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In this study, we report a novel approach to fabricate an organic/inorganic magnetic hybrid system capable of self-healing, wherein a polycaprolactone-poly(furfuryl glycidyl ether) copolymer (PCLF) serving as the structure template was first synthesized, followed by the incorporation of iron oxide nanoparticles-decorated multiwalled carbon nanotubes (IONPs-MWCNTs) and 1,1′-(methylenedi-4,1-phenylene)bismaleimide (BMI) into the polymer matrix to form a covalently crosslinked hybrid network via a Diels−Alder (DA) reaction. For this system, the reactive combination of diene and dienophile from furan/maleimide, MWCNT/furan, and MWCNT/maleimide could facilely induce multiple DA reactions that imparted a versatile route to efficiently introduce IONPs-MWCNTs into the organic polymer hosts, resulting in a uniform distribution of IONPs-MWCNTs that led to a hybrid system with superparamagnetic properties. Beside the magnetic behavior, such material synergistically exhibited a superior ability for healing scratch defects via a retro-DA reaction. Therefore, this crosslinked PCLF/BMI/IONPs-MWCNTs hybrid system which exhibits multifunctional properties including superparamagnetic behavior and self-repairability can serve as an intelligent material for developing advanced electromagnetic applications. [ABSTRACT FROM AUTHOR]

In this study, a novel biobased poly(ethylene brassylate)-poly(furfuryl glycidyl ether) copolymer (PEBF) copolymer was synthesized and applied as a structure-directing template to incorporate graphene and 1,1′-(methylenedi-4,1-phenylene)bismaleimide (BMI) to fabricate a series of self-healing organic/inorganic hybrid materials. This ternary material system provided different types of diene/dienophile pairs from the furan/maleimide, graphene/furan, and graphene/maleimide combinations to build a crosslinked network via multiple Diels–Alder (DA) reactions and synergistically co-assembled graphene sheets into the polymeric matrix with a uniform dispersibility. The PEBF/graphene/BMI hybrid system possessed an efficient self-repairability for healing structural defects and an electromagnetic interference shielding ability in the Ku-band frequency range. We believe that the development of the biobased self-healing hybrid system provides a promising direction for the creation of a new class of materials with the advantages of environmental friendliness as well as durability, and shows potential for use in advanced electromagnetic applications. [ABSTRACT FROM AUTHOR]

In this work, a smart copolymer, Poly(nipam-co-IAM) was synthesized by copolymerization of N-isopropylacrylamide (nipam) and itaconamic acid (IAM) through reversible addition-fragmentation chain-transfer (RAFT) polymerization. Poly(nipam-co-IAM) has been studied previously synthesized via radical polymerization without stereo-control, and this work used cumyl dithiobenzoate and Ytterbium(III) trifluoromethanesulfonate as RAFT and stereo-control agents, respectively. The stereo-control result in this work shows that tacticity affects the lower critical solution temperature (LCST) and/or the profile of phase separation of Poly(nipam-co-IAM). In the pH 7 and pH 10 buffer solutions, the P(nipam-co-IAM) copolymer solutions showed soluble–insoluble–soluble transitions, i.e., both LCST and upper critical solution temperature (UCST) transitions, which had not been found previously, and the insoluble to soluble transition (redissolved behavior) occurred at a relatively low temperature. The insoluble to soluble transition of P(nipam-co-IAM) in alkaline solution occurred at a temperature of less than 45 °C. However, the redissolved behavior of P(nipam-co-IAM) was found only in the pH 7 and pH 10 buffer solutions and this redissolved behavior was more prominent for the atactic copolymers than in the isotactic-rich ones. In addition, the LCST results under our experimental range of meso content did not show a significant difference between the isotactic-rich and the atactic P(nipam-co-IAM). Further study on the soluble-insoluble-soluble (S-I-S) transition and the application thereof for P(nipam-co-IAM) copolymers will be conducted. [ABSTRACT FROM AUTHOR]

A series of semi-interpenetrating polymer network (semi-IPN) hydrogels were synthesized and investigated in this study. Linear copolymer poly(N-isopropylacrylamide-co-itaconamic acid) p(NIPAM-co-IAM), which is formed by copolymerization of N-isopropylacrylamide (NIPAM) and itaconamic acid (IAM, 4-amino-2-ethylene-4-oxobutanoic acid), was introduced into a solution of NIPAM to form a series of pH and thermo dual-responsive p(NIPAM-co-IAM)/pNIPAM semi-IPN hydrogels by free radical polymerization. The structural, morphological, chemical, and physical properties of the linear copolymer and semi-IPN hydrogels were investigated. The semi-IPN hydrogel showed high thermal stability according to thermal gravimetric analyzer (TGA). Scanning electronic microscopy (SEM) images showed that the pore size was in the range of 119~297 µm and could be controlled by the addition ratio of the linear copolymer in the semi-IPN structure. The addition of linear copolymer increased the fracture strain from 57.5 ± 2.9% to 91.1 ± 4.9% depending on the added amount, while the compressive modulus decreased as the addition increased. Moreover, the pH and thermo dual-responsive properties were investigated using differential scanning calorimetry (DSC) and monitoring the swelling behavior of the hydrogels. In deionized (DI) water, the equilibrium swelling ratio of the hydrogels decreased as the temperature increased from 20 °C to 50 °C, while it varied in various pH buffer solutions. In addition, the swelling and deswelling rates of the hydrogels also significantly increased. The results indicate that the novel pH-thermo dual-responsive semi-IPN hydrogels were synthesized successfully and may be a potential material for biomedical, drug delivery, or absorption application. [ABSTRACT FROM AUTHOR]

In this work, a smart copolymer, Poly(nipam-co-IAM) was synthesized by copolymerization of N -isopropylacrylamide (nipam) and itaconamic acid (IAM) through reversible addition-fragmentation chain-transfer (RAFT) polymerization. Poly(nipam-co-IAM) has been studied previously synthesized via radical polymerization without stereo-control, and this work used cumyl dithiobenzoate and Ytterbium(III) trifluoromethanesulfonate as RAFT and stereo-control agents, respectively. The stereo-control result in this work shows that tacticity affects the lower critical solution temperature (LCST) and/or the profile of phase separation of Poly(nipam-co-IAM). In the pH 7 and pH 10 buffer solutions, the P(nipam-co-IAM) copolymer solutions showed soluble⁻insoluble⁻soluble transitions, i.e., both LCST and upper critical solution temperature (UCST) transitions, which had not been found previously, and the insoluble to soluble transition (redissolved behavior) occurred at a relatively low temperature. The insoluble to soluble transition of P(nipam-co-IAM) in alkaline solution occurred at a temperature of less than 45 °C. However, the redissolved behavior of P(nipam-co-IAM) was found only in the pH 7 and pH 10 buffer solutions and this redissolved behavior was more prominent for the atactic copolymers than in the isotactic-rich ones. In addition, the LCST results under our experimental range of meso content did not show a significant difference between the isotactic-rich and the atactic P(nipam-co-IAM). Further study on the soluble-insoluble-soluble (S-I-S) transition and the application thereof for P(nipam-co-IAM) copolymers will be conducted.

Copolymerization of N -isopropylacrylamide (NIPAM), itaconamic acid (IAM; 4-amino-2-methylene-4-oxobutanoic acid) and β-cyclodextrin was investigated in this study. β-cyclodextrin was at first modified by reacting with allyl glycidyl ether to substitute its OH end groups with moieties containing double bonds to facilitate the subsequent radical copolymerization with NIPAM and IAM. It was reported that poly(NIPAM-IAM) can respond to the change of temperature as well as pH value. In this study, the structure of β-cyclodextrin was introduced to poly(NIPAM-IAM) copolymers because of its cavity structure capable of encapsulating a variety of drug molecules. The tri-component copolymers, poly(CD-NIPAM-IAM), were synthesized with different monomeric ratios of NIPAM/IAM/β-CD and the hydrogels of the tri-component copolymers were also synthesized by additionally adding N , N '-methylenebisacrylamide as a cross-linking agent. The results show that the lower critical solution temperature (LCST) of the copolymer (or hydrogel) increases as the molar fraction of IAM increases. The transmission electron microscopic (TEM) images of linear copolymers (no cross-linking) show that molecules undergo self-assembly to have a distinct core-shell structure, compared to poly(CD-NIPAM) which contains no IAM. On the other hand, the scanning electron microscopic (SEM) images of hydrogels show that the pores gradually become sheet-like structures as the molar fraction of IAM increases to enhance the water absorption capacity. In order to exhibit the thermal and pH sensitivities of poly(CD-NIPAM-IAM) as the drug carrier, the drug release of the newly synthesized hydrogels at 37 °C and different pH values, pH = 2 and pH = 7.4, was investigated using atorvastatin which was used primarily as a lipid-lowering drug. The drug release experimental result shows that poly(CD-NIPAM-IAM) as a drug carrier was pH-sensitive and has the largest release rate at pH = 7.4 at 37 °C, indicating it is useful to release drugs in a neutral or alkaline (intestinal) environment.