Combining magnetic nanoparticles and icosahedral boron clusters in biocompatible inorganic nanohybrids for cancer therapy.

The potential biomedical applications of the MNPs nanohybrids coated with m-carboranylphosphinate (1-MNPs) as a theranostic biomaterial for cancer therapy were tested. The cellular uptake and toxicity profile of 1-MNPs from culture media by human brain endothelial cells (hCMEC/D3) and glioblastoma multiform A172 cell line were demonstrated. Prior to testing 1-MNPs' in vitro toxicity, studies of colloidal stability of the 1-MNPs' suspension in different culture media and temperatures were carried out. TEM images and chemical titration confirmed that 1-MNPs penetrate into cells. Additionally, to explore 1-MNPs' potential use in Boron Neutron Capture Therapy (BNCT) for treating cancer locally, the presence of the m-carboranyl coordinated with the MNPs core after uptake was proven by XPS and EELS. Importantly, thermal neutrons irradiation in BNCT reduced by 2.5 the number of cultured glioblastoma cells after 1-MNP treatment, and the systemic administration of 1-MNPs in mice was well tolerated with no major signs of toxicity.

All inorganic coordination polymers have been made possible with the m-carboranylphosphinate ligand.

New examples of 1D coordination polymers (CPs) and complexes containing the purely inorganic carboranylphosphinate ligand [1-OPH(O)-1,7-closo-C2B10H11]- are reported. The reaction of Na[1-OPH(O)-1,7-closo-C2B10H11] salt with MCl2 (M = Mn, Co, Ni, Cu, Zn and Cd) in MeOH or EtOH leads to compounds 1-8. All compounds have been exhaustively characterized by analytical and spectroscopic techniques. X-ray analysis and spectroscopy characterization revealed the differences between the isolated compounds: 1D polymeric chains (CPs) with carboranylphosphinate ligand bridges have been obtained with MnII, CdII or ZnII centres, whereas compounds with low nuclearity have been isolated with CuII, CoII and NiII. No polymeric structures were obtained in the CoII and NiII complexes due to the higher affinity of these metals for water than that for the m-carboranylphosphinate and accordingly, these complexes generate supramolecular hydrophobic/hydrophilic structures. The reactivity of manganese polymer 1 with water leads to the breakage of the polymer with the formation of a new mononuclear compound 2, and that in methanol leads back to the initial polymer 1. However, the reactivity of polymer 1 with 2,2'-bpy maintains the core present in the initial polymer, leading to the CP 3, which in methanol/water medium produces species of lower nuclearity. The magnetic properties of the compounds studied show weak antiferromagnetic coupling.

Merging Icosahedral Boron Clusters and Magnetic Nanoparticles: Aiming toward Multifunctional Nanohybrid Materials.

All-inorganic-made nanohybrid icosahedral boron cluster magnetic nanoparticles have been prepared. These magnetic nanoparticles (MNPs) consist of a magnetic core and an inorganic carboranylphosphinate shell. The phosphinate is directly bonded to the iron atoms of the surface in a bidentated coordination mode. The nanoparticles have been characterized by TEM, X-ray powder diffraction, infrared spectroscopy, energy dispersive X-ray analysis, high resolution X-ray photoelectron spectroscopy, magnetometry measurements, and redox titration, among other techniques. These studies have led to a composition (1-OPH(O)-1,7-closo-C2B10H11)8(2Fe3O4·Fe2O3)13 that implies a surface coverage of 61.3 ± 7.4% by the ligand. When these MNPs go through sterilization in one autoclave, the magnetic hysteresis studies suggest minimal change before and after sterilization; this could erroneously indicate that there have not been any changes in the MNP composition. However, the Fe2+ titration demonstrates that after sterilization only 1/7 of the Fe is Fe2+, leading to a core formula of Fe3O4·2Fe2O3 with a concomitant loss of ligand to a final ratio of 1:70 (carborane: Fe), and a final coverage by the ligand of 11.2 ± 1.4%. These studies bring relevant information on the behavior of the widely used MNPs and clearly show how the sterilization process needed for biological tests may alter the composition of the core and the loading of a peripheral ligand. In the particular case reported here, the liberated ligand has not been oxidized nor altered through the sterilization process.

Biomimetic Inspired Core-Canopy Quantum Dots: Ions Trapped in Voids Induce Kinetic Fluorescence Switching.

Closely packed hollow spheres connected through pillars to a CdSe quantum dot (QD) core produce channels through which ions navigate. This particular structure is well represented by [CdSe@CarbOPH(O)]@Cl/[N(Caprylyl)3 Me1 ] indicating that in the channels between the canopy made by the carboranyl spheres (carboranylphosphinate, CarbOPH(O)) and the CdSe core exist chloride anions. Due to the close packing, the spheres produce openings. These are converted into gates because [N(Caprylyl)3 Me1 ] acts as a plug. The [CdSe@CarbOPH(O)]@Cl/assembly is negatively charged because the Cd positive charges are outnumbered by the negative charges due to the Se, the phosphinic acid and, very importantly, the trapped chloride anions, and this negative load is compensated by the cationic surfactant. Here, it is shown that this synergism produces an unprecedented phenomenon, namely, kinetic fluorescence switching. It is observed that the material shines brightly then loses its brightness and, upon the application of kinetic energy, shines back to the maximum power. This process continues for an extended period of time, up to half a year, at least. This new type of architecture in QDs is named as core-canopy QDs. In this case, this study demonstrates one property, the kinetic fluorescence switching, as a consequence of the trapping of Cl- in the QDs channels, but other properties can be envisaged with the judicious choice of the anions or even the pillar connecting the hollow sphere with the ground.

m-Carboranylphosphinate as Versatile Building Blocks To Design all Inorganic Coordination Polymers.

The first examples of coordination polymers of manganese(II) and a nickel(II) complex with a purely inorganic carboranylphosphinate ligand are reported, together with its exhaustive characterization. X-ray analysis revealed 1D polymeric chains with carboranylphosphinate ligands bridging two manganese(II) centers. The reactivity of polymer 1 with water and Lewis bases has also been studied.

Carboranylphosphinic Acids: A New Class of Purely Inorganic Ligands.

Purely inorganic carboranyl phosphinates were prepared, and the influence of the cluster on the reactivity of the phosphinate group was studied. Electron-withdrawal by the carboranyl carbon atoms, combined with space-filling efficiency and enhanced aromaticity of the cluster cage, renders the phosphorus more difficult to oxidize. This enables carboranyl phosphinates to survive harsh oxidizing conditions, a property which is uncommon in organic phosphinates.