RESUMEN
The influence of surfactant, cross-linker, and initiator on the final structure and thermoresponse of poly(N-isopropylmethacrylamide) (pNIPMAM) microgels was evaluated. The goals were to control particle size (into the nanorange) and transition temperature (across the physiologically accessible range). The concentration of the reactants used in the synthesis was varied, except for the monomer, which was kept constant. The thermoresponsive suspensions formed were characterized by dynamic light scattering, small-angle X-ray scattering, atomic force microscopy, and rheology. Increasing surfactant, sodium dodecyl sulfate content, produced smaller microgels, as expected, into the nanorange and with greater internal entanglement, but with no change in phase transition temperature (LCST), which is contrary to previous reports. Increasing cross-linker, N,N-methylenebis acrylamide, content had no impact on particle size but reduced particle deformability and, again contrary to previous reports of decreases, progressively increased the LCST from 39 to 46 °C. The unusual LCST trends were confirmed using different rheological techniques. Initiator, potassium persulfate, content was found to weakly influence the outcomes. An optimized content was identified that provides functional nanogels in the 100 nm (swollen) size range with controlled LCST, just above physiological temperature. The study contributes chemistry-derived design rules for thermally responsive colloidal particles with physiologically accessible LCST for a variety of biomedical and soft robotics applications.
RESUMEN
Responsive magnetic nanomaterials offer significant advantages for innovative therapies, for instance, in cancer treatments that exploit on-demand delivery on alternating magnetic field (AMF) stimulus. In this work, biocompatible magnetic bionanocomposite films are fabricated from chitosan by film casting with incorporation of magnetite nanoparticles (MNPs) produced by facile one pot synthesis. The influence of synthesis conditions and MNP concentration on the films' heating efficiency and heat dissipation are evaluated through spatio-temporal mapping of the surface temperature changes by video-thermography. The cast films have a thickness below 100 µm, and upon exposure to AMF (663 kHz, 12.8 kA m-1 ), induce exceptionally strong heating, reaching a maximum temperature increase of 82 °C within 270 s irradiation. Further, it is demonstrated that the films can serve as substrates that supply heat for multiple hyperthermia scenarios, including: i) non-contact automated heating of cell culture medium, ii) heating of gelatine-based hydrogels of different shapes, and iii) killing of cancerous melanoma cells. The films are versatile components for non-contact stimulus with translational potential in multiple biomedical applications.
RESUMEN
Green fluorescent protein (GFP), the most widely used fluorescent protein for in vivo monitoring of biological processes, is known to undergo photooxidation reactions. However, the most fundamental property underpinning photooxidation, the electron detachment energy, has only been measured for the deprotonated GFP chromophore in the gas phase. Here, we use multiphoton ultraviolet photoelectron spectroscopy in a liquid-microjet and high-level quantum chemistry calculations to determine the electron detachment energy of the GFP chromophore in aqueous solution. The aqueous environment is found to raise the detachment energy by around 4 eV compared to the gas phase, similar to calculations of the chromophore in its native protein environment. In most cases, electron detachment is found to occur resonantly through electronically excited states of the chromophore, highlighting their importance in photo-induced electron transfer processes in the condensed phase. Our results suggest that the photooxidation properties of the GFP chromophore in an aqueous environment will be similar to those in the protein.
