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    Synthesis and characterization of stiff, self-crosslinked thermoresponsive DMAA hydrogels
    (MDPI, 2020-06-01)
    Stiff thermosensitive hydrogels (HG) were synthesized by self-crosslinking free radical polymerization of N, N-dimethylacrylamide (DMAA) and N-isopropylacrylamide (NIPAAm), adjusting the degree of swelling by carboxylate-containing sodium acrylate (NaAc) or a 2-oxazoline macromonomer (MM). The formation of hydrogels was possible due to the self-crosslinking property of DMAA when polymerized with peroxodisulfate initiator type. The MM was synthetized by the ring-opening cationic polymerization of 2-methyl-2-oxazoline (MeOxa) and methyl-3-(oxazol-2-yl)-propionate (EsterOxa), and contained a polymerizable styryl endgroup. After ester hydrolysis of EsterOxa units, a carboxylate-containing MM was obtained. The structure of the hydrogels was confirmed by 1Hhigh-resolution (HR)-MASNMRspectroscopy. Suitable conditions and compositions of the comonomers have been found, which allowed efficient self-crosslinking as well as a thermoresponsive swelling in water. Incorporation of both the polar comonomer and the macromonomer, in small amounts furthermore allowed the adjustment of the degree of swelling. However, the macromonomer was better suited to retain the thermoresponsive behavior of the poly (NIPAAm) due to a phase separation of the tangling polyoxazoline side chains. Thermogravimetric analysis determined that the hydrogels were stable up to ~ 350 ffiC, and dynamic mechanical analysis characterized a viscoelastic behavior of the hydrogels, properties that are required, for example, for possible use as an actuator material.
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    Removal of Methylene Blue by Hydrogels based on N, N-Dimethylacrylamide and 2-Oxazoline macromonomer
    (Springer, 2020-09-01)
    New hydrogels (HG) were synthesized in aqueous medium by free radical polymerization of N,N-dimethylacrylamide (DMAA) and 2-oxazoline macromonomer (MM) initiated by potassium persulfate (KPS) and catalyzed by N,N,N,N′-tetramethylethylenediamine (TEMED). In this polymerization, the monomer DMAA was also used as a crosslinker because it has the ability of self-crosslinking in the presence of peroxodisulfate initiator type. The macromonomer (DP = 24) was a gradient copolymer of 2-methyl-2-oxazoline and methyl-3-(oxazol-2-yl)-propionate with a styryl end group. 1H high-resolution (HR)-MAS NMR spectroscopy allowed to confirm the structure of hydrogels and to determine the molar content of DMAA and MM in each of them. Hydrogels (HG-H) containing carboxylic groups were obtained by basic hydrolysis of HG. Hydrolyzed hydrogels (HG-H) were used for the adsorption of methylene blue (MB) in aqueous medium. It was found that the MB adsorption increased as the initial MB concentration increased, and maximum adsorption capacities were found. The influence of pH value on MB adsorption was evaluated, showing that the MB adsorption capacity of the hydrogels was higher at pH value ≥ 5.7. Adsorption isotherms were studied using Langmuir and Freundlich models. The latter model describes best the process suggesting a possible adsorption mechanism through electrostatic interactions between MB and HG-H hydrogels. The MB adsorbed inside the hydrogels, could be removed with an acidic solution and therefore the hydrogel could be applied to adsorb MB again.
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    Tailored peptide nanomaterials for receptor-targeted prostate cancer imaging
    (Royal Society of Chemistry, 2024-11-05)
    We report the development of a peptide-based optical nanoprobe specifically tailored for prostate cancer imaging. The imaging probe is comprised of cyclic peptide nanotubes, formed via the aqueous co-assembly of four cyclic D,L-alternating octapeptides. The inherent properties of these cyclic building blocks have been carefully selected to enhance their efficacy in imaging applications, through the addition of a cancer targeting peptide and a fluorescent dye. Comprehensive characterization using scanning electron microscopy (FESEM) and low-voltage transmission electron microscopy (LV-TEM) confirms the formation of nanotubes through co-assembly of the cyclic peptides. The resulting nanotubes show an average diameter of 28 nm. Circular dichroism (CD) spectroscopy validates the formation of stable beta-sheet hydrogen bonding structures at both 20 and 37 °C, ensuring their suitability for biomedical applications. Evaluation of PSMA-binding specificity of the resulting peptide nanotubes is assessed using confocal fluorescence microscopy demonstrating receptor-mediated uptake in prostate cancer cells. We anticipate this strategy will provide the basis for the utilization of co-assembled systems for advancing molecular imaging techniques in prostate cancer and other cancers.
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