On the origin of functionalization in one-pot radiation synthesis of nanogels from aqueous polymer solutions

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-sculpture…

Radiation-tailored xyloglucan-doxorubicin nanoparticles for cancer therapy

Polysaccharides are long chains of monosaccharides linked by glycosidic bonds. They are widely utilized in biomedical applications, for tissue engineering and wound management, and as excipients of pharmaceutical formulations. In cancer therapy, the development of nanoscale drug delivery systems aims at addressing issues related to the low efficacy of chemotherapeutics and protein drugs due to poor solubility and stability, and to off-target effects that severely affect patients’ body conditions. Biocompatibility, availability of functional groups, amenability of chemical derivatisation and multifunctional conjugation with drugs and targeting ligands make polysaccharide nanoparticles intere…

Numerical Simulation of the Kinetics of Radical Decay in Single-Pulse High-Energy Electron-Irradiated Polymer Aqueous Solutions

A new method for the numerical simulation of the radiation chemistry of aqueous polymer solutions is introduced. The method makes use of a deterministic approach combining the conventional homogeneous radiation chemistry of water with the chemistry of polymer radicals and other macromolecular species. The method is applied on single-pulse irradiations of aqueous polymer solutions. The speciation of macromolecular species accounts for the variations in the number of alkyl radicals per chain, molecular weight, and number of internal loops (as a consequence of an intramolecular radical-radical combination). In the simulations, the initial polymer molecular weight, polymer concentration, and do…

The role of molecular oxygen in the formation of radiation-engineered multifunctional nanogels

Abstract Nanogels are very promising biomedical nanodevices. The classic “radiation chemistry-based” approach to synthetize nanogels consists in the irradiation with pulsed electron beams of dilute, N2O-saturated, aqueous solutions of water-soluble polymers of the “crosslinking type”. Nanogels with controlled size and properties are produced in a single irradiation step with no recourse to initiators, organic solvents and surfactants. This paper combines experimental syntheses, performed with two e-beam irradiation setups and dose-ranges, starting from poly(N-vinyl pyrrolidone) solutions of various concentrations, both in N2O-saturated and air-saturated initial conditions, with the numerica…

Multifunctional nanogels from e-beam irradiation of PVP aqueous solutions, only

Nanogels (NGs) are 3D networks of crosslinked hydrophilic polymers with nanoscalar dimensions. Due to their structure and physico-chemical properties, they are a promising nanomaterial platform for site-specific drug delivery and diagnostic nanodevices.

New insights on the mechanism of PVP nanogels radiation synthesis

In this work, the H2O2 build-up for several system compositions and irradiation conditions was investigated, by using the Ghormley triiodide method. Interestingly, the application of the method has revealed the occurrence of two concurrent reactions, the expected one responsible for the I3 - production (by reaction with the H2O2 formed upon irradiation) and one that is responsible for I3 - consumption. Both the concentrations of I3 - -forming and I3 - -consuming species are dose-dependent and polymer concentration-dependent. The kinetic study of the two reactions and some further experiments carried out with model molecules will be described. We believe that the results of this study can of…

Inorganic/organic hybrid nanoparticles synthesized in a two-step radiation-driven process

In this work, we have synthesized inorganic-organic hybrid nanoparticles via radiation synthesis of inorganic nanoparticles (Ag and CeO2) in aqueous dispersions containing radiation-synthesized poly(N-vinyl pyrrolidone) (PVP) nanogels (NG). The experiments show that there are strong interactions between the inorganic precursors (Ag+ and Ce3+) and the nanogel prior to irradiation. The two hybrid systems (Ag/NG and CeO2/NG) were characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD confirms the formation of crystalline Ag and CeO2. TEM reveals that the inorganic nanoparticles are evenly distributed in/on the nanogel. Both XRD and TEM show that size of the…

Radiation-Engineered Functional Nanoparticles in Aqueous Systems.

Controlled synthesis of nanoscalar and nanostructured materials enables the development of novel functional materials with fine-tuned optical, mechanical, electronic, magnetic, conductive and catalytic properties that are of use in numerous applications. These materials have also found their potential use in medicine as vehicles for drug delivery, in diagnostics or in combinations thereof. In principle, nanoparticles can be divided into two broad categories, organic and inorganic nanoparticles. For both types of nanoparticles there are numerous possible synthetic routes. Considering the large difference in nature of these materials and the elementary reactions involved in the synthetic rout…

Temporal control of xyloglucan self-assembly by radiation-induced degradation

Xyloglucan is a natural polysaccharide present as storage material in seeds and structural materials in the primary cells walls of higher plants. Xyloglucan from tamarind seed is composed of B(1,4)-D-glucan backbone, partially substituted by a-(1,6)-linked xylose units, some of which are B-D-galactosylated at O-2. In its native form the polymer is water-soluble and forms gel in the presence of moderate amounts of alcohols. When a given fraction of galactosyl residues are removed, the polymer acquires the ability to form gels in aqueous solution at physiological temperatures, a property of great interest for biomedical/pharmaceutical applications. Gelation on increasing temperature can be as…

Gamma irradiation of xyloglucans and hydroxypropyl cellulose in dry and humid solid state to tune molecular weight distribution

Numerical Simulations of Nanogel Synthesis Using Pulsed Electron Beam

In this work, a new method for numerical simulation of the radiation chemistry of aqueous polymer solutions exposed to a sequence of electron pulses is presented. The numerical simulations are based on a deterministic approach encompassing the conventional homogeneous radiation chemistry of water as well as the chemistry of polymer radicals. The multitude of possible reactions in the macromolecular system is handled by allowing for a large number of macromolecular species. The speciation of macromolecular species is done to account for variations in molecular weight, number of alkyl radicals per chain, number of peroxyl radicals per chain, number of oxyl radicals per chain, and number of in…

Understanding generation of multifunctional nanogels in chemical-free e-beam irradation synthesis

Radiation engineered nanogels are the core of very promising theranostic nanodevoces. They can be produced starting from aqueous solutions of chemically inert polymers by pulsed e-beam irradiation.