Incorporation of dumbbell-shaped and Y-shaped cross-linkers in adjustable pullulan/polydopamine hydrogels for selective adsorption of cationic dyes.

Hydrogel adsorbents have attracted considerable attention due to their sludge minimization, good water permeability and renewable performance. Here, a promising strategy for the one-step preparation of pullulan/polydopamine hybird hydrogels (PPGels) was presented. Dumbbell-shaped cross-linker neopentyl glycol diglycidyl ether (NGDE, 2 arms) and Y-shaped cross-linker trimethylolpropane triglycidyl ether (TTE, 3 arms) were selected to study the relationship between cross-linker structure and hydrogel performances. The NGDE possessing less molecular repulsive force and higher reactivity demonstrated more effective cross-linking with the pullulan, which leaded to a decrease in pore size of the hydrogel. Meanwhile, the introduction of polydopamine significantly enhanced the adsorption ability and gave the resulting hybrid gel the specific selectivity toward cationic dyes (96 mg/g for crystal violet, 25.8 mg/g for methylene blue and barely not adsorption for azophloxine). Our data suggested that the electrostatic interaction played a vital role in the dye adsorption process, and the adsorption data could be explained by pseudo-second-order model and Langmuir isotherm model. Furthermore, the obtained PPGel could be easily separated after adsorption. This study describes the relationship between cross-linker structure and properties of pullulan/polydopamine hybrid gels, which provides a new strategy to create polysaccharide-based adsorbents for wastewater remediation.

Salecan-Based pH-Sensitive Hydrogels for Insulin Delivery.

Stimuli-responsive polymeric hydrogels are promising and appealing delivery vehicles for protein/peptide drugs and have made protein/peptide delivery with both dosage- and spatiotemporal-controlled manners possible. Here a series of new Salecan-based pH-sensitive hydrogels were fabricated for controlled insulin delivery via the graft copolymerization reaction between Salecan and 2-acrylamido-2-methyl-1-propanesulfonic acid. In this study, on one hand, Salecan played a key role in modifying the structure and the pore size of the developing hydrogel. On the other hand, Salecan tuned the water content and the water release rate of the obtained hydrogel, leading to a controllable release rate of the insulin. More importantly, in vitro release experiments validated that the release of insulin from this intelligent system could be also tailored by the environmental pH of the release medium. For SGA2, the amount of encapsulated insulin released at gastric conditions (pH 1.2) was relatively low (about 26.1 wt % in 24 h), while that released at intestinal conditions (pH 7.4) increased significantly (over 50 wt % in 6 h). Furthermore, toxicity assays demonstrated that the designed hydrogel carriers were biocompatible. These characteristics make the Salecan-based hydrogel a promising candidate for protein/peptide drug delivery device.

Fenton-like catalyst Fe3O4@polydopamine-MnO2 for enhancing removal of methylene blue in wastewater.

Fenton technology has been proven an effective way to remove dyes from wastewater. However, the demanding pH of reaction condition restricted its wide application. In this study, we report a novel Fenton-like catalyst (Fe3O4@PDA-MnO2) facilely synthesized by polydopamine (PDA) coating and MnO2 depositing onto the surface of Fe3O4 nanoparticles. This method for preparing magnetic Fe3O4@PDA-MnO2 catalyst could avoid the agglomeration of MnO2 nanoparticles and make the catalyst collect easily from the solution. The resultant Fe3O4@PDA-MnO2 nanoparticles possess core-shell nanostructure. Fe3O4@PDA-MnO2 catalyst could cooperate with hydrogen peroxide to form a Fenton-like reagent for the removal of methylene blue (MB) and performed excellent catalytic activities towards MB, including high degradation efficiency of 97.36% after 240 min. Besides, Fe3O4@PDA-MnO2 can retain excellent reusability after 5 using-cycles. More importantly, the catalyst can be used in a wide pH range from 2 to 12 in Fenton systems, demonstrating that the degradation process is independent on pH which is different from most reported studies. Also, Fe3O4@PDA-MnO2 could still keep more than 75% removal efficiency of MB in industrial wastewater treatment application. Therefore, the synthesized Fe3O4@PDA-MnO2 would be a promising device for the removal of dyes from wastewater.

Synthesis and characterization of a multi-sensitive polysaccharide hydrogel for drug delivery.

Salecan is a novel water soluble polysaccharide produced by a salt-tolerant strain Agrobacterium sp. ZX09. Poly(dimethylaminoethyl methacrylate) (PDMAEMA) is a pH, thermo, and ionic strength multi-sensitive polymer with anti-bacterial property. Here, we report a semi-interpenetrating polymer network (semi-IPN) hydrogel based on salecan and PDMAEMA. The obtained hydrogel is simultaneous sensitive to pH, ionic strength and temperature: the swelling ratio maximizes at pH 1.2 and shrinks at pH value greater than 3; besides, water content of the hydrogel decreases as the ionic strength increases; in terms of temperature, the hydrogel swells/deswells at temperatures below/above 40°C. Cytotoxicity test shows the hydrogel is non-cytotoxic to COS-7 cells. Protein drug insulin was selected as model drug to test the in vitro release behavior of the hydrogel. Results show the release rate increases with the swelling ratio of the hydrogel. In addition, when the temperature is higher than the lower critical solution temperature (LCST) of PDMAEMA, the hydrogel shrinks to extrude more drug molecules. Moreover, the release rate and release amount were higher in acid condition (pH 1.2) than at pH 7.4. In summary, this polysaccharide hydrogel is a promising material for drug delivery.

Preparation of a Salecan/poly(2-acrylamido-2-methylpropanosulfonic acid-co-[2-(methacryloxy)ethyl]trimethylammonium chloride) Semi-IPN Hydrogel for Drug Delivery.

Salecan is a water-soluble bacterial polysaccharide consisting of glucopyranosyl units linked by α-1,3 and ß-1,3 glycosidic bonds. salecan is suitable for the development of hydrogels for biomedical applications, given its outstanding physicochemical and biological profiles. In this study we designed a new semi-interpenetrating polymer network hydrogel that introduces the salecan polysaccharide into a stimuli-responsive poly(2-acrylamido-2-methylpropanosulfonic acid-co-[2-(methacryloxy)ethyl]trimethylammonium chloride) (PAM) hydrogel matrix for controlled insulin release. We found that salecan not only tunes the structure and pore size of the PAM hydrogels, but also endows them with adjustable water release rates. More importantly, in vitro drug loading/release assays demonstrated that insulin is efficiently loaded into the resulting hydrogels and can be released in an on-demand manner by controlling the pH and salecan dose. Furthermore, cell viability and cell adhesion experiments verified the cell compatibility of these hydrogel carriers. Together, these results make salecan-incorporated PAM hydrogels promising materials for drug delivery.

Synthesis and characterization of a novel cationic hydrogel base on salecan-g-PMAPTAC.

Salecan is a biological macromolecular and biocompatible polysaccharide that has been investigated for recent years. Herein, we report a novel cationic hydrogel fabricated by graft-polymerizing 3-(methacryloylamino)propyl-trimethylammonium chloride (MAPTAC) onto salecan chains. The obtained hydrogels were transparent, solid-elastic, macro-porous, ion-sensitive, and non-cytotoxic. The swelling ratios increased with salecan content, while mechanical strength does the opposite. Moreover, drug delivery test was studied as a potential application. Diclofenac sodium (DS) and insulin were selected as model drugs. Interestingly, in drug loading process, DS molecules exhibited highly affinity to these cationic hydrogels. Almost all the DS molecules in loading solution were absorbed and spread into the hydrogel. For drug release profiles, insulin-loaded hydrogel showed an initial rapid release and a sustained release. As a comparison, DS-loaded hydrogel exhibited a more sustained release profile. Results suggested salecan-g-PMAPTAC hydrogel could be a good candidate for anionic drug loading and delivery.

Synthesis and characterization of a novel pH-thermo dual responsive hydrogel based on salecan and poly(N,N-diethylacrylamide-co-methacrylic acid).

Salecan is a water-soluble microbial polysaccharide produced by Agrobacterium sp. ZX09, a salt-tolerant strain isolated from a soil sample in our laboratory. Previous work inspired us salecan is a good candidate to fabricate hydrogels. Poly(N,N-diethylacrylamide) is one type of thermo sensitive polymer which is not investigated extremely as poly(N-isopropylacrylamide). Here, we report a novel pH-thermo dual responsive hydrogel based on salecan and poly(N,N-diethylacrylamide-co-methacrylic acid) semi-interpenetrating polymer networks (semi-IPNs). The physicochemical property of this hydrogel was investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analyses (TGA), rheological test and Scanning Electron Microscopy (SEM). It was interesting that the storage modulus (G') and pore size of the hydrogel could be tuned by adjusting the content of salecan and crosslinker. The pH-thermo dual responsive property was demonstrated by swelling behavior test: the swelling ratio of the hydrogel decreased continuously as the temperature increased from 25 °C to 37 °C, while it was pH-dependent as well. Especially, when exposed to a higher temperature (37 °C) and acidic environment (pH 4.0), drug-loaded hydrogel would have a quick release. Finally, the cytotoxicity of drug-free hydrogels was investigated on A549 and HepG2 cells, results showed that it was non-toxic while the DOX released from hydrogels had comparable cytotoxicity with respect to free DOX. In conclusion, the novel salecan/poly(N,N-diethylacrylamide-co-methacrylic acid) semi-interpenetrating polymer network hydrogels were pH-thermo dual responsive and may be a promising candidate for drug delivery system.