Synthesis, classification and properties of hydrogels: their applications in drug delivery and agriculture.

Absorbent polymers or hydrogel polymer materials have an enhanced water retention capacity and are widely used in agriculture and medicine. The controlled release of bioactive molecules (especially drug proteins) by hydrogels and the encapsulation of living cells are some of the active areas of drug discovery research. Hydrogel-based delivery systems may result in a therapeutically advantageous outcome for drug delivery. They can provide various sequential therapeutic agents including macromolecular drugs, small molecule drugs, and cells to control the release of molecules. Due to their controllable degradability, ability to protect unstable drugs from degradation and flexible physical properties, hydrogels can be used as a platform in which various chemical and physical interactions with encapsulated drugs for controlled release in the system can be studied. Practically, hydrogels that possess biodegradable properties have aroused greater interest in drug delivery systems. The original three-dimensional structure gets broken down into non-toxic substances, thus confirming the excellent biocompatibility of the gel. Chemical crosslinking is a resource-rich method for forming hydrogels with excellent mechanical strength. But in some cases the crosslinker used in the synthesis of the hydrogels may cause some toxicity. However, the physically cross-linked hydrogel preparative method is an alternative solution to overcome the toxicity of cross-linkers. Hydrogels that are responsive to stimuli formed from various natural and synthetic polymers can show significant changes in their properties under external stimuli such as temperature, pH, light, ion changes, and redox potential. Stimulus-responsive hydrogels have a wider range of applications in biomedicine including drug delivery, gene delivery and tissue regeneration. Stimulus-responsive hydrogels loaded with multiple drugs show controlled and sustained drug release and can act as drug carriers. By integrating stimulus-responsive hydrogels, such as those with improved thermal responsiveness, pH responsiveness and dual responsiveness, into textile materials, advanced functions can be imparted to the textile materials, thereby improving the moisture and water retention performance, environmental responsiveness, aesthetic appeal, display and comfort of textiles. This review explores the stimuli-responsive hydrogels in drug delivery systems and examines super adsorbent hydrogels and their application in the field of agriculture.

Ionic Network Based on Dynamic Ionic Liquids for Electronic Tattoo Application.

Electronic tattoos as an emerging epidermal electronic are alluring in the field of wearable electronics for their lightweight and noninvasive properties. However, the combination of flexibility, skin biocompatibility, adhesion, repairability, and erasability remains a challenge for fabricating electronic tattoos. Hence, a dynamic ionic liquid is prepared which is ideally suited for making an electronic tattoo with these challenging features at the same time. Such an intrinsically flexible electronic tattoo can be firmly attached to human skin with negligible irritation. More importantly, the existence of dynamic covalent chemistry provides the electronic tattoo with healing and erasable abilities under mild redox conditions. Owing to the high ionic conductivity of ionic liquids, the electronic tattoo exhibits excellent sensing performance in response to the temperature variation and tensile strain, which can intelligently monitor body temperature, pulse, and movement. As an extension of the application, a specially designed quadrilateral electronic tattoo can sense and distinguish multiple signals simultaneously. This concept of electronic tattoo based on the dynamic ionic liquid shows great potentials in the applications of intelligent wearable electronics.

Synthesis of a pH-responsive nano-cellulose/sodium alginate/MOFs hydrogel and its application in the regulation of water and N-fertilizer.

In order to circumvent the water eutrophication caused by nitrogen loss in agriculture, slow-release and high-water containing fertilizers have captured much attention. Considering the unstable release of traditional slow-released fertilizers, novel strategies need to be designed to meet the steady release of fertilizers. Herein, by integrating cellulose-based hydrogel with MIL-100(Fe), a pH-sensitive Cellulose/MOFs hydrogel (CAM) with a high surface area (45.25 m2/g) was devised. The volume changes and the water adsorption of the hydrogels were uncovered from pH 3 to pH 11, where the highest water adsorption (100 g/g) was achieved at pH 11. Besides, a pH-sensitive urea slow release fertilizer (U-CAM) was also designed. The urea release of the U-CAM at pH 11 was much slower than that of the U-CAM at pH 3, which indicated its potential application in arid regions. In parallel with a favorable water-holding capacity, the totally loss of the soil moisture loaded with U-CAM was slowed down by 18 days as compared with the pure soil. The positive effect of the U-CAM on the growth of wheat was indexed with the germination rate, number of tillers, photosynthetic rate and chlorophyll content of the crop, which verified their further application in irrigating farming.

Chitosan-poly(vinyl alcohol) intelligent films fortified with anthocyanins isolated from Clitoria ternatea and Carissa carandas for monitoring beverage freshness.

Biodegradable chitosan-poly(vinyl alcohol) films containing natural anthocyanin-rich extracts were prepared using solvent casting method and employed as intelligent indicators for monitoring beverages freshness. The surface and cross-sectional scanning electron micrograph indicated a compact structure for the intelligent films, whereas the atomic force micrograph indicated a 16.22 and 20.31 nm increase in surface roughness for Clitoria ternatea and Carissa carandas extract incorporated films, respectively. Moreover, the test films demonstrated enhanced radical scavenging efficacy. The extracts and anthocyanin incorporated films presented excellent colorimetric changes at pH 2 to 8. In addition, the C. ternatea test films showed changes in color for juice stored at 25 °C after 72 h. Photo-degradability results indicated stability of test films stored in dark at 4 °C and 25 °C, whereas leaching study indicated the release of ≤2.0% anthocyanin after 24 h. The cytocompatibilty assay showed that the test and control films were biocompatible with a viability of >80% on HaCat cells. The results demonstrated that the incorporation of anthocyanins-rich extracts into chitosan-poly(vinyl alcohol) did not significantly interfere with the films properties (p > 0.05). The natural anthocyanin incorporated films demonstrated good pH sensing property that could be further explored for monitoring of beverages freshness.

A Biodegradable Chitosan-Polyurethane Cryogel with Switchable Shape Memory.

Cryogels are matrices that are formed in moderately frozen solutions of monomeric or polymeric precursors. They have the advantages of interconnected macropores, structural stability, and compressibility. Meanwhile, thermally induced shape memory is an attractive feature of certain functional materials. Although there have been several studies concerning shape-memory cryogels, little work has been conducted on shape-memory cryogels with biodegradability. In this study, a water-based biodegradable difunctional polyurethane with a shape-memory property was synthesized and used as the nanoparticulate crosslinker to react with chitosan to form a shape-memory cryogel. The thermally induced shape-memory mechanism was clarified using in situ wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS) during the shape-memory process. The in situ WAXS showed the changes of crystallinity in the crosslinker and the cryogel during the shape fixation and recovery processes. The in situ SAXS revealed the orientation of crystallinity of the crosslinker and the cryogel as the mechanism for shape memory. The strip-shape cryogel was deformed at 50 °C to U-shape and fixed at - 20 °C, which was squeezable at 25 °C and returned to the strip-shape at 50 °C in air. The shape recovery was further tested in water at two different temperatures. The injected cryogel recovered the U-shape in 4 °C water, representing elastic recovery, and transformed to a long strip in 37 °C water, representing the switchable shape memory. Moreover, the shape-memory cryogel sheet with a large dimension (10 mm × 10 mm × 1.1 mm cryogel sheet) or with complex structures (N, T, and U shapes) could be fixed as a rod, injected through a 16 G needle, and return to its original shape in 37 °C water, all of which could not be achieved by the conventional cryogel. Human mesenchymal stem cells grown in the shape-memory cryogel scaffolds displayed long-term proliferation and chondrogenic potential. Their unique injectability and cytocompatibility suggested potential applications of shape-memory cryogels as injectable and expandable templates for tissue engineering and minimally invasive surgery.

Thiol-Reactive Clickable Cryogels: Importance of Macroporosity and Linkers on Biomolecular Immobilization.

Macroporous cryogels that are amenable to facile functionalization are attractive platforms for biomolecular immobilization, a vital step for fabrication of scaffolds necessary for areas like tissue engineering and diagnostic sensing. In this work, thiol-reactive porous cryogels are obtained via photopolymerization of a furan-protected maleimide-containing poly(ethylene glycol) (PEG)-based methacrylate (PEGFuMaMA) monomer. A series of cryogels are prepared using varying amounts of the masked hydrophilic PEGFuMaMA monomer, along with poly(ethylene glycol) methyl ether methacrylate and poly(ethylene glycol) dimethacrylate, a hydrophilic monomer and cross-linker, respectively, in the presence of a photoinitiator. Subsequent activation to the thiol-reactive form of the furan-protected maleimide groups is performed through the retro Diels-Alder reaction. As a demonstration of direct protein immobilization, bovine serum albumin is immobilized onto the cryogels. Furthermore, ligand-directed immobilization of proteins is achieved by first attaching mannose- or biotin-thiol onto the maleimide-containing platforms, followed by ligand-directed immobilization of concanavalin A or streptavidin, respectively. Additionally, we demonstrate that the extent of immobilized proteins can be controlled by varying the amount of thiol-reactive maleimide groups present in the cryogel matrix. Compared to traditional hydrogels, cryogels demonstrate enhanced protein immobilization/detection. Additionally, it is concluded that utilization of a longer linker, distancing the thiol-reactive maleimide group from the gel scaffold, considerably increases protein immobilization. It can be envisioned that the facile fabrication, conjugation, and control over the extent of functionalization of these cryogels will make these materials desirable scaffolds for numerous biomedical applications.

Reprogrammable Permanent Shape Memory Materials Based on Reversibly Crosslinked Epoxy/PCL Blends.

: Epoxy/Polycaprolactone (PCL) blends cured with a conventional diamine (4,4'-diaminodiphenylmethane, DDM) and with different amounts of a disulfide containing diamine (4, 4´-dithioaniline, DSS) were prepared through melting. The curing process was studied by FTIR and differential scanning calorimetry (DSC) and the mechanical behavior of the networks was studied by DMA. The shape memory properties and the recyclability of the materials were also analyzed. All blends showed a very high curing degree and temperature activated shape memory effect, related to the glass transition of the epoxy resin. The PCL plasticized the mixture, allowing tailoring of the epoxy glass transition. In addition, in the blends cured with DSS, as a consequence of the disulfide exchange reaction, the permanent shape could be erased and a new shape could be reprogrammed. Using this strategy, reprogrammable permanent shape memory materials were obtained.

Biocompatible film sensors containing red radish extract for meat spoilage observation.

pH-sensitive films were developed based on biocompatible materials and natural pH sensitive dye. The films were successfully fabricated using starch/gelatin and red radish anthocyanin. The colors of films could be differentiated by naked eye within 5 min changing from orange to grey-purple at pH 2-12 and captured by a smartphone. The color parameters were evaluated by the Image J software. In addition, the color change of films was observed in ammonia gas atmosphere. The color stability of sensing films was evaluated and the results indicated that the films had great stability and were able to store more than two weeks. The results from intra-day and inter-day color response study showed good precision. Finally, the pH-sensitive films could be applied to real samples for real-time meat spoilage observation.

A biodegradable functional water-responsive shape memory polymer for biomedical applications.

Shape memory polymers (SMPs) have exhibited great potential in biomedical applications. However, the typical triggers of shape recovery such as heat, UV light, and electricity may be harmful to humans. Accordingly, water-responsive SMPs have become significant, especially for in vivo applications, due to the intrinsic biocompatibility and ready availability of water. However, the reported water-responsive SMPs are limited and relatively complicated. Here, we design a new water-responsive SMP, poly(butanetetrol fumarate) (PBF); the properties of PBF could be modulated by curing. The cured PBF scaffolds exhibited high shape recovery and fixity rates (>95%). PBF showed good biodegradability, and it could support the attachment, viability and alkaline phosphatase activity of osteoblasts. Furthermore, PBF could be readily functionalized via pendant hydroxyl groups, which was demonstrated by the immobilization and controlled release of bone morphogenetic protein 2. We expect that PBF will be useful for various biomedical applications including water-responsive scaffolds, sensors or actuators.