Efficacy of Different Compositions of Cerium Oxide Nanoparticles in Tumor-Stroma Interaction.

The biomedical application of cerium oxide nanoparticles (nanoceria) is a focal point of research for a few years. The biochemical effects of nanoceria depend on various factors including particle size, oxidation state of cerium, oxygen vacancies on the surface, use of dispersants or coatings, pH and cell type. Due to their autocatalytic redox-activity, these particles are considered to act as a specific anti-cancer tool with less side effects on healthy cells and tissues, as the particles kill tumor cells, while protecting healthy cells from oxidative damage. In the present study, four different types of nanoceria were investigated with regard to their impact on biochemical parameters in vitro, which play a pivotal role in tumor-stroma interaction. The obtained data and presented in vitro test parameters will be helpful in designing nanoceria compositions, which are ideally suited for anticancer therapy, either as a 'stand alone drug' or in combination with other chemotherapeutics.

Stabilizing Alginate Confinement and Polymer Coating of CO-Releasing Molecules Supported on Iron Oxide Nanoparticles To Trigger the CO Release by Magnetic Heating.

Maghemite (Fe2O3) iron oxide nanoparticles (IONPs) were synthesized, modified with covalent surface-bound CO-releasing molecules of a tri(carbonyl)-chlorido-phenylalaninato-ruthenium(II) complex (CORM), and coated with a dextran polymer. The time- and temperature-dependent CO release from this CORM-3 analogue was followed by a myoglobin assay. A new measurement method for the myoglobin assay was developed, based on confining "water-soluble" polymer-coated Dextran500k@CORM@IONP particles in hollow spheres of nontoxic and easily prepared calcium alginate. Dropping a mixture of Dextran500k@CORM@IONP and sodium alginate into a CaCl2 solution leads to stable hollow spheres of Ca(2+) cross-linked alginate which contain the Dextran500k@CORM@IONP particles. This "alginate-method" (i) protects CORM-3 analogues from rapid CO-displacement reactions with a protein, (ii) enables a spatial separation of the CORM from its surrounding myoglobin assay with the alginate acting as a CO-permeable membrane, and (iii) allows the use of substances with high absorptivity (such as iron oxide nanoparticles) in the myoglobin assay without interference in the optical path of the UV cell. Embedding the CORM@IONP nanoparticles in the alginate vessel represents a compartmentation of the reactive component and allows for close contact with, yet facile separation from, the surrounding myoglobin assay. The half-life of the CO release from Dextran500k@CORM@IONP particles surrounded by alginate was determined to be 890 ± 70 min at 20 °C. An acceleration of the CO release occurs at higher temperature with a half-life of 172 ± 27 min at 37 °C and 45 ± 7 min at 50 °C. The CO release can be triggered in an alternating current magnetic field (31.7 kA m(-1), 247 kHz, 39.9 mT) through local magnetic heating of the susceptible iron oxide nanoparticles. With magnetic heating at 20 °C in the bulk solution, the half-life of CO release from Dextran500k@CORM@IONP particles decreased to 155 ± 18 min without a noticeable temperature increase in the dispersion. At 37 and 50 °C, the half-life for the CO release triggered by local magnetic heating was 65 ± 5 min and 30 ± 3 min, respectively. Thus, at a physiological temperature of 37 °C, magnetic heating accelerates the CO release of the IONP-bound CORM by a factor of ∼ 2.6. The activation energy for CO release from a CORM-3 analogue was determined to be EA = 78 kJ/mol.

Antitumor properties of platinum(iv) prodrug-loaded silk fibroin nanoparticles.

Platinum(iv) complexes take advantage of the exclusive conditions that occur within the tumor to carry out their cytotoxic activity. On the other hand, silk fibroin has natural properties which make it very interesting as a biomaterial: high biocompatibility, biodegradability, low immunogenicity, high cellular penetration capacity and high reactive surface. Herein we report the preparation of silk fibroin nanoparticles (SFNs) loaded with the hydrophobic Pt(iv) complex cis,cis,trans-[Pt(NH(3))(2)Cl(2)(O(2)CC(6)H(5))(2)] (PtBz). Only a small fraction of the loaded PtBz is released (less than 10% after 48 h). PtBz-SFNs trigger strong cytotoxic effects against human ovarian carcinoma A2780 cells and their cisplatin-resistant variant A2780cisR cells. Interestingly, PtBz-SFNs are very cytotoxic (nanomolar IC(50) values) toward the triple negative breast tumor cell line MDA-MB-231, and also toward SK-BR-3 and MCF-7, while maintaining an excellent selectivity index.

Colloidal nickel/gallium nanoalloys obtained from organometallic precursors in conventional organic solvents and in ionic liquids: noble-metal-free alkyne semihydrogenation catalysts.

Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)2] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)3] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)4]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively semihydrogenate 1-octyne and diphenylacetylene (tolan) to 1-octene and diphenylethylene, respectively, with a yield of about 90% and selectivities of up to 94 and 87%. Ni-NPs yield alkanes with a selectivity of 97 or 78%, respectively, under the same conditions.

Metal carbonyls supported on iron oxide nanoparticles to trigger the CO-gasotransmitter release by magnetic heating.

Magnetic iron oxide, maghemite (Fe2O3) nanoparticles with covalent surface-bound CO-releasing molecules (CORMs) can be triggered to release CO through heating in an alternating magnetic field. In the proof-of-concept study the rate of CO-release from [RuCl(CO3)(µ-DOPA)]@maghemite nanoparticles was doubled upon exposure to an external alternating magnetic field (31.7 kAm(-1), 247 kHz, 25 °C, 39.9 mTesla, DOPA = dioxyphenyl-alaninato).