Self-assembled poly(ethylene glycol) methyl ether-grafted gelatin nanogels for efficient delivery of curcumin in cancer treatment

Curcumin (CUR) is a natural active ingredient that attracted much attention for its chemotherapeutic activity against tumors without causing toxicity in healthy cells. However, it has certain limitations for being used in chemotherapy such as low aqueous solubility and hydrolytic instability in the physiological environment. In this study, self-assembled poly(ethylene glycol) methyl ether-grafted gelatin (Gel-mPEG) nanogels were fabricated as delivery systems to improve the applicability of CUR in cancer treatment. CUR-loaded Gel-mPEG nanogels exhibited desired size range, relatively colloidal stability, and provided enhanced CUR stability in aqueous solutions. Especially, they showed significant high CUR loading capacity and better anticancer activity than free CUR as compared to previously reported CUR-loaded nanogels according to the best of our knowledge. Moreover, the in vitro release of CUR from the nanogels was controlled and prolonged up to 96 h. These results demonstrated that Gel-mPEG nanogels are the promising modality for the efficient delivery of CUR in cancer treatment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47544.     

Methacrylate hydrogels reinforced with bacterial cellulose

Composite hydrogels consisting of nanofibrous bacterial cellulose (BC) embedded in a biocompatible polymeric matrix of various methacrylates were synthesized by UV polymerization using the ‘ever‐wet’ technique. The effect of monomer(s) type and ratio, system dilution at polymerization, monomer(s) hydrophilicity, crosslink density and cellulose/hydrogel ratio was investigated. The effect of BC reinforcement on equilibrium swelling depends on whether the neat gel swells more when brought into contact with water. The major improvement achieved by introduction of 1%–2% BC concerns mechanical properties. Compared with neat gels, the storage shear modulus G′ increased by a factor 10‐20, and the loss part G″ also rose significantly. The compression modulus ranged from 2 to 5.5 MPa for composites swollen to equilibrium (20‐70 wt% water). The BC‐hydrogel composites are considered for application in the tissue engineering area. Copyright © 2012 Society of Chemical Industry     

Improved protein resistance of silicone hydrogels by grafting short peptides for ophthalmological application

A simple and facile approach to impart the antifouling properties of silicone hydrogels was developed in this report. Short peptides were first tethered to silicone hydrogels through terminal amino group-induced epoxy ring-opening click reaction. The modified silicone hydrogels have improved hydrophilicity and protein adsorption resistance because of the formation of zwitterionic structure of the grafted peptides. Furthermore, glycylglycine and diglycyl glycine-modified silicone hydrogel contact lenses were fabricated. They exhibited favorable antifouling property and no damage to rabbits’ eyes after continuous wearing. The short peptide modified silicone hydrogel contact lenses have potential application in ophthalmology.     

In situ-forming injectable hydrogels for regenerative medicine

Regenerative medicine involves interdisciplinary biomimetic approaches for cell therapy and tissue regeneration, employing the triad of cells, signals, and/or scaffolds. Remarkably, the field of therapeutic cells has evolved from the use of embryonic and adult stem cells to the use of induced pluripotent stem cells. For application of these cells in regenerative medicine, cell fate needs to be carefully controlled via external signals, such as the physical properties of an artificial extracellular matrix (ECM) and biologically active molecules in the form of small molecules, peptides, and proteins. It is therefore crucial to develop biomimetic scaffolds, reflecting the nanoenvironment of three-dimensional (3D) ECM in the body. Here, we describe in situ-forming injectable hydrogel systems, prepared using a variety of chemical crosslinkers and/or physical interactions, for application in regenerative medicine. Selective and fast chemical reactions under physiological conditions are prerequisites for in situ formation of injectable hydrogels. These hydrogels are attractive for regenerative medicine because of their ease of administration, facile encapsulation of cells and biomolecules without severe toxic effects, minimally invasive treatment, and possibly enhanced patient compliance. Recently, the Michael addition reaction between thiol and vinyl groups, the click reaction between bis(yne) molecules and multiarm azides, and the Schiff base reaction have been investigated for generation of injectable hydrogels, due to the high selectivity and biocompatibility of these reactions. Noncovalent physical interactions have also been proposed as crosslinking mechanisms for in situ forming injectable hydrogels. Hydrophobic interactions, ionic interactions, stereocomplex formation, complementary pair formation, and host–guest interactions drive the formation of 3D polymeric networks. In particular, supramolecular hydrogels have been developed using the host–guest chemistry of cyclodextrin (CD) and cucurbituril (CB), which allows highly selective, simple, and biocompatible crosslinking. Molecular recognition and complex formation of supramolecules, without the need for additional additives, have been successfully applied to the 3D network formation of polymer chains. Finally, we review the current state of the art of injectable hydrogel systems for application in regenerative medicine, including cell therapy and tissue regeneration.     

Novel bioresorbable hydrogels prepared from chitosan‐graft‐polylactide copolymers

A series of biodegradable chitosan‐graft‐polylactide (CS‐g‐PLA) copolymers were prepared by grafting of poly(L ‐lactide) (PLLA) or poly(D ‐lactide) (PDLA) precursor to the backbone of chitosan using N,N′‐carbonyldiimidazole as coupling agent. The composition of the copolymers was varied by adjusting the chain length of PLA as well as the ratio of chitosan to PLA. The copolymers synthesized via this ‘graft‐onto’ method present interesting properties as shown by NMR and infrared spectroscopy, gel permeation chromatography and solubility tests. Hydrogels were prepared by mixing water‐soluble CS‐g‐PLLA and CS‐g‐PDLA solutions. Gelation was assigned to stereocomplexation between PLLA and PDLA blocks as evidenced by differential scanning calorimetry and wide‐angle X‐ray diffraction measurements. Thymopentin (TP5) was taken as a model drug to evaluate the potential of these CS‐g‐PLA hydrogels as drug carriers. An initial burst and a final release up to 82% of TP5 were observed from high‐performance liquid chromatography analysis. Copyright © 2011 Society of Chemical Industry     

High porosity,responsive hydrogel copolymers from emulsion templating

Hydrogels, three‐dimensional hydrophilic polymer network structures, can absorb many times their dry weight in water. PolyHIPEs are highly porous polymers synthesized within high internal phase emulsions (HIPEs). Here, the water uptakes in novel hydrogel polyHIPE copolymers of hydroxyethyl methacrylate (HEMA, a non‐ionic monomer) and methacrylic acid (MAA, an ionic monomer) were investigated. The PHEMA‐based polyHIPE had a density of 0.14 g cm^?3, void diameters of 50–100 µm and a void‐dominated Fickian water uptake of around 10.4 g g^?1. The polyHIPE density increased, and the porous structure became less polyHIPE‐like, with increasing MAA content, reflecting a reduction in the stability of the HIPE. The water uptake increased with increasing pH for all the copolymers and the water absorption mechanism changed from Fickian at pH 2 to anomalous, dominantly case II, at pH 10. The maximum uptake of 18.2 g g^?1 at pH 10, for a HEMA to MAA mass ratio of 1/1, was ascribed to hydrogel‐swelling‐driven void expansion. The hydrogel's absorptive and responsive properties were amplified by the polyHIPE's porous structure. These results demonstrate that the compositions of hydrogel polyHIPE copolymers can be designed to enhance their water uptake. © 2015 Society of Chemical Industry     

Processing–formulation–performance relationships of polypropylene/short flax fiber composites

This work is a comprehensive study of the effect of extrusion process parameters and formulation on the properties of polypropylene (PP)/short flax fiber composites. The parameters that were varied during the twin‐screw extrusion process were screw configuration, revolutions per minute (rpm), extrusion temperature, and flow rate. The effect of the feeding zone location of cellulosic fiber was also considered. This study investigates the effect of the formulation, cellulosic fiber content, the presence of a coupling agent, and of a reactive additive on composite performance. The composites were characterized in terms of morphology and microstructure, fiber length, rheological, thermal, and mechanical properties. Sensibility to humidity and recyclability were also considered. When compared with as‐received PP, the tensile strength of injection‐molded parts increased with cellulosic content by up to 40 vol %, and the tensile modulus increased 3.5 times when a combination of coupling and reactive agents was used. Exposed to controlled humidity of 50% during 1 year, these composites exhibited a very low level of humidity uptake around 0.85 wt %. The processability of these materials using a cast film line and the mechanical properties of extruded sheets are also presented. Furthermore, these materials demonstrate a good recyclability using injection molding by keeping the integrality of their mechanical properties after five reprocessing cycles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41528.     

Compression molding and melt‐spinning of the blends of poly(lactic acid) and poly(butylene succinate‐co‐adipate)

Poly(lactic acid) (PLA) is a biobased polymer made from biomass having high mechanical properties for engineering materials applications. However, PLA has certain limited properties such as its brittleness and low heat distortion temperature. Thus, the aim of this study is to improve toughness of PLA by blending with poly(butylene succinate‐co‐adipate) (PBSA), the biodegradable polymer having high toughness. Polymer blends of PLA and PBSA were prepared using a twin screw extruder. The melt rheology and the thermal property of the blends were examined. Further the blends were fabricated into compression molded parts and melt‐spun fiber and were subjected to tensile and impact tests. When the PBSA content was low, PBSA phase was finely dispersed in the PLA matrix. On the other hand, when the PBSA content was high, this minor phase dispersed as a large droplet. Mechanical properties of the compression molded parts were affected by the dispersion state of PBSA minor component in PLA matrix. Impact strength of the compression molded parts was also improved by the addition of soft PBSA. The improvement was pronounced when the PBSA phase was finely dispersed in PLA matrix. However, the mechanical property of the blend fibers was affected by the postdrawing condition as well as the PBSA content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41856.     

Swelling kinetics,mechanical properties,and release characteristics of chitosan‐based semi‐IPN hydrogels

Two series of pH‐sensitive semi‐interpenetrating network hydrogels (semi‐IPN) based on chitosan (CS) natural polymer and acrylamide (AAm) and/or N‐hydroxymethyl acrylamide (HMA) monomers by varying the monomer and CS ratios were synthesized by free radical chain polymerization. 5‐Fluorouracil (5‐FU), a model anticancer drug, has been added to the feed composition before the polymerization. The characterization of gels indicated that the drug is molecularly dispersed in the polymer matrix. The swelling kinetics of drug‐loaded gels have decreased with increased HMA content at 37°C in both distilled water and buffer solutions with a pH of 2.1 or 7.4. Elastic modulus of the gels increased with the increase in HMA content and higher CS concentration enhanced the elastic modulus positively. Moreover, cumulative release percentages of the gels for 5‐FU were ca. 10% higher in pH 2.1 than those in pH 7.4 media. It was determined that they can be suitable for the use in both gastric and colon environments. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41886.