Synthesis and physicochemical investigation of chitosan-built hydrogel with induced glucose sensitivity

There is an urgent need to treat diabetes, and therefore, this work reports on a chitosan-built hydrogel functionalized by a glucose sensing moiety, which simulates pancreatic activity. The effect of external stimuli on various internal properties was investigated to establish the action of the hydrogel. The model drugs, fluorescein (D1) and rhodamine (D2), with a diol architecture, were investigated spectroscopically with 75.94% loading and 65.63% release. Consequently, a ligand to glucose ratio of 2:1 in comparison with a ligand to model drug ratio of 1:1 was addressed. The system was expected to lead to findings on applications for the self-controlled release of insulin in response to blood glucose levels.     

HPMC-based granules for prolonged release of phytostrengtheners in agriculture

One of the main aims in agriculture is to guarantee soil wellness, which is a fundamental requirement to produce high-quality crops with high yields. Focused on this aim, periodical administrations of nutrients or phytostrengtheners are often necessary. The most relevant disadvantages of these administrations are the high dosage number required and the low availability of the substance within the soil. For these reasons, a crucial goal to increase the economic and environmental sustainability of the cultivation process is to reduce the dosage number, which can be obtained increasing the active substance availability in the soil. A granular hydroxypropyl methylcellulose (HPMC) matrix, produced using the wet granulation process, was used to encapsulate a phytostrengthener and to guarantee its controlled release. The granular product was characterized in terms of granules properties and phytostrengtheners leaching within the soil. The results showed good flowability and mechanical properties of the granules as well as the possibility to reduce the product leaching with the phytostrengtheners encapsulation in the HPMC matrices.     

Novel superabsorbent materials from bacterial cellulose

A novel process for the production of superabsorbent materials (hydrogels) from bacterial cellulose (BC) was developed. Prior to crosslinking with a water‐soluble polyethylene glycol diacrylate (PEGDA), BC was first carboxymethylated and functionalized with glycidyl methacrylate. The degree of crosslinking influenced the swelling properties of the hydrogels. The use of greater amounts of PEGDA enhanced the formation of a thicker macromolecular network containing fewer capillary spaces in the crosslinked gel. The maximum water retention value of the hydrogels containing 2.5–3.5 mmol of carboxyl groups per gram of gel reached 125 g g^?1 in distilled water, and 29 g g^?1 in saline (0.9% NaCl solution). The highly porous hydrogel architecture with a pore size of 350–600 µm created a high specific surface area. This enables rapid mass penetration in superabsorbent applications. The superabsorbent hydrogels reached 80% of their maximum water absorption capacity in 30 min. © 2018 Society of Chemical Industry     

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     

A novel method of making PVF porous foam without using the pore forming agent

Different with the conventional method of manufacturing poly(vinyl formal) (PVF) porous foam by using the pore‐forming agents such as wheat or potato starches, a novel method without using the pore‐forming agent is introduced in this article. Through the help of images taken by a scanning electron microscope, the formation process of the present PVF foam will be discussed in terms of the spinodal decomposition (SD) phase separation principle. Additionally, the effect of poly(vinyl alcohol) concentration and reaction temperature on the pore structure of the PVF foam will be investigated. Moreover, the water adsorption capacities of the PVF foams obtained by the present method will be studied in details through the analyses of pore‐size distribution, mechanical modulus, and thermal property. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41270.     

Multilayer‐coated NPK compound fertilizer hydrogel with controlled nutrient release and water absorbency

A novel trilayered controlled‐release nitrogen, phosphorous, and potassium (NPK) fertilizer hydrogel was prepared by dipping the NPK fertilizer granules sequentially in 7% w v^?1 poly(vinyl alcohol) (PVA) and 2% w v^?1 chitosan (CS) solutions and then cross‐linking the CS layer (cross‐CS) via glutaraldehyde vapor deposition. Different NPK fertilizer hydrogels were then synthesized by inverse suspension polymerization of the dried PVA/cross‐CS bilayer‐coated fertilizer granules in various molar ratios of acrylamide (AM) and acrylic acid (AA) monomers, and polymerization with varying molar ratios of ammonium persulfate, N,N,N′,N′‐tetramethylethylenediamine and N,N′‐methylenebisacrylamide (N‐MBA). The water dissolution time of the obtained PVA/cross‐CS/poly (AA‐co‐AM) trilayer‐coated NPK fertilizer hydrogel granules was prolonged, while the water absorbency increased with increasing AA contents, and decreased with increasing N‐MBA contents in the outer poly(AA‐co‐AM) coating. The optimal trilayer‐coated NPK fertilizer hydrogel obtained released 84 ± 18, 63 ± 12, and 36 ± 15% of the N, P, and K nutrients, respectively, after a 30‐day immersion in water. The release phenomena of the N, P, and K nutrients of the fertilizer hydrogel obeyed both the Korsmeyer‐Peppas and Ritger‐Peppas models with a pseudo‐Fickian diffusion mechanism. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41249.