We describe an environmentally friendly, top-down approach to the synthesis of Au₈₉Fe₁₁ nanoparticles (NPs). The plasmonic response of the gold moiety and the magnetism of the iron moiety coexist in the Au₈₉Fe₁₁ nanoalloy with strong modification compared to single element NPs, revealing a non-linear surface plasmon resonance dependence on the iron fraction and a transition from paramagnetic to a spin-glass state at low temperature. These nanoalloys are accessible to conjugation with thiolated molecules and they are promising contrast agents for magnetic resonance imaging.

Magnetic resonance imaging (MRI) is at the forefront of non-invasive medical imaging techniques. It provides good spatial and temporal resolution that can be further improved by the use of contrast agents (CAs), providing a valuable tool for diagnostic purposes. Ultrasmall superparamagnetic iron oxide (USPIO) nanoparticles are attractive MRI contrast agents due to their negative (T₂) contrast enhancement capability and biocompatibility. Clusters of USPIOs with polymer material are of particular interest since they can sustain additional functionalities like drug delivery and targeting. Aiming to establish a relationship between the morphology of the clusters and their efficacy as MRI contrast agents (relaxometric properties), we prepared – using three different maghemite (γ-Fe₂O₃) USPIO diameters – a series of hybrid copolymer/iron oxide CAs presenting two different geometries (micellar or vesicular). The NMR relaxometry profiles confirmed the nature of the physical mechanisms inducing the increase of nuclear relaxation rates at low (magnetic anisotropy) and high (Curie relaxation) magnetic fields. A heuristic model, first proposed by Roch, Muller, Gillis, and Brooks, allowed the fitting of the whole longitudinal relaxivity r₁(ν) profile, for samples with different magnetic core sizes. We show that both types of clusters exhibit transverse relaxivity (r₂) values comparable to or higher than those of common contrast agents, over the whole tested frequency range. Moreover, in-depth analysis revealed substantially a linear relationship between r₂ and the number of encapsulated USPIOs divided by the diameter of the clusters (N_USPIO/D_H), for each USPIO size. The cluster structure (i.e. micelle or vesicle) appeared to have a mild influence on the transverse relaxivity value. Indeed, the r₂ value was mainly governed by the individual size of the USPIOs, correlated with both the cluster external diameter and the magnetic material volume fraction.

Magnetic nanoparticles (MNPs) are capable of generate heating power under the influence of alternating magnetic fields (AMF); this behaviour recently opened new scenarios for advanced biomedical applications, mainly as new promising tumor therapies. In this paper we have tested magnetic nanoparticles called magnetosomes (MNs): a class of MNPs naturally produced by magnetotactic bacteria. We extracted MNs from Magnetospirillum gryphiswaldense strain MSR-1 and tested the interaction with cellular elements and anti-neoplastic activity both in vitro and in vivo, with the aim of developing new therapeutic approaches for neoplastic diseases. In vitro experiments performed on Human Colon Carcinoma HT-29 cell cultures demonstrated a strong uptake of MNs with no evident signs of cytotoxicity and revealed three phases in the interaction: adherence, transport and accumulation in Golgi vesicles. In vivo studies were performed on subcutaneous tumors in mice; in this model MNs are administered by direct injection in the tumor volume, then a protocol consisting of three exposures to an AMF rated at 187 kHz and 23kA/m is carried out on alternate days, over a week. Tumors were monitored by Magnetic Resonance Imaging (MRI) to obtain information about MNs distribution and possible tissue modifications induced by hyperthermia. Histological analysis showed fibrous and necrotic areas close to MNs injection sites in mice subjected to a complete thermotherapy protocol. These results, although concerning a specific tumor model, could be useful to further investigate the feasibility and efficacy of protocols based on MFH. Magnetic nanoparticles naturally produced and extracted from bacteria seem to be promising candidates for theranostic applications in cancer therapy.

Polarization transfer efficiency in liquid-state dynamic nuclear polarization (DNP) depends on the interaction between polarizing agents (PAs) and target nuclei modulated by molecular motions. Hereby, we show how translational and rotational diffusion differently affect the DNP efficiency. These contributions were disentangled by measuring ¹H-DNP enhancements of toluene and chloroform doped with nitroxide derivatives at 0.34 T as a function of either the temperature or the size of the PA. The results were employed to analyse ¹³C-DNP data at higher fields, where the polarization transfer is also driven by the Fermi contact interaction. In this case, bulky nitroxide PAs perform better than the small TEMPONE radical due to structural fluctuations of the ring conformation. These findings will help in designing PAs with features specifically optimized for liquid state DNP at various fields.