Ka I Lee

Super-tough and thermo-healable hydrogel – promising for shape-memory absorbent fiber

Recoverable hydrogels with high stretch and toughness have been synthesized by a one-step radical polymerization. They consist of covalently crosslinked polyacrylamide (PAAm) and ionically crosslinked carrageenan. Such double network (DN) hydrogels can be stretched beyond 20 times their initial length, and their fracture energy reached a high value of ∼9500 J m-2. By comparing hydrogel tensile properties at different temperatures, the contribution of ionic network to the toughness was quantitatively determined in percentage for the first time. The stretched hydrogels were completely healed by short treatment at a mild temperature. Through drying at stretch, they were also transformed into stiff absorbent fibers that still preserved their shape memory of wet state.

Polyethylenimine coated bacterial cellulose nanofiber membrane and application as adsorbent and catalyst

Bacterial cellulose (BC) nanofiber membranes were simply aminalized by a flush-coating and post-crosslinking method. Firstly, wet BC membranes were flushed through by an aqueous solution of polyethylenimine (PEI) and glycerol diglycidyl ether (GDE) under vacuum suction, then further heated up to 70 °C to crosslink the resultant coating on the surface of the nanofibers. The PEI coated bacterial cellulose (BC@PEI) nanofiber membrane presented excellent adsorption performance for Cu(2+) and Pb(2+) ions from aqueous solutions. Desorption of these ions was achieved using ethylene diamine tetraacetic acid treatment. This cycle of adsorption and desorption was repeated for several times with good remain adsorption performance (over 90%). Furthermore, the adsorbed Cu(2+) ions can be reduced to copper nanoparticles, and showed excellent catalytic performance for methylene blue reduction in aqueous solution. The catalytic performance can remained after several times of usage.

Reversible Mechanochromism of a Luminescent Elastomer

A novel mechanochromic elastomer was manufactured by doping bis(benzoxazolyl)stibene (BBS) into a thermoplastic polyurethane. Both solution casting and melt compounding approaches were tried with a range of BBS concentrations, and an optimal concentration of 0.5% was selected to investigate the mechanochromic mechanism in detail. When the blend film was stretched up to 100%, its emission peaks at 475 and 413 nm changed in intensity ratio from 6.3 to 1.8. When it was released, both the film size and emission peaks largely recovered. By a short annealing at 120 °C, their full recovery was achieved. Its reversion mechanism was proposed and proved by X-ray diffraction. In comparison to previous mechanochromic materials, this smart elastomer is easy to prepare, highly sensitive to stress, facilely renewable in usage, and totally based on biocompatible materials, having potential applications like stress sensors, intelligent devices, and alarming packages.

Antibacterial modification of an injectable, biodegradable, non-cytotoxic block copolymer-based physical gel with body temperature-stimulated sol-gel transition and controlled drug release.

Biomaterials are being extensively used in various biomedical fields; however, they are readily infected with microorganisms, thus posing a serious threat to the public health care. We herein presented a facile route to the antibacterial modification of an important A-B-A type biomaterial using poly (ethylene glycol) methyl ether (mPEG)- poly(ε-caprolactone) (PCL)-mPEG as a typical model. Inexpensive, commercial bis(2-hydroxyethyl) methylammonium chloride (DMA) was adopted as an antibacterial unit. The effective synthesis of the antibacterial copolymer mPEG-PCL-∼∼∼-PCL-mPEG (where ∼∼∼ denotes the segment with DMA units) was well confirmed by FTIR and (1)H NMR spectra. At an appropriate modification extent, the DMA unit could render the copolymer mPEG-PCL-∼∼∼-PCL-mPEG highly antibacterial, but did not largely alter its fascinating intrinsic properties including the thermosensitivity (e.g., the body temperature-induced sol-gel transition), non-cytotoxicity, and controlled drug release. A detailed study on the sol-gel-sol transition behavior of different copolymers showed that an appropriate extent of modification with DMA retained a sol-gel-sol transition, despite the fact that a too high extent caused a loss of sol-gel-sol transition. The hydrophilic and hydrophobic balance between mPEG and PCL was most likely broken upon a high extent of quaternization due to a large disturbance effect of DMA units at a large quantity (as evidenced by the heavily depressed PCL segment crystallinity), and thus the micelle aggregation mechanism for the gel formation could not work anymore, along with the loss of the thermosensitivity. The work presented here is highly expected to be generalized for synthesis of various block copolymers with immunity to microorganisms. Light may also be shed on understanding the phase transition behavior of various multiblock copolymers.

Highly water-absorbing silk yarn with interpenetrating network via in situ polymerization

Silk was modified via in situ polymerization of two monomers acrylamide and sodium acrylate by swelling in an effective LiBr dissolution system. Swelling of natural silks in LiBr solutions of low concentration was clearly observed under optical microscope, and their conformational changes were revealed by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Dissolution tests and FTIR spectra of these modified silks suggested the presence of interpenetrating network of polyacrylamide and poly(sodium acrylate) in the silk yarns. These modified silks exhibited superior water absorption to that of raw silk and greatly improved mechanical properties in both dry and wet states. These novel modified silks also showed low cytotoxicity towards skin keratinocytes, having potential applications in biomedical textiles. This modification method by in situ polymerization after swelling in LiBr provides a new route to highly enhance the properties and performance of silk for various applications.