RESUMEN

Metal-organic framework (MOF) modified with iron oxide, Fe3O4-MOF, is a perspective drug delivery agent, enabling magnetic control and production of active hydroxyl radicals, •OH, via the Fenton reaction. This paper studies cytotoxic and radical activities of Fe-containing nanoparticles (NPs): Fe3O4-MOF and its components - bare Fe3O4 and MOF (MIL-88B). Luminous marine bacteria Photobacteriumphosphoreum were used as a model cellular system to monitor bioeffects of the NPs. Neither the NPs of Fe3O4-MOF nor MOF showed cytotoxic effects in a wide range of concentrations (<10 mg/L); while Fe3O4 was toxic at >3·10-3 mg/L. The NPs of Fe3O4 did not affect the bacterial bioluminescence enzymatic system; their toxic effect was attributed to cellular membrane processes. The integral content of reactive oxygen species (ROS) was determined using a chemiluminescence luminol assay. Bacteria mitigated excess of ROS in water suspensions of Fe3O4-MOF and MOF, maintaining bioluminescence intensity closer to the control; this resulted in low toxicity of these NPs. We estimated the activity of •OH radicals in the NPs samples with physical and chemical methods - spin capture technology (using electron paramagnetic resonance spectroscopy) and methylene blue degradation. Physico-chemical interpretation of cellular responses is provided in terms of iron content, iron ions release and •OH radical production.

Asunto(s)

Compuestos Férricos , Radical Hidroxilo , Estructuras Metalorgánicas , Photobacterium , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/farmacología , Photobacterium/efectos de los fármacos , Compuestos Férricos/química , Radical Hidroxilo/química , Radical Hidroxilo/metabolismo , Especies Reactivas de Oxígeno/metabolismo , Espectroscopía de Resonancia por Spin del Electrón , Supervivencia Celular/efectos de los fármacos

RESUMEN

The current study evaluates the role of reactive oxygen species (ROS) in bioeffects of magnetite nanoparticles (MNPs), such as bare (Fe3O4), humic acids (Fe3O4-HA), and 3-aminopropyltriethoxysilane (Fe3O4-APTES) modified MNPs. Mössbauer spectroscopy was used to identify the local surrounding for Fe atom/ions and the depth of modification for MNPs. It was found that the Fe3O4-HA MNPs contain the smallest, whereas the Fe3O4-APTES MNPs contain the largest amount of Fe2+ ions. Bioluminescent cellular and enzymatic assays were applied to monitor the toxicity and anti-(pro-)oxidant activity of MNPs. The contents of ROS were determined by a chemiluminescence luminol assay evaluating the correlations with toxicity/anti-(pro-)oxidant coefficients. Toxic effects of modified MNPs were found at higher concentrations (>10−2 g/L); they were related to ROS storage in bacterial suspensions. MNPs stimulated ROS production by the bacteria in a wide concentration range (10−15−1 g/L). Under the conditions of model oxidative stress and higher concentrations of MNPs (>10−4 g/L), the bacterial bioassay revealed prooxidant activity of all three MNP types, with corresponding decay of ROS content. Bioluminescence enzymatic assay did not show any sensitivity to MNPs, with negligible change in ROS content. The results clearly indicate that cell-membrane processes are responsible for the bioeffects and bacterial ROS generation, confirming the ferroptosis phenomenon based on iron-initiated cell-membrane lipid peroxidation.

Asunto(s)

Nanopartículas de Magnetita , Especies Reactivas de Oxígeno , Nanopartículas de Magnetita/toxicidad , Nanopartículas de Magnetita/química , Bacterias , Oxidantes

RESUMEN

FeCo and FeNi nanoalloy particles encapsulated in a nitrogen-doped carbonized shell (FeCo/C-N and FeNi/C-N) were synthesized by thermolysis at 400 °C of polyacrylamide complexes after frontal polymerization of co-crystallizate of Fe and Co or Ni nitrates and acrylamide. During the thermolysis of polyacrylamide complexes in a self-generated atmosphere, Co(II) or Ni(II) and Fe(III) cations are reduced to form FeCo and FeNi nanoalloy particles, while polyacrylamide simultaneously forms a nitrogen-doped carbon shell layer. This unique architecture provides high chemical and thermal stability of the resulting nanocomposites. The average crystallite size of FeCo and FeNi nanoparticles is 10 and 12 nm, respectively. The nanocomposites were studied by X-ray diffraction, atomic force microscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The nanocomposites have been tested as antifriction and antiwear additives in lubricating oils. The optimal concentrations of nanoparticles were determined, at which the antifriction and antiwear properties of the lubricant manifest themselves in the best possible way.

RESUMEN

We report here our successful attempt to obtain self-healing supramolecular hydrogels with new metal-containing monomers (MCMs) with pendent 4-phenyl-2,2':6',2″-terpyridine metal complexes as reversible moieties by free radical copolymerization of MCMs with vinyl monomers, such as acrylic acid and acrylamide. The resulting metal-polymer hydrogels demonstrate a developed system of hydrogen, coordination and electron-complementary π-π stacking interactions, which play a critical role in achieving self-healing. Kinetic data show that the addition of a third metal-containing comonomer to the system decreases the initial polymerization rate, which is due to the specific effect of the metal group located in close proximity of the active center on the growth of radicals.

RESUMEN

Current paper presents biological effects of magnetite nanoparticles (MNPs). "Relations of MNP' characteristics (zeta-potential and hydrodynamic diameters) with effects on bacteria and their enzymatic reactions were the main focus.". Photobacterium phosphoreum and bacterial enzymatic reactions were chosen as bioassays. Three types of MNPs were under study: bare Fe3O4, Fe3O4 modified with 3-aminopropyltriethoxysilane (Fe3O4/APTES), and humic acids (Fe3O4/HA). Effects of the MNPs were studied at a low concentration range (< 2 mg/L) and attributed to availability and oxidative activity of Fe3+, high negative surface charge, and low hydrodynamic diameter of Fe3O4/HA, as well as higher Fe3+ content in suspensions of Fe3O4/HA. Low-concentration suspensions of bare Fe3O4 provided inhibitory effects in both bacterial and enzymatic bioassays, whereas the MNPs with modified surface (Fe3O4/APTES and Fe3O4/HA) did not affect the enzymatic activity. Under oxidative stress (i.e., in the solutions of model oxidizer, 1,4-benzoquinone), MNPs did not reveal antioxidant activity, moreover, Fe3O4/HA demonstrated additional inhibitory activity. The study contributes to the deeper understanding of a role of humic substances and silica in biogeochemical cycling of iron. Bioluminescence assays, cellular and enzymatic, can serve as convenient tools to evaluate bioavailability of Fe3+ in natural dispersions of iron-containing nanoparticles, e.g., magnetite, ferrihydrite, etc.

RESUMEN

Metallopolymers (MPs) or metal-containing polymers have shown great potential as new drug delivery systems (DDSs) due to their unique properties, including universal architectures, composition, properties and surface chemistry. Over the past few decades, the exponential growth of many new classes of MPs that deal with these issues has been demonstrated. This review presents and assesses the recent advances and challenges associated with using MPs as DDSs. Among the most widely used MPs for these purposes, metal complexes based on synthetic and natural polymers, coordination polymers, metal-organic frameworks, and metallodendrimers are distinguished. Particular attention is paid to the stimulus- and multistimuli-responsive metallopolymer-based DDSs. Of considerable interest is the use of MPs for combination therapy and multimodal systems. Finally, the problems and future prospects of using metallopolymer-based DDSs are outlined. The bibliography includes articles published over the past five years.