffraction (XRD),1H NMR and transmission electron microscopy (TEM).

Distinguishing channel-type crystal structure from dispersed structure in 13-cyclodextrin based polyrotaxanes via FTIR spectroscopy

Combining with XRD analysis, Fourier transform infrared （FTIR） spectroscopy is employed to discern the self-assembled structures of β-cyclodextrins （β-CDs） threaded onto the polymer backbone in the polyrotaxanes （PRs） by means of the relative changes of absorption intensity of the characteristic peaks of β-CDs at 1153 and 1025 cm^-1. For quantitative analysis, six parameters are proposed to describe the relative absorption intensity variations of these peaks associated with a channel-type crystal structure or a dispersed structure of β-CDs entrapped. Among them, absorbance ratio （AR）, relative absorbance difference （RAD） and transmittance difference （TD） values are suitable. When the AR, RAD and TD data get below 1.04, 4.8 and 1.27, respectively, the PRs obtained would possess a dispersed structure. If these values go beyond 1.32, 34,5 and 9.47, respectively, they would hold a channel-type crystal structure. This finding provides a useful judgment to distinguish the self-assembled structures of β-CDs residing along the polymer backbone in the PRs.

Slightly Cross-Linked Polyrotaxanes Made by Linking α-Cyclodextrins Entrapped in Polyrotaxanes Using Hexamethylene Diisocyanate

In this study polyrotaxane （PR）-based triblock copolymers were first synthesized via the atom transfer radical polymerization （ATRP） of N-isopropylacrylamide initiated with the self-assembly of a distal 2-bromoisobutyryl end-capped Pluronie 17R4 with a varying amount of a-cyclodextrins （a-CDs） in the presence of CuCI/PMDETA at 25 ℃ in aqueous solution. The a-CDs entrapped on the copolymer chain were then linked with hexamethylene diisocyanate to give rise to novel slightly cross-linked polyrotaxanes （SCPRs） in DMF at 45 ℃. The structures of the PR-based triblock copolymers and SCPRs were characterized by 1H NMR, 13C CP/MAS, GPC and TGA analy- ses. The number-average molecular weight of the resulting SCPRs was nearly three and five times of their precursor after linking with a low polydispersity index range of 1.08--1.28. The thermo-responsive transition of both PR-based supramolecular polymers in aqueous solution was demonstrated by turbidity measurements and the self-aggregated morphologies were also evidenced by TEM observations.

Structure and Mechanical Properties of Waterborne Polyurethane-based Composites Filled with Self-assembled Supramolecular Nanoplatelets

New composites of waterborne polyurethane （WPU） as a matrix were prepared by incorporating rigid supramolecular nanoplatelets （SNs） as filler, which were self-assembled by the selective inclusion of β-cyclodextrin （β-CD） onto poly（propylene oxide） （PPO） segment in the poly（ethylene oxide）- block-PPO-block-poly（ethylene oxide） （PEO-b-PPO-b-PEO）. It is worth noting that, when the loading level of SN is lower than 3wt%, the SNs with moderate PEO length result in the simultaneous increase in strength, elongation and Young＇s modulus in contrast with neat WPU. If there is no stretching free PEO chain, both strength and elongation decrease in spite of an increase in Young＇s modulus. However, too long PEO chains result in the decrease of mechanical performances while the relatively higher loading-level of SNs also inhibits the enhancement of strength and elongation.

Synthesis and Structural Characterization of a New Hydrogen-bonded Polyrotaxane of [Co(H_2O)_6]_(2+) with 1,1′-(Propane-1,3-diyl)dipyridinium-4-carboxylate

A new double betaine 1,1′-（propane-1,3-diyl）dipyridinium-4-carboxylate L has been synthesized. Reaction of 1, 1′-（propane-1,3-diyl）dipyridinium-4-carboxylate tetrahydrate 1 with Co（ClO4）2-6H2O leads to the formation of a new Co（Ⅱ） coordination compound, namely [Co（H2O）6]-2H2O-2L-2ClO4 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1. monoclinic, space group C2/c, a = 18.945（4）, b = 7.700（2）, c = l 1.888（2）A,β = 101.67（3）°, V = 1698.3（6） A^3, Z = 4, F（000） = 760.0, Dc = 1.402 g/cm^3, the final R = 0.0607 and wR = 0.1607 for 950 observed reflections （1 〉 2σ（I））; and those for 2： monoclinic, space group P21/c, a = 17.982（1）, b = 15.879 （1）, c = 7.0716（5）/A,β= 100.675（1）°, V= 1984.3（3） ,A^3 Z= 4, F（000） = 1010.0, Dc = 1.631 g/cm^3, the final R = 0.0316 and wR = 0.0896 for 3784 observed reflections （1 〉20（I））. Crystal structure analysis indicates that in 1, molecules of L in a ＂V-shaped＂ conformation are linked to chains sustained by O-H…O hydrogen bonds between carboxylate groups and solvent water molecules. The chains are joined by O-H…O and C-H…O hydrogen bonds to further expand into a three-dimensional structure. For 2, molecules of L in a ＂Z-shaped＂ conformation are linked by hydrogen bonds between carboxylate groups and aqua ligands to form a chain of loops running down the b axis. The （2D→2D） polythreading in compound 2 represents the mode of parallel interpenetration of 2D sheets, having polyrotaxane character.

Stretchable poly[2]rotaxane elastomers

Mechanically interlocked polymers(MIPs)are promising candidates for the construction of elastomeric materials with desirable mechanical performance on account of their abilities to undergo inherent rotational and translational mechanical movements at the molecular level.However,the investigations on their mechanical properties are lagging far behind their structural fabrication,especially for linear polyrotaxanes in bulk.Herein,we report stretchable poly[2]rotaxane elastomers(PREs)which integrate numerous mechanical bonds in the polymeric backbone to boost macroscopic mechanical properties.Specifically,we have synthesized a hydroxyfunctionalized[2]rotaxane that subsequently participates in the condensation polymerization with diisocyanate to form PREs.Benefitting from the peculiar structural and dynamic characteristics of the poly[2]rotaxane,the representative PRE exhibits favorable mechanical performance in terms of stretchability(∼1200%),Young’s modulus(24.6 MPa),and toughness(49.5 MJ/m^(3)).Moreover,we present our poly[2]rotaxanes as model systems to understand the relationship between mechanical bonds and macroscopic mechanical properties.It is concluded that the mechanical properties of our PREs are mainly determined by the unique topological architectures which possess a consecutive energy dissipation pathway including the dissociation of host−guest interaction and consequential sliding motion of the wheel along the axle in the[2]rotaxane motif.

Polyrotaxane-Based Functional Materials Enabled by Molecular Mobility and Conformational Transition

Slide-ring structured polyrotaxanes with high molecular mobility and reversible conformational transition ability can achieve high performance and multifunctionality of the material in various applications.There have been many reviews describing advances in the research of rotaxanes and polyrotaxanes.However,most of them typically focus on the precise synthesis of mechanically interlocked molecules and the control of microscopic molecular shuttles.In this review,we examine the effects of motion activity and conformational transition due to molecular slide on the performance of polyrotaxanes and the latest functional applications.Different designs of polyrotaxane-based functional materials are presented to improve the potential for applications including self-healing stretchable elastomers/gels,stimuli-responsive smart devices,battery electrode binders,and biomedical drug delivery.It is anticipated that this review will provide insights and guidance for future developments in the design,synthesis and application of polyrotaxane-based functional materials.

Imparting Pulley Effect and Self-healability to Cathode Binder of Li-S Battery for Improvement of the Cycling Stability

To construct structurally stable sulfur cathode of Li-S battery with improved cycling performance,poly(acrylic acid)(PAA)crosslinked by cationic hydroxypropyl polyrotaxane(HPRN+)via dynamically reversible boronic ester bonds is synthesized and serves as the cathode binder.The smart polymer networks offer multifunction including buffering the volume change of the cathode during charge/discharge through the pulley effect of polyrotaxanes(PR),suppressing the shuttle effect by adsorption of polysulfide using the plentiful carboxyl,hydroxyl and quaternary ammonium cationic groups,and self-healing the micro-damages to ensure stable conduction pathways of the electrode.As a result,the Li-S batteries based on this novel multifunctional binder and simple commercial sulfur/carbon composites cathode exhibit excellent specific capacity and cycling stability.In particular,the specific capacity decay per cycle of the cell is only 0.064%along with high Coulombic efficiency after 550 cycles at 1.0 C,which is superior to most of the reported binders.Even under high sulfur loading,moreover,the cathode can deliver superior areal capacity and cycling stability.This proposed binder provides a new way for the design of high-stability sulfur cathodes.

SYNTHESIS AND PROPERTIES OF COPOLYMERS CONTAINING CUCURBIT[6]URIL-BASED PSEUDOROTAXANE STRUCTURE

Novel copolymers based on acrylamide （AM） and complex pseudorotaxane monomer N＇-（3-vinylbenzyl）-l,4- diaminobutane dihydrochloride with cucurbit[6]uril （CB[6]） （3VBCB） were prepared via free-radical polymerization in aqueous solution, and characterized by XH-NMR, FT-IR, elemental analysis and static light scattering. The compositions of the copolymers （PAM3VBCB） with pseudorotaxane units were determined by 1H-NMR and elemental analysis. Thermal properties of the copolymers were studied by TGA, and the effects of the copolymer concentration and pH on the average hydrodynamic radius （Rh） of the copolymer molecules were studied by dynamic light scattering （DLS）. The experiment data show that CB[6] beads are localized on 1,4-diaminobutane units in side chains of the copolymers. TGA results show that thermal stability of the copolymer increases with increasing the content of pseudorotaxane unit because of the enhanced rigidity and the bulky steric hindrance of 3VBCB in side chains of PAM3VBCB. DLS data show that the average hydrodynamic radius of copolymer molecules increases with the increase in the copolymer concentration, and both the pH and electrical conductivity of PAM3VBCB solutions demonstrate an acute change with addition of NaOH because of CB[6] dethreading from the side chains of PAM3VBCB. CB[6] threading and dethreading of PAM3VBCB could be controlled by addition of BaC12 and Na2SO4.

One-pot synthesis of well-organized heteropolyrotaxane via self-sorting strategy

Two novel [3]pseudorotaxanes can be selectively synthesized from four components through self-sorting processes, which provides a new strategy for the construction of a well-organized heteropolyrotaxane.