Radiation-engineered poly(N-vinyl pyrrolidone) nanogels are very interesting biocompatible nanocarriers for i.v. administration of therapeutics and contrast agents for bioimaging. The manufacturing process is fast and effective, it grants excellent control of particle size and simultaneous sterilization of the formed nanogels. Interestingly, primary amino groups and carboxyl groups, useful for (bio)conjugation, are also formed in a dose-dependent fashion. In this paper, by means of both numerical simulations and experiments, the origin of nanogel size control and functionalization is investigated. This understanding offers a new dimension for the design and production of radiation-sculptured multifunctional nanocarriers from aqueous solutions of polymers
The effect of c-rays sterilization at ambient (23 C) and at dry ice temperatures (À78 C) on two biodegradable semicrystalline polyesters, namely poly(L-lactide) (PLLA) and poly(e-caprolactone) (PCL), was studied. The radical processes generated by irradiation were investigated by electron paramagnetic resonance (EPR) spectroscopy, whereas postradiation changes were monitored for 5 months by scanning calorimetry, thermogravimetric analysis, and apparent viscosity measurements. It was confirmed that the radiation sterilization initiates degradation in both studied polymers, however, the effect is smaller in PCL than in PLLA, and that the range of changes might be limited by lowering temperature of the exposure to c-rays. Newly formed oxygen containing functional groups confirmed by EPR and thermogravimetric analysis methods are produced in the irradiated polyesters. In PCL, the process might give rise to thermally induced cross-linking via oxygen containing intermolecular bridges. During storage, in both irradiated materials, morphology determined by differential scanning calorimetry is changing -PCL ability toward crystallization decreases insignificantly, whereas in PLLA the tendency is opposite -on irradiation a contribution of crystalline phase is growing considerably, from 18 and 19% to 41 and 31% for PLLA irradiated at 23 C and at À78 C, respectively.
Poly(N-vinyl pyrrolidone)-based-nanogels (NGs), produced by e-beam irradiation, are conjugated with monoclonal antibodies (mAb) for active targeting purposes. The uptake of immuno-functionalized nanogels is tested in an endothelial cell line, ECV304, using confocal and epifluorescence microscopy. Intracellular localization studies reveal a faster uptake of the immuno-nanogel conjugate with respect to the 'bare' nanogel. The specific internalization pathway of these immuno-nanogels is clarified by selective endocytosis inhibition experiments, flow cytometry and confocal microscopy. Active targeting ability is also verified by conjugating a monoclonal antibody which recognizes the αvβ3 integrin on activated endothelial cells. Epifluorescence images of the 'wound healing assay' on ECV304 cells provide evidence of nanogels localization only in the target cells. Therefore, the immuno-nanogels produced have the potential to recognize specific cell types in heterogeneous systems, which makes them promising candidates for targeted drug delivery applications.
The thermo-mechanical properties and nanostructural features of epoxy aromatic resins cationically cured by UV-visible or electron beam radiation have been studied by FT-NIR spectroscopy, dynamic mechanical analysis (DMA), dielectric spectroscopy (DS), and atomic force microscopy (AFM). The influence of formulation (nature and content of onium salt) and of curing parameters (doses, thermal treatment) on the thermophysical have been investigated. The presence of several relaxation domains observed by DMA and DS analysis confirms the presence of heterogeneities in the cured materials. Network formation is described by the percolation of glassy nanoclusters which are evidenced by AFM analyses.AFM probing by quantitative nanomechanical measurements confirms the gradual build-up of the local Young's modulus in good agreement with the macroscopic value.
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