Hydrogel is a good drug carrier, widely used in the sustained-release aspect of tumor drugs, which can achieve the continuous release of drugs to the tumor sites. In this study, diethylene glycol monomethyl ether methacrylate (MEO2MA) and poly (ethylene glycol) methyl ether methacrylate (OEGMA) are temperature-sensitive monomers. N-Methacryloyl-L-Histidine (Mist) is pH sensitive monomer and ligand for metal coordination bond. The temperature-sensitive monomers and pH sensitive monomer with stereocomplex of modified polylactic acid (HEMA-PLLA30/PDLA30) were mixed, under 2,2’-azobis (2-methylpropionitrile) (AIBN) as radical initiator, polymer was formed by free-radical polymerization. The polymer was then immersed in ZnSO4 solution, the imidazole group of Mist monomer forms a tridentate metal coordination bond with Zn2+, temperature/pH double-responsive and physical double-crosslinked hydrogel was finally obtained. Comparing the hydrogen bond hydrogel, hydrogen bond and metal coordination bond double crosslinking hydrogel, metal coordination bond hydrogel, testing thermal stability, viscoelasticity, swelling, and morphology of three hydrogels. In addition, using UV-Visible spectroscopy (UV-Vis) to test the sustained release of the hydrophobic drug doxorubicin hydrochloride (DOX-HCl) in the human tumor environment (37 °C, pH = 5). We found that the temperature/pH double-responsive and physical double-crosslinked hydrogel had the most potential for the sustained drug release.
Medical titanium alloy Ti-6Al-4V (TC4) has been widely used in the medical field, especially in human tissue repair. However, TC4 has some shortcomings, which may cause problems with biocompatibility and mechanical compatibility in direct contact with the human body. To solve this problem, physical gels are formed on the surface of TC4, and the storage modulus of the formed physical gel matches that of the human soft tissue. 2-bromoisobutyryl bromide (BIBB) and dopamine (DA) were used to form initiators on the surface of hydroxylated medical titanium alloy. Different initiators were formed by changing the ratio of BIBB and DA, and the optimal one was selected for subsequent reactions. Under the action of the catalyst, L-lactide and D-lactide were ring-opened polymerized with hydroxyethyl methacrylate (HEMA), respectively, to form macromolecular monomers HEMA-PLLA29 and HEMA-PDLA29 with a polymerization degree of 29. The two macromolecular monomers were stereo-complexed by ultrasound to form HEMA-stereocomplex polylactic acid (HEMA-scPLA29). Based on two monomers, 2-(2-methoxyethoxy) ethyl methacrylate (MEO2MA) and oligo (ethylene oxide) methacrylate (OEGMA), and the physical crosslinking agent HEMA-scPLA29, physical gels are formed on the surface of TC4 attached to the initiator via Atom Transfer Radical Addition Reaction (ATRP) technology. The hydrogels on the surface of titanium alloy were characterized and analyzed by a series of instruments. The results showed that the storage modulus of physical glue was within the range of the energy storage modulus of human soft tissue, which was conducive to improving the mechanical compatibility of titanium alloy and human soft tissue.
Medical titanium alloy Ti-6Al-4V (TC4) is an ideal surgical implant material for human tissue repair and replacement. TC4 implantation will be in close contact with human soft tissue and has mechanical compatibility problems. In order to solve this problem, the hydrogel was formed on the surface of TC4 by utilizing the adhesion of dopamine, and the storage modulus of the formed hydrogel matched that of human soft tissue. In this paper, the surface of TC4 was first modified with dopamine (DA) and 2-bromoisobutyryl bromide (BIBB). 2-(2-methoxyethoxy) ethyl methacrylate (MEO2MA), oligo (ethylene oxide) methacrylate (OEGMA) and 2-methacryloyloxyethyl phosphorylcholine (MPC) are used as monomers, and methylenebisacrylamide (MBA) is used as cross-linking agent. Thermosensitive hydrogels were formed on the surface of modified TC4 by the ATRP technique. The successful synthesis of initiator and hydrogels on TC4 was demonstrated by Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). The morphology of the hydrogel was observed by the scanning electron microscope (SEM), and the water absorption and temperature sensitivity were investigated by the swelling property. The thermal and mechanical properties of these gels were measured using thermal analysis system (TAS) and dynamic mechanical analyzer (DMA). The results show that the hydrogel on TC4 has good thermal stability and storage modulus that matches human soft tissue.
Stimulus-responsive hydrogels have been widely used in the field of drug delivery because of their three-dimensional pore size and the ability to change the drug release rate with the change in external environment. In this paper, the temperature-sensitive monomer 2-methyl-2-acrylate-2-(2-methoxyethoxy-ethyl) ethyl ester (MEO2MA) and oligoethylene glycol methyl ether methacrylate (OEGMA) as well as the pH-sensitive monomer N,N-Diethylaminoethyl methacrylate (DEAEMA) were used to make the gel with temperature and pH response. Four kinds of physicochemical double-crosslinked amphiphilic co-network gels with different polymerization degrees were prepared by the one-pot method using the stereocomplex between polylactic acid as physical crosslinking and click chemistry as chemical crosslinking. By testing morphology, swelling, thermal stability and mechanical properties, the properties of the four hydrogels were compared. Finally, the drug release rate of the four gels was tested by UV–Vis spectrophotometer. It was found that the synthetic hydrogels had a good drug release rate and targeting, and had great application prospect in drug delivery.
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