Unveiling the role of surface, size, shape and defects of iron oxide nanoparticles for theranostic applications.

Iron oxide nanoparticles (IONPs) are well-known contrast agents for MRI for a wide range of sizes and shapes. Their use as theranostic agents requires a better understanding of their magnetic hyperthermia properties and also the design of a biocompatible coating ensuring their stealth and a good biodistribution to allow targeting of specific diseases. Here, biocompatible IONPs of two different shapes (spherical and octopod) were designed and tested in vitro and in vivo to evaluate their abilities as high-end theranostic agents. IONPs featured a dendron coating that was shown to provide anti-fouling properties and a small hydrodynamic size favoring an in vivo circulation of the dendronized IONPs. While dendronized nanospheres of about 22 nm size revealed good combined theranostic properties (r2 = 303 mM s-1, SAR = 395 W gFe-1), octopods with a mean size of 18 nm displayed unprecedented characteristics to simultaneously act as MRI contrast agents and magnetic hyperthermia agents (r2 = 405 mM s-1, SAR = 950 W gFe-1). The extensive structural and magnetic characterization of the two dendronized IONPs reveals clear shape, surface and defect effects explaining their high performance. The octopods seem to induce unusual surface effects evidenced by different characterization techniques while the nanospheres show high internal defects favoring Néel relaxation for magnetic hyperthermia. The study of octopods with different sizes showed that Néel relaxation dominates at sizes below 20 nm while the Brownian one occurs at higher sizes. In vitro experiments demonstrated that the magnetic heating capability of octopods occurs especially at low frequencies. The coupling of a small amount of glucose on dendronized octopods succeeded in internalizing them and showing an effect of MH on tumor growth. All measurements evidenced a particular signature of octopods, which is attributed to higher anisotropy, surface effects and/or magnetic field inhomogeneity induced by tips. This approach aiming at an analysis of the structure-property relationships is important to design efficient theranostic nanoparticles.

Whither Magnetic Hyperthermia? A Tentative Roadmap.

The scientific community has made great efforts in advancing magnetic hyperthermia for the last two decades after going through a sizeable research lapse from its establishment. All the progress made in various topics ranging from nanoparticle synthesis to biocompatibilization and in vivo testing have been seeking to push the forefront towards some new clinical trials. As many, they did not go at the expected pace. Today, fruitful international cooperation and the wisdom gain after a careful analysis of the lessons learned from seminal clinical trials allow us to have a future with better guarantees for a more definitive takeoff of this genuine nanotherapy against cancer. Deliberately giving prominence to a number of critical aspects, this opinion review offers a blend of state-of-the-art hints and glimpses into the future of the therapy, considering the expected evolution of science and technology behind magnetic hyperthermia.

Influence of Atomic Doping on Thermal Stability of Ferrite Nanoparticles-Structural and Magnetic Studies.

In this paper, a series of experiments are reported where ferrite nanoparticles were synthesized with different substitution percentages (5, 10, 15, or 20%) of Fe2+ by Co2+, Mn2+, or Ni2+ ions. Afterwards, the prepared nanoparticles were thermally treated between 50 and 500 °C in air for 24 h in order to observe how doping influences the oxidation process induced by temperature elevation and access to O2. Nanoparticles were imaged before and after thermal treatment by transmission electron microscopy and were analyzed by X-ray diffraction, vibrating sample magnetometry, and Mössbauer spectroscopy. Presented studies reveal that the amount and kind of doped transition metals (of replaced Fe2+) strongly affect the oxidation process of ferrite nanoparticles, which can govern the application possibility. Each transition element suppresses the oxidation process in comparison to pure Fe-oxides, with the highest impact seen with Ni2+.

Impact of urban street canyon architecture on local atmospheric pollutant levels and magneto-chemical PM10 composition: An experimental study in Antwerp, Belgium.

As real-life experimental data on natural ventilation of atmospheric pollution levels in urban street canyons is still scarce and has proven to be complex, this study, experimentally evaluated the impact of an urban street canyon opening on local atmospheric pollution levels, during a 2-week field campaign in a typical urban street canyon in Antwerp, Belgium. Besides following up on atmospheric particulate matter (PM), ultrafine particles (UFPs) and black carbon (BC) levels, the magneto-chemical PM10 composition was quantified to identify contributions of specific elements in enclosed versus open street canyon sections. Results indicated no higher overall PM, UFP and BC concentrations at the enclosed site compared to the open site, but significant day-to-day variability between both monitoring locations, depending on the experienced wind conditions. On days with oblique wind regimes (4 out of 14), natural ventilation was observed at the open location while higher element contributions of Ca, Fe, Co, Ni, Cu, Zn and Sr were exhibited at the enclosed location. Magnetic properties correlated with the PM10 filter loading, and elemental content of Fe, Cr, Mn and Ti. Magnetic bivariate ratios identified finel-grained magnetite carriers with grain sizes below 0.1 µm, indicating similar magnetic source contributions at both monitoring locations. Our holistic approach, combining atmospheric monitoring with magneto-chemical PM characterization has shown the complex impact of real-life wind flow regimes, different source contributions and local traffic dynamics on the resulting pollutant concentrations and contribute to a better understanding on the urban ventilation processes of atmospheric pollution.

Evaluating the potential of topsoil magnetic pollution mapping across different land use classes.

Soil magnetic measurements are used increasingly to estimate the impact of airborne, combustion-related particulate matter (PM) pollution in dense measurement grids. Although many studies have proven the potential of topsoil magnetic measurements in environmental monitoring, their application is not straightforward when factors such as parent material or land use have to be accounted for. Often, the influence of land use on the soil magnetic signal is circumvented by targeting forest soils, where deposited magnetic particles are best preserved in the topsoil. However, when large forests are absent, e.g. in densely populated areas or environments with more heterogeneous land use, this approach often impedes reliable and comprehensive spatial sampling. We evaluated if topsoil magnetic pollution mapping across different land use classes, against a homogeneous geological environment of sandy soils, could help increase the spatial reliability of results in regional scale surveys. Although detailed magnetic property analysis and evaluation of trace metal concentrations in soils on arable land, forest and pasture showed the impact of atmospheric pollution, topsoil susceptibility measurements did not allow delineating the magnetic footprint of PM pollution. Land use strongly influenced the distribution of magnetic particles through soil, and the evaluation of anomalous magnetic topsoil enhancement required the integration of downhole susceptibility soundings. We conclude that topsoil susceptibility mapping remains a useful tool to evaluate PM pollution impact, yet its application potential across land use classes is limited.