Some PluronicF68 (F68) triblock copolymer properties demonstrate surprising applications in selective drug administration, such as the transportation of hydrophobic anti-inflammatories through epithelial barriers. Nuclear magnetic resonance (1H-NMR) spectroscopy was carried out for micelle precursor dispersions and F68 films modified with a synthetic imogolite (IMO) biocompatible hydrogel. Theoretical calculations and morphological assessment for the process of morphogenesis of dendritic crystallization were performed by molecular docking and atomic force microscopy (AFM) of the Sudan III-IMO-F68 composite, which was more hydrophobic than Sudan III-F68 and carried out the prolonged release of the Sudan III “drug” captured by a water–octanol interface determined by standard absorbance. Surface fusions were measured and compared to the unmodified matrix. However, despite the superior properties of the composite, the critical micelle concentration (CMC) was practically unmodified because solitary IMO strands attached to Sudan III formed Sudan III-IMO. These strands unraveled in a stable manner by expanding like a “spiderweb” in hydrophilic interfaces according to NMR analysis of the hydrogen one H1 polarization of Sudan III and F68 methyl, whose correlation relates hydrophobicity of Sudan III-IMO-F68 with dendrite properties from F68 concentrations. CMC and surface fusions equivalent to F68 surface properties, calculated by differential scanning calorimetry and dynamic Raman spectroscopy, were determined by AFM and high-resolution ellipsometry. Our results show highly specialized pharmacological applications since micelle surfaces expand, triggering maximum deliveries of “Drugs” from its interior to the physiological environment. The implanted sensor prototype determined equilibria reached Sudan III according to temperature (32–50 °C) and time it took to cross the membrane model 1-octanol (48 h). The findings suggest that the targested design of a F68-IMO-“Drug” would function as a microdevice for the prolonged release of hydrophobic drugs. In addition, the said microdevice could regenerate the damaged tissue in the central nervous system or other organs of the body. This is due to the fact that it could perform both tasks simultaneously, given the properties and characteristics acquired by the compatible material depending on the temperature of the physiological environment.
Properties of poly(binaphthoxyphosphazene)s were investigated employing molecular dynamics simulations in the original microcanonical ensemble. In particular we have applied our methodology to the case of isotactic poly-(2,2´-dioxy-1,1´-binaphthylphosphazene) (P-DBNP) in order to estimate the vitreous transition temperature Tg, the energy barrier Δμβ for β-relaxation of the BNP unit, and the thermodynamic entropy of the system. According to our results, the transition is consistent with the Adam-Gibbs model and the specific rotation of α and β-relaxations, which varies significantly with the molecular weight Mw. Our results suggest a rapid interconversion between the different proportions of the chiral R and S repeating units (70% and 30%, respectively) of the non-isotactic copolymer below 523K and a slow atropisomerization of the DBNP units above 523K which, in agreement with recent predictions on glassy polymer matrices, becomes much faster as the temperature approaches Tg~573K.
The control of the glass transition temperature (Tg) in functionalized polymers is crucial for materials engineering and pharmaceutical applications. Tailoring must overcome experimental and theoretical issues regarding the thermodynamical phenomena involved. In this work, we study the glass transition of poly(monoitaconate)s and poly(diitaconate)s systems functionalized by internal plasticization. Differential scanning calorimetry (DSC) and Raman spectroscopy are used to determine Tg, whereas thermal degradation analysis (TGA) is used to determinate the temperature limit where conformers relax independently, defined as T* in the Adams–Gibbs model. Our results show that the values of Tg obtained through DSC and Raman are consistent and that TGA can be used to estimate a lower bound limit for T*. We mainly conclude that a larger steric hindrance between the carboxylic group in the side chain and the backbone increases Tg and decreases the variation of specific heat and configurational entropy at different domain regions. Similar behavior is observed when chlorine atoms are substituted in the phenethyl groups.
ABSTRACTTriblock copolymers with surface‐active properties, referred to as Pluronic, have shown potential medical applications such as drug delivery to selective targets in the human body. In particular, the transport of anti‐inflammatory substances to the brain is required for illness treatment, thus the study of delivery agents that cross the blood–brain barrier is relevant. In this article we study the effects of the micelle formation on the morphologic and cytotoxic properties of Pluronic F68. We determinate the critical micellar concentration (CMC) by standard tensiometric and absorbance measurements, and also we analyze the morphology of polymers by atomic force microscopy. Our observations indicate that the morphological properties of F68 are drastically modified in the CMC range, as well as the ability to increase the viability of neuroblastoma cells maintained under culture conditions, as compared with nontreated cells. Our conclusions highlight the close correlation between morphological and physiochemical properties of Pluronic, which must be further understood in order to achieve highly controlled pharmacological uses. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2159–2164, 2013