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The thermoresponsive properties of poloxamine (tetra-branch PEO-PPO block copolymer) hydrogels are related to several variables. Of particular interest to this study were the molecular weight of the polymer, the molar ratio between PEO and PPO blocks, and the concentration of the aqueous solution. Accurately controlling the thermoresponsive behaviors of the polymer is critical to the application of such materials; therefore, the structure–property relationship of tetra-branch PEO-PPO block copolymer was studied by synthesis via anionic ring-opening polymerization (AROP). The structure–property relationships were studied by measuring the thermoresponsive behavior via differential scanning calorimetry (DSC) and developing an empirical model which statistically fit the collected data. This empirical model was then used for designing poloxamines that have critical micellization temperatures (CMT) between room temperature and physiological temperature. The model was validated with three polymers that targeted a CMT of 308 K (35°C). The empirical model showed great success in guiding the synthesis of poloxamines showing a temperature difference of less than 3 K between the predicted and the observed CMTs. This study showed a great potential of using an empirical model to set synthesis parameters to control the properties of the polymer products.more » « lessFree, publicly-accessible full text available December 31, 2025
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To investigate the influence of manganese substitution on the saturation magnetization of manganese ferrite nanoparticles, samples with various compositions (MnxFe3−xO4,x = 0, 0.25, 0.5, 0.75, and 1) were synthesized and characterized. The saturation magnetization of such materials was both calculated using density functional theory and measured via vibrating sample magnetometry. A discrepancy was found; the computational data demonstrated a positive correlation between manganese content and saturation magnetization, while the experimental data exhibited an inverse correlation. X-ray diffraction (XRD) and magnetometry results indicated that the crystallite diameter and the magnetic diameter decrease when adding more manganese, which could explain the loss of magnetization of the particles. For 20 nm nanoparticles, with increasing manganese substitution level, the crystallite size decreases from 10.9 nm to 6.3 nm and the magnetic diameter decreases from 15.1 nm to 3.5 nm. Further high resolution transmission electron microscopy (HRTEM) analysis confirmed the manganese substitution induced defects in the crystal lattice, which encourages us to find ways of eliminating crystalline defects to make more reliable ferrite nanoparticles.more » « less
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Abstract To produce multi-dopant ferrite nanoparticles, the ‘Extended LaMer’ and seed-mediated growth techniques were combined by first utilizing traditional thermal decomposition of metal acetylacetonates to produce seed particles, followed by a continuous injection of metal oleate precursors to increase the volume of the seed particles. With the choice of precursors for the seeding and dripping stage, we successfully synthesized particles with manganese precursor for seeding and cobalt precursor for dripping (Mn0.18Co1.04Fe1.78O4, 17.6 ± 3.3 nm), and particles with cobalt precursors for seeding and manganese precursors for dripping (Mn0.31Co0.74Fe1.95O4, 19.0 ± 1.9 nm). Combining transmission electron microscopy, energy-dispersive x-ray spectroscopy, x-ray diffraction, and vibrating sample magnetometry, we conclude that the seed-mediated drip method is a viable method to produce multi-dopant ferrite nanoparticles, and the size of the particles was mostly determined by the seeding stage, while the magnetic properties were more affected by the dripping stage.more » « less
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