Radiation synthesis of poly(acrylic acid) nanogels for drug delivery applications – post-synthesis product colloidal stability

Synthesis of polymer nanogels (NGs) for biomedical applications is considered to be a very promising application in radiation engineering. Under high-dose pulse irradiation of dilute aqueous polymer solution, reactive species generated by water radiolysis can create multiple radicals on each macromolecule and consequently induce intramolecular cross-linking of polymer chains, resulting in NG formation. The obtained products are free from harmful monomers, initiators, and cross-linking agents, which makes them potentially applicable for drug delivery applications. One of the biggest challenges in handling and use of nanoparticles, however, is the colloidal stability, when aqueous suspensions are stored for prolonged periods. Therefore, development of the best protocols for the particular nanocarrier storage is key. To address this need, we have performed the prospective study in which we systematically assessed the influence of various processing and storage scenarios feasible in our lab, on the colloidal stability of the radiation-synthesized poly(acrylic acid) (PAA) NG particles in suspension. This allowed us to choose the optimal way of handling the product after its synthesis. We confirmed that none of the strategies we used and tested are substantially detrimental to our product. Filtration with 0.2-μm filters was proven sufficient for sample purification and prolonged storage in aqueous suspension did not exert a negative effect on the colloidal stability of particles suspension. We have also demonstrated that lyoprotectant-free lyophilization was suitable for our polymer nanoparticles. This is an important fact for further application of particles as nanocarriers for biologically active compounds such as targeting ligands or therapeutic moieties.

Determination of the through-plane profile of vanadium species in hydrated Nafion studied with micro X-ray absorption near-edge structure spectroscopy – proof of concept

Vanadium-ion transport through the polymer membrane results in a significant decrease in the capacity of vanadium redox flow batteries. It is assumed that five vanadium species are involved in this process. Micro X-ray absorption near-edge structure spectroscopy (micro-XANES) is a potent method to study chemical reactions during vanadium transport inside the membrane. In this work, protocols for micro-XANES measurements were developed to enable through-plane characterization of the vanadium species in Nafion 117 on beamline P06 of the PETRA III synchrotron radiation facility (DESY, Hamburg, Germany). A Kapton tube diffusion cell with a diameter of 3 mm was constructed. The tube diameter was chosen in order to accommodate laminar flow for cryogenic cooling while allowing easy handling of the cell components by hand. A vertical step size of 2.5 µm and a horizontal step size of 5 µm provided sufficient resolution to resolve the profile and good statistics after summing up horizontal rows of scan points. The beam was confined in the horizontal plane to account for the waviness of the membrane. The diffusion of vanadium ions during measurement was inhibited by the cryogenic cooling. Vanadium oxidation, e.g. by water radiolysis (water percentage in the hydrated membrane ∼23 wt%), was mitigated by the cryogenic cooling and by minimizing the dwell time per pixel to 5 ms. Thus, the photo-induced oxidation of V3+ in the focused beam could be limited to 10%. In diffusion experiments, Nafion inside the diffusion cell was exposed on one side to V3+ electrolyte and on the other side to VO2 +. The ions were allowed to diffuse across the through-plane orientation of the membrane during one of two short defrost times (200 s and 600 s). Subsequent micro-XANES measurements showed the formation of VO2+ from V3+ and VO2 + inside the water body of Nafion. This result proves the suitability of the experimental setup as a powerful tool for the determination of the profile of vanadium species in Nafion and other ionomeric membranes.

RAFT-Mediated Radiation Grafting on Natural Fibers in Aqueous Emulsion

Using aqueous emulsion as the medium in radiation-induced graft polymerization (RIGP) offers an environment-friendly shift from organic solvents while increasing polymerization efficiency through known water radiolysis-based graft initiation. In the present paper, we further extend the applicability of RIGP in emulsion under the influence of reversible addition fragmentation chain transfer (RAFT) mechanisms. Emulsions prepared with Tween 20 showed good colloidal stability for several hours. Subjecting it to simultaneous irradiation with abaca fibers resulted in successful grafting, supported by gravimetric, IR, SEM, and TG analysis. A correlation was drawn between smaller monomer micelles and the enhancement of grafting driven by diffusion and surface area coverage. RAFT mechanisms were also conserved based on molecular weight evolution. RAFT-mediated RIGP in aqueous emulsion shows good potential as a versatile and green surface modification technique for natural fibers for various functional applications.

A Geant4-DNA Evaluation of Radiation-Induced DNA Damage on a Human Fibroblast

Accurately modeling the radiobiological mechanisms responsible for the induction of DNA damage remains a major scientific challenge, particularly for understanding the effects of low doses of ionizing radiation on living beings, such as the induction of carcinogenesis. A computational approach based on the Monte Carlo technique to simulate track structures in a biological medium is currently the most reliable method for calculating the early effects induced by ionizing radiation on DNA, the primary cellular target of such effects. The Geant4-DNA Monte Carlo toolkit can simulate not only the physical, but also the physico-chemical and chemical stages of water radiolysis. These stages can be combined with simplified geometric models of biological targets, such as DNA, to assess direct and indirect early DNA damage. In this study, DNA damage induced in a human fibroblast cell was evaluated using Geant4-DNA as a function of incident particle type (gammas, protons, and alphas) and energy. The resulting double-strand break yields as a function of linear energy transfer closely reproduced recent experimental data. Other quantities, such as fragment length distribution, scavengeable damage fraction, and time evolution of damage within an analytical repair model also supported the plausibility of predicting DNA damage using Geant4-DNA.The complete simulation chain application “molecularDNA”, an example for users of Geant4-DNA, will soon be distributed through Geant4.

Nuclear-driven production of renewable fuel additives from waste organics

Non-intermittent, low-carbon energy from nuclear or biofuels is integral to many strategies to achieve Carbon Budget Reduction targets. However, nuclear plants have high, upfront costs and biodiesel manufacture produces waste glycerol with few secondary uses. Combining these technologies, to precipitate valuable feedstocks from waste glycerol using ionizing radiation, could diversify nuclear energy use whilst valorizing biodiesel waste. Here, we demonstrate solketal (2,2-dimethyl-1,3-dioxolane-4-yl) and acetol (1-hydroxypropan-2-one) production is enhanced in selected aqueous glycerol-acetone mixtures with γ radiation with yields of 1.5 ± 0.2 µmol J−1 and 1.8 ± 0.2 µmol J−1, respectively. This is consistent with the generation of either the stabilized, protonated glycerol cation (CH2OH-CHOH-CH2OH2+ ) from the direct action of glycerol, or the hydronium species, H3O+, via water radiolysis, and their role in the subsequent acid-catalyzed mechanisms for acetol and solketal production. Scaled to a hypothetically compatible range of nuclear facilities in Europe (i.e., contemporary Pressurised Water Reactor designs or spent nuclear fuel stores), we estimate annual solketal production at approximately (1.0 ± 0.1) × 104 t year−1. Given a forecast increase of 5% to 20% v/v% in the renewable proportion of commercial petroleum blends by 2030, nuclear-driven, biomass-derived solketal could contribute towards net-zero emissions targets, combining low-carbon co-generation and co-production.

An Alternative Conceptual Model for the Spent Nuclear Fuel–Water Interaction in Deep Geologic Disposal Conditions

For the long-term safety assessment of direct disposal of spent nuclear fuel in deep geologic repositories, knowledge on the radionuclide release rate from the UO2 matrix is essential. This work provides a conceptual model to explain the results of leaching experiments involving used nuclear fuel or simulant materials in confirmed reducing conditions. Key elements of this model are: direct effect of radiation from radiolytic species (including defects and excited states) in the solid and in the first water layers in contact with its surface; and excess H2 may be produced due to processes occurring at the surface of the spent fuel and in confined water volumes, which may also play a role in keeping the spent fuel surface in a reduced state. The implication is that the fractional radionuclide release rate used in most long-term safety assessments (10−7 year−1) is over estimated because it assumes that there is net UO2 oxidation caused by radiolysis, in contrast with the alternative conceptual model presented here. Furthermore, conventional water radiolysis models and radiation chemical yields published in the literature are not directly applicable to a heterogeneous system such as the spent fuel–water interface. Suggestions are provided for future work to develop more reliable models for the long-term safety assessment of spent nuclear fuel disposal.

Radiolytic Synthesis and Characterization of Selenium Nanoparticles: Comparative Biosafety Evaluation with Selenite and Ionizing Radiation

Selenium nanoparticles (SeNPs) were synthesized by irradiating a solution containing sodium selenite (Se+4) as the precursor in YPG liquid medium with gamma-rays. Spherical particles were formed after reactions of sodium selenite with hydrated electrons (eaq-) and hydrogen radicals (H•) produced following water radiolysis. No hazardous reducing agents were employed. The obtained nanoparticles were morphologically characterized, and their physicochemical and structural parameters were analyzed. SeNPs characterization showed all selenium in the Se0 state. We incubated Saccharomyces cerevisiae cells with the SeNPs for 24 h and then challenged the cells with ionizing radiation. After radiation exposure, cells were assessed for cell viability, lipid peroxidation, protein carbonylation, free radical generation, and total sulfhydryl content. The synthesized SeNPs were considered safe and less toxic at the concentration employed than the same selenite concentration. Except for the protein carbonylation results, there were no other significant modifications in viability or the oxidative stress parameters in SeNP-treated cells. It was concluded that 1 mM of the synthesized SeNPs does not trigger oxidative stress. Furthermore, we verified that SeNPs attenuate the reactive oxygen species generation after in vitro ionizing radiation exposure. These observations open up tremendous possibilities for radiosensitizer development.