Photothermally Active Cryogel Devices for Effective Release of Antimicrobial Peptides: On-Demand Treatment of Infections.

There has been significant interest in the use of peptides as antimicrobial agents, and peptide containing hydrogels have been proposed as biological scaffolds for various applications. Limited stability and rapid clearance of small molecular weight peptides pose challenges to their widespread implementation. As a common approach, antibacterial peptides are physically loaded into hydrogel scaffolds, which leads to continuous release through the passive mode with spatial control but provides limited control over drug dosage. Although utilization of peptide covalent linkage onto hydrogels addresses partially this problem, the peptide release is commonly too slow. To alleviate these challenges, in this work, maleimide-modified antimicrobial peptides are covalently conjugated onto furan-based cryogel (CG) scaffolds via the Diels-Alder cycloaddition at room temperature. The furan group offers a handle for specific loading of the peptides, thus minimizing passive and burst drug release. The porous nature of the CG matrix provides rapid loading and release of therapeutic peptides, apart from high water uptake. Interfacing the peptide adduct containing a CG matrix with a reduced graphene oxide-modified Kapton substrate allows "on-demand" photothermal heating upon near-infrared (NIR) irradiation. A fabricated photothermal device enables tunable and efficient peptide release through NIR exposure to kill bacteria. Apart from spatial confinement offered by this CG-based bandage, the selective ablation of planktonic Staphylococcus aureus is demonstrated. It can be envisioned that this modular "on-demand" peptide-releasing device can be also employed for other topical applications by appropriate choice of therapeutic peptides.

Chitosan Gels and Cryogels Cross-Linked with Diglycidyl Ethers of Ethylene Glycol and Polyethylene Glycol in Acidic Media.

Here we show that the efficacy of the chitosan interaction with diglycidyl ethers of glycols significantly depends on pH and the nature of acid used to dissolve chitosan. In solutions of hydrochloric acid, cross-linking with diglycidyl ethers of ethylene glycol (EGDGE) and polyethylene glycol (PEGDGE) at room and subzero temperatures yields mechanically stable chitosan gels and cryogels, while in acetic acid solutions only weak chitosan gels can be formed under the same conditions. A combination of elemental analysis, FT-IR spectroscopy, and solid state 13C and 15N NMR spectroscopy was used to elucidate possible differences in the mechanism of chitosan cross-linking in alkaline and acidic media at room and subzero temperatures. We have proved that in acidic media diglycidyl ethers of glycols interacted with chitosan mainly via hydroxyl groups at the C6 position of the glucosamine unit. Besides, not only cross-linkages but also grafts were formed at room temperature. The cryo-concentration effect facilitates cross-linkages formation at -10 °C and, despite lower modification degrees compared to those of gels obtained at room temperature, supermacroporous chitosan cryogels with Young's moduli up to 90 kPa can be fabricated in one step. Investigations of chitosan cryogels biocompatibility in a mouse model have shown that a moderate inflammatory reaction around the implants is accompanied by formation of a normal granulation tissue. No toxic, immunosuppressive, and sensitizing effects on the recipient's tissues have been observed.

Removal of iron by chelation with molecularly imprinted supermacroporous cryogel.

Iron chelation therapy can be used for the selective removal of Fe(3+) ions from spiked human plasma by ion imprinting. N-Methacryloyl-(L)-glutamic acid (MAGA) was chosen as the chelating monomer. In the first step, MAGA was complexed with the Fe(3+) ions to prepare the precomplex, and then the ion-imprinted poly(hydroxyethyl methacrylate-N-methacryloyl-(L)-glutamic acid) [PHEMAGA-Fe(3+)] cryogel column was prepared by cryo-polymerization under a semi-frozen temperature of - 12°C for 24 h. Subsequently, the template, of Fe(3+) ions was removed from the matrix by using 0.1 M EDTA solution. The values for the specific surface area of the imprinted PHEMAGA-Fe(3+) and non-imprinted PHEMAGA cryogel were 45.74 and 7.52 m(2)/g respectively, with a pore size in the range of 50-200 µm in diameter. The maximum Fe(3+) adsorption capacity was 19.8 µmol Fe(3+)/g cryogel from aqueous solutions and 12.28 µmol Fe(3+)/g cryogel from spiked human plasma. The relative selectivity coefficients of ion-imprinted cryogel for Fe(3+)/Ni(2+) and Fe(3+)/Cd(2+) were 1.6 and 4.2-fold greater than the non-imprinted matrix, respectively. It means that the PHEMAGA-Fe(3+) cryogel possesses high selectivity to Fe(3+) ions, and could be used many times without significantly decreasing the adsorption capacity.

Multiresponsive macroporous semi-IPN composite hydrogels based on native or anionically modified potato starch.

Macroporous semi-interpenetrating polymer networks (semi-IPN) composite hydrogels were synthesized by cross-linking polymerization of acrylamide (AAm) with N,N'-methylenebisacrylamide (BAAm) in the presence of potato starch (PS) or an anionic polyelectrolyte derived from PS (PA), below the freezing point of the reaction solution (-18 °C). The composite cryogels have been further modified by the partial hydrolysis of the amide groups in poly(acrylamide) (PAAm) matrix, under alkaline conditions. The influence of the entrapped polymer on the properties of the composite gels, both before and after the hydrolysis, has been evaluated by the swelling kinetics, FT-IR spectroscopy, scanning electron microscopy, and external stimuli responsiveness. The potential of the anionic composite cryogels as intelligent hydrogels has been evaluated by the investigation of the deswelling/reswelling kinetics as a function of solvent nature, ionic strength, and environment pH. Cryogels with fast responsivity at variation of the external stimuli, which withstood repeated deswelling/reswelling cycles, have been obtained at a low cross-linker ratio (one mole BAAm for 80 moles of AAm) and a monomer concentration around 3 wt%.