Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 56
Filtrar
1.
Molecules ; 29(7)2024 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-38611913

RESUMO

The synthesis of multicomponent and high-entropy compounds has become a rapidly developing field in advanced inorganic chemistry, making it possible to combine the properties of multiple elements in a single phase. This paper reports on the synthesis of a series of novel high-entropy layered rare earth hydroxychlorides, namely, (Sm,Eu,Gd,Y,Er)2(OH)5Cl, (Eu,Gd,Tb,Y,Er)2(OH)5Cl, (Eu,Gd,Dy,Y,Er)2(OH)5Cl, and (Eu,Gd,Y,Er,Yb)2(OH)5Cl, using a homogeneous hydrolysis technique under hydrothermal conditions. Elemental mapping proved the even distribution of rare earth elements, while luminescence spectroscopy confirmed efficient energy transfer between europium and other rare earth cations, thus providing additional evidence of the homogeneous distribution of rare earth elements within the crystal lattice. The average rare earth cation radii correlated linearly with the unit cell parameters (0.868 < R2 < 0.982) of the high-entropy layered rare earth hydroxychlorides. The thermal stability of the high-entropy layered rare earth hydroxychlorides was similar to that of individual hydroxychlorides and their binary solid solutions.

2.
Molecules ; 29(9)2024 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-38731646

RESUMO

Crystalline cerium(III) phosphate (CePO4), cerium(IV) phosphates, and nanocrystalline ceria are considered to be promising components of sunscreen cosmetics. This paper reports on a study in which, for the first time, a quantitative comparative analysis was performed of the UV-shielding properties of CePO4, Ce(PO4)(HPO4)0.5(H2O)0.5, and CePO4/CeO2 composites. Both the sun protection factor and protection factor against UV-A radiation of the materials were determined. Ce(PO4)(HPO4)0.5(H2O)0.5 was shown to have a sun protection factor of 2.9, which is comparable with that of nanocrystalline ceria and three times higher than the sun protection factor of CePO4. Composites containing both cerium dioxide and CePO4 demonstrated higher sun protection factors (up to 1.8) than individual CePO4. When compared with the TiO2 Aeroxide P25 reference sample, cerium(III) and cerium(IV) phosphates demonstrated negligible photocatalytic activity. A cytotoxicity analysis performed using two mammalian cell lines, hMSc and NCTC L929, showed that CePO4, Ce(PO4)(HPO4)0.5(H2O)0.5, and nanocrystalline ceria were all non-toxic. The results of this comparative study indicate that cerium(IV) phosphate Ce(PO4)(HPO4)0.5(H2O)0.5 is more advantageous for use in sunscreens than either cerium(III) phosphate or CePO4/CeO2 composites, due to its improved UV-shielding properties and low photocatalytic activity.

3.
Int J Mol Sci ; 24(2)2023 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-36674757

RESUMO

Novel radioprotectors are strongly demanded due to their numerous applications in radiobiology and biomedicine, e.g., for facilitating the remedy after cancer radiotherapy. Currently, cerium-containing nanomaterials are regarded as promising inorganic radioprotectors due to their unrivaled antioxidant activity based on their ability to mimic the action of natural redox enzymes like catalase and superoxide dismutase and to neutralize reactive oxygen species (ROS), which are by far the main damaging factors of ionizing radiation. The freshwater planarian flatworms are considered a promising system for testing new radioprotectors, due to the high regenerative potential of these species and an excessive amount of proliferating stem cells (neoblasts) in their bodies. Using planarian Schmidtea mediterranea, we tested CeO2 nanoparticles, well known for their antioxidant activity, along with much less studied CeF3 nanoparticles, for their radioprotective potential. In addition, both CeO2 and CeF3 nanoparticles improve planarian head blastema regeneration after ionizing irradiation by enhancing blastema growth, increasing the number of mitoses and neoblasts' survival, and modulating the expression of genes responsible for the proliferation and differentiation of neoblasts. The CeO2 nanoparticles' action stems directly from their redox activity as ROS scavengers, while the CeF3 nanoparticles' action is mediated by overexpression of "wound-induced genes" and neoblast- and stem cell-regulating genes.


Assuntos
Cério , Nanopartículas , Planárias , Animais , Raios X , Mitógenos/metabolismo , Mediterranea/metabolismo , Antioxidantes/farmacologia , Antioxidantes/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Cério/farmacologia , Planárias/genética
4.
Int J Mol Sci ; 24(6)2023 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-36982493

RESUMO

In this work, new composite films were prepared by incorporating the disintegrated bacterial cellulose (BCd) nanofibers and cerium oxide nanoparticles into chitosan (CS) matrices. The influence of the amount of nanofillers on the structure and properties of the polymer composites and the specific features of the intermolecular interactions in the materials were determined. An increase in film stiffness was observed as a result of reinforcing the CS matrix with BCd nanofibers: the Young's modulus increased from 4.55 to 6.3 GPa with the introduction of 5% BCd. A further increase in Young's modulus of 6.7 GPa and a significant increase in film strength (22% increase in yield stress compared to the CS film) were observed when the BCd concentration was increased to 20%. The amount of nanosized ceria affected the structure of the composite, followed by a change in the hydrophilic properties and texture of the composite films. Increasing the amount of nanoceria to 8% significantly improved the biocompatibility of the films and their adhesion to the culture of mesenchymal stem cells. The obtained nanocomposite films combine a number of favorable properties (good mechanical strength in dry and swollen states, improved biocompatibility in relation to the culture of mesenchymal stem cells), which allows us to recommend them for use as a matrix material for the culture of mesenchymal stem cells and wound dressings.


Assuntos
Quitosana , Nanocompostos , Nanofibras , Quitosana/química , Celulose/química , Nanofibras/química , Resistência à Tração , Nanocompostos/química
5.
Int J Mol Sci ; 24(19)2023 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-37833949

RESUMO

In the ongoing search for practical uses of rare-earth metal nanoparticles, cerium dioxide nanoparticles (nanoceria) have received special attention. The purpose of this research was to study the biomedical effects of nanocrystalline forms of cerium oxide obtained by different synthesis schemes and to evaluate the effect of different concentrations of nanoceria (from 10-2 to 10-6 M) on cells involved in the regeneration of skin cell structures such as fibroblasts, mesenchymal stem cells, and keratinocytes. Two different methods of nanoceria preparation were investigated: (1) CeO-NPs-1 by precipitation from aqueous solutions of cerium (III) nitrate hexahydrate and citric acid and (2) CeO-NPs-2 by hydrolysis of ammonium hexanitratocerate (IV) under conditions of thermal autoclaving. According to the X-ray diffraction, transmission electron microscopy, and dynamic light scattering data, CeO2-1 consists of individual particles of cerium dioxide (3-5 nm) and their aggregates with diameters of 60-130 nm. CeO2-2 comprises small aggregates of 8-20 nm in diameter, which consist of particles of 2-3 nm in size. Cell cultures of human fibroblasts, human mesenchymal stem cells, and human keratinocytes were cocultured with different concentrations of nanoceria sols (10-2, 10-3, 10-4, 10-5, and 10-6 mol/L). The metabolic activity of all cell types was investigated by MTT test after 48 and 72 h, whereas proliferative activity and cytotoxicity were determined by quantitative cell culture counting and live/dead test. A dependence of biological effects on the method of nanoceria preparation and concentration was revealed. Data were obtained with respect to the optimal concentration of sol to achieve the highest metabolic effect in the used cell cultures. Hypotheses about the mechanisms of the obtained effects and the structure of a fundamentally new medical device for accelerated healing of skin wounds were formulated. The method of nanoceria synthesis and concentration fundamentally and significantly change the biological activity of cell cultures of different types-from suppression to pronounced stimulation. The best biological activity of cell cultures was determined through cocultivation with sols of citrate nanoceria (CeO-NPs-1) at a concentration of 10-3-10-4 M.


Assuntos
Cério , Nanopartículas , Humanos , Cério/farmacologia , Cério/química , Nanopartículas/química
6.
Molecules ; 28(9)2023 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-37175221

RESUMO

The enzyme-like activity of metal oxide nanoparticles is governed by a number of factors, including their size, shape, surface chemistry and substrate affinity. For CeO2 nanoparticles, one of the most prominent inorganic nanozymes that have diverse enzymatic activities, the size effect remains poorly understood. The low-temperature hydrothermal treatment of ceric ammonium nitrate aqueous solutions made it possible to obtain CeO2 aqueous sols with different particle sizes (2.5, 2.8, 3.9 and 5.1 nm). The peroxidase-like activity of ceria nanoparticles was assessed using the chemiluminescent method in different biologically relevant buffer solutions with an identical pH value (phosphate buffer and Tris-HCl buffer, pH of 7.4). In the phosphate buffer, doubling CeO2 nanoparticles' size resulted in a two-fold increase in their peroxidase-like activity. The opposite effect was observed for the enzymatic activity of CeO2 nanoparticles in the phosphate-free Tris-HCl buffer. The possible reasons for the differences in CeO2 enzyme-like activity are discussed.


Assuntos
Cério , Nanopartículas Metálicas , Nanopartículas , Tamanho da Partícula , Antioxidantes , Peroxidases
7.
Molecules ; 28(3)2023 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-36770832

RESUMO

Recently, human mesenchymal stem cells (hMSc) have attracted a great deal of attention as potential therapeutic agents in the treatment of socially significant diseases. Despite substantial advances in stem-cell therapy, the biological mechanisms of hMSc action after transplantation remain unclear. The use of magnetic resonance imaging (MRI) as a non-invasive method for tracking stem cells in the body is very important for analysing their distribution in tissues and organs, as well as for ensuring control of their lifetime after injection. Herein, detailed experimental data are reported on the biocompatibility towards hMSc of heavily gadolinium-doped cerium oxide nanoparticles (Ce0.8Gd0.2O2-x) synthesised using two synthetic protocols. The relaxivity of the nanoparticles was measured in a magnetic field range from 1 mT to 16.4 T. The relaxivity values (r1 = 11 ± 1.2 mM-1 s-1 and r1 = 7 ± 1.2 mM-1 s-1 in magnetic fields typical of 1.5 and 3 T MRI scanners, respectively) are considerably higher than those of the commercial Omniscan MRI contrast agent. The low toxicity of gadolinium-doped ceria nanoparticles to hMSc enables their use as an effective theranostic tool with improved MRI-contrasting properties.


Assuntos
Gadolínio , Nanopartículas , Humanos , Nanopartículas/uso terapêutico , Células-Tronco , Meios de Contraste , Imageamento por Ressonância Magnética/métodos
8.
Molecules ; 28(1)2023 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-36615607

RESUMO

The chemical immobilization of cobalt(II) ions in a silica aerogel matrix enabled the synthesis of the first representative example of aerogel-based single-ion magnets. For the synthesis of the lyogels, methyl-trimethoxysilane and N-3-(trimethoxysilyl)propyl ethylenediamine were co-hydrolyzed, then the ethylenediamine groups that were immobilized on the silica matrix enabled the subsequent binding of cobalt(II) ions. Lyogels with various amounts of ethylenediamine moieties (0.1-15 mol %) were soaked in isopropanol solutions of cobalt(II) nitrate and further supercritically dried in carbon dioxide to obtain aerogels with a specific surface area of 210-596 m2·g-1, an apparent density of 0.403-0.740 cm3·g-1 and a porosity of 60-78%. The actual cobalt content in the aerogels was 0.01-1.50 mmol per 1 g of SiO2, which could easily be tuned by the concentration of ethylenediamine moieties in the silica matrix. The introduction of cobalt(II) ions into the ethylenediamine-modified silica aerogel promoted the stability of the diamine moieties at the supercritical drying stage. The molecular prototype of the immobilized cobalt(II) complex, bearing one ethylenediamine ligand [Co(en)(MeCN)(NO3)2], was synthesized and structurally characterized. Using magnetometry in the DC mode, it was shown that cobalt(II)-modified silica aerogels exhibited slow magnetic relaxation in a nonzero field. A decrease in cobalt(II) concentration in aerogels from 1.5 mmol to 0.14 mmol per 1 g of SiO2 resulted in a weakening of inter-ion interactions; the magnetization reversal energy barrier likewise increased from 4 to 18 K.


Assuntos
Imãs , Dióxido de Silício , Dióxido de Silício/química , Cobalto/química , Magnetismo , Etilenodiaminas
9.
Molecules ; 29(1)2023 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-38202688

RESUMO

A new silver(I) cluster [Ag8L4(Py)(Pype)]·4Py·11H2O (I) with 3-benzyl-4-phenyl-1,2,4-triazol-5-thiol (L) was synthesized via the direct reaction of AgNO3 and L in MeOH, followed by recrystallization from a pyridine-piperidine mixture. The compound I was isolated in a monocrystal form and its crystal structure was determined via single crystal X-ray diffraction. The complex forms a "butterfly" cluster with triazol-5-thioles. The purity of the silver complex and its stability in the solution was confirmed via NMR analysis. Excitation and emission of the free ligand and its silver complex were studied at room temperature for solid samples. The in vitro biological activity of the free ligand and its complex was studied in relation to the non-pathogenic Mycolicibacterium smegmatis strain. Complexation of the free ligand with silver increases the biological activity of the former by almost twenty times. For the newly obtained silver cluster, a bactericidal effect was established.


Assuntos
Luminescência , Prata , Prata/farmacologia , Ligantes , Antibacterianos/farmacologia , Compostos de Sulfidrila
10.
Int J Mol Sci ; 23(23)2022 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-36499698

RESUMO

In this study, organo-inorganic nanohybrids LHGd-MTSPP with enzyme-like activity were prepared by in situ intercalation of anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin and its complexes with Zn(II) and Pd(II) (MTSPP, M = 2H, Zn(II) and Pd(II)) into gadolinium layered hydroxide (LHGd). The combination of powder XRD, CHNS analysis, FT-IR, EDX, and TG confirmed the layered structure of the reaction products. The basal interplanar distances in LHGd-MTSPP samples were 22.3-22.6 Å, corresponding to the size of an intercalated tetrapyrrole molecule. According to SEM data, LHGd-MTSPP hybrids consisted of individual lamellar nanoparticles 20-50 nm in thickness. The enzyme-like activity of individual constituents, LHGd-Cl and sulfoporphyrins TSPP, ZnTSPP and PdTSPP, and hybrid LHGd-MTSPP materials, was studied by chemiluminescence analysis using the ABAP/luminol system in phosphate buffer solution. All the individual porphyrins exhibited dose-dependent antioxidant properties with respect to alkylperoxyl radicals at pH 7.4. The intercalation of free base TSPP porphyrin into the LHGd preserved the radical scavenging properties of the product. Conversely, in LHGd-MTSPP samples containing Zn(II) and Pd(II) complexes, the antioxidant properties of the porphyrins changed to dose-dependent prooxidant activity. Thus, an efficient approach to the design and synthesis of advanced LHGd-MTSPP materials with switchable enzyme-like activity was developed.


Assuntos
Porfirinas , Porfirinas/química , Gadolínio , Espectroscopia de Infravermelho com Transformada de Fourier , Hidróxidos/química
11.
Molecules ; 27(15)2022 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-35956978

RESUMO

A method is proposed for the preparation of stable sols of nanocrystalline cerium dioxide in nonpolar solvents, based on surface modification of CeO2 nanoparticles obtained by thermal hydrolysis of concentrated aqueous solutions of ammonium cerium(IV) nitrate with residues of 2-ethylhexanoic and octanoic acids. The synthesis was carried out at temperatures below 100 °C and did not require the use of expensive and toxic reagents. An assessment of the radical-scavenging properties of the obtained sols using the superoxide anion-radical neutralization model revealed that they demonstrate notable antioxidant activity. The results obtained indicate the potential of the nanoscale cerium dioxide sols in nonpolar solvents to be used for creating nanobiomaterials possessing antioxidant properties.


Assuntos
Cério , Nanopartículas , Antioxidantes/química , Cério/química , Nanopartículas/química , Solventes
12.
Molecules ; 26(20)2021 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-34684781

RESUMO

In this study, an ionic liquid (IL), 1-butyl-3-methylimidazolium acetate, was used to prepare ionogels with microcrystalline cellulose (MCC) and halloysite (Hal). SEM, XRD, TG, DSC, FTIR spectroscopy, conductometry and mechanical tests were used to study the morphology, structure, thermal behaviour and electrophysical and mechanical characteristics of synthesised ionogels. XRD analysis showed a slight decrease in the interlayer space of halloysite in ionogels containing MCC, which may have been associated with the removal of residual water molecules resulting from hydrophilic IL anions and polymer macromolecules. A change in conductivity and glass-transition temperature of the ionic liquid was revealed due to intercalation into halloysite (a confinement effect) and modification with cellulose. For triple IL/Hal/MCC ionogels, the characteristic thermal degradation temperatures were higher than the corresponding values for IL/Hal composites. This indicates that the synthesised IL/Hal/MCC ionogels are characterised by a greater thermal stability than those of IL/Hal systems.

13.
Chemistry ; 26(53): 12188-12193, 2020 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-32608019

RESUMO

Two new cerium(IV) phosphates were obtained: cerium(IV) hydroxidophosphate, Ce(OH)PO4 , and cerium(IV) oxidophosphate, Ce2 O(PO4 )2 , which were shown to complement the classes of isostructural compounds M(OH)PO4 and R2 O(PO4 )2 , where M=Th, U and R=Th, U, Np, Zr. Ce2 O(PO4 )2 oxidophosphate is formed by elimination of H2 O from the crystal structure of Ce(OH)PO4 during its thermal decomposition. The structures of Ce(OH)PO4 and Ce2 O(PO4 )2 are related to each other with the same Cmce space group and similar unit cell parameters (a=6.9691(3) Å, b=9.0655(4) Å, c=12.2214(4) Å, V=772.13(8) Å3 , Z=8; a=7.0220(4) Å, b=8.9894(5) Å, c=12.544(1) Å, V=791.8(1) Å3 , Z=4, respectively).

14.
Chemphyschem ; 20(15): 1985-1996, 2019 08 05.
Artigo em Inglês | MEDLINE | ID: mdl-31190363

RESUMO

Understanding ammonia oxidation over metal oxide surfaces is crucial for improving its detection with resistive type gas sensors. Formation of NOx during this process makes sensor response and calibration unstable. Cr-doping of nanocrystalline metal oxides has been reported to suppress NO2 sensitivity and improve response towards NH3 , however the exact mechanism of such chromium action remained unknown. Herein, by using EPR spectroscopy we demonstrate formation of Cr(VI) lattice defects on the surface of nanocrystalline Cr-doped SnO2 . Enhancement of Cr-doped SnO2 surface acidity and ammonia adsorption as a result has been revealed by using in situ IR spectroscopy. Moreover, a decrease in concentration of free electrons in the conduction band has been shown as a result of substitutional Cr(III) defects formation. Weaker NOx chemisorption during ammonia oxidation over SnO2 surface after Cr doping has been found with the use of mass-spectrometry assisted NH3 thermo-programmed desorption. The given example of surface acidity adjustment and electronic configuration by means of doping may find use in the design of new gas-sensing metal oxide materials.

15.
Molecules ; 25(1)2019 Dec 30.
Artigo em Inglês | MEDLINE | ID: mdl-31905983

RESUMO

Tungsten oxide-based bulk and nanocrystalline materials are widely used as photocatalytic and photo- and electrochromic materials, as well as materials for biomedical applications. In our work, we focused our attention on the effect of sodium cations on the structure and photochromic properties of the WO3@PVP aqueous sols. To establish the effect, the sols were synthesized by either simple pH adjusting of sodium or ammonium tungstates' solutions, or using an ion exchange technique to remove the cations from the materials to the greatest possible extent. We showed that the presence of sodium cations in WO3@PVP favors the formation of reduced tungsten species (W+5) upon UV irradiation of the materials, strongly affecting their photochromic and photocatalytic properties. The pronounced photoreductive properties of WO3@PVP sols in photocatalytic reactions were demonstrated. Due to photoreductive properties, photochromic sols of tungsten oxide can act as effective photoprotectors in photooxidation processes. We believe that our work provides a considerable contribution to the elucidation of photochromic and redox phenomena in WO3-based materials.


Assuntos
Nanopartículas/química , Óxidos/química , Povidona/química , Sódio/química , Tungstênio/química , Catálise , Cátions , Concentração de Íons de Hidrogênio , Estrutura Molecular , Tamanho da Partícula , Processos Fotoquímicos , Espalhamento a Baixo Ângulo , Raios Ultravioleta , Difração de Raios X
16.
Inorg Chem ; 56(6): 3421-3428, 2017 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-28256834

RESUMO

The first member, Y2(OH)5.46(B12H12)0.23Cl0.08·4.98H2O, of a new family of boron-containing substances, closo-dodecaborate intercalated layered rare-earth hydroxides, was synthesized using a microwave-assisted hydrothermal method. The structure and composition of this compound were studied by X-ray diffraction, transmission and scanning electron microscopy, thermal analysis, inductively coupled plasma mass spectrometry, IR spectroscopy, and X-ray photoelectron spectroscopy. The title compound had the composition Y2(OH)5.46(B12H12)0.23Cl0.08·4.98H2O and crystallized in a form of plate-like, aggregated particles less than 10 nm thick. The coordination of closo-dodecaborate anions with yttrium hydroxide host layers was demonstrated.

17.
Inorg Chem ; 53(16): 8397-406, 2014 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-25102316

RESUMO

Platinum acetate blue (PAB) of the empirical formula Pt(OOCMe)2.5±0.25, a byproduct in the synthesis of crystalline platinum(II) acetate Pt4(OOCMe)8, is an X-ray amorphous substance containing platinum in the oxidation state between (II) and (III). Typical PAB samples were studied with X-ray diffraction, differential thermal analysis-thermogravimetric, extended X-ray absorption fine structure, scanning electron microscopy, transmission electron microscopy, magnetochemistry, and combined quantum chemical density functional theory-molecular mechanics modeling to reveal the main structural features of the PAB molecular building blocks. The applicability of PAB to the synthesis of platinum complexes was demonstrated by the preparation of the new homo- and heteronuclear complexes Pt(II)(dipy)(OOCMe)2 (1), Pt(II)(µ-OOCMe)4Co(II)(OH2) (2), and Pt(III)2(OOCMe)4(O3SPhMe)2 (3) with the use of PAB as starting material.

18.
Nanomaterials (Basel) ; 14(9)2024 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-38727363

RESUMO

Their unique physicochemical properties and multi-enzymatic activity make CeO2 nanoparticles (CeO2 NPs) the most promising active component of the next generation of theranostic drugs. When doped with gadolinium ions, CeO2 NPs constitute a new type of contrast agent for magnetic resonance imaging, possessing improved biocatalytic properties and a high level of biocompatibility. The present study is focused on an in-depth analysis of the enzyme-like properties of gadolinium-doped CeO2 NPs (CeO2:Gd NPs) and their antioxidant activity against superoxide anion radicals, hydrogen peroxide, and alkylperoxyl radicals. Using an anion-exchange method, CeO2:Gd NPs (~5 nm) with various Gd-doping levels (10 mol.% or 20 mol.%) were synthesized. The radical-scavenging properties and biomimetic activities (namely SOD- and peroxidase-like activities) of CeO2:Gd NPs were assessed using a chemiluminescent method with selective chemical probes: luminol, lucigenin, and L-012 (a highly sensitive luminol analogue). In particular, gadolinium doping has been shown to enhance the radical-scavenging properties of CeO2 NPs. Unexpectedly, both bare CeO2 NPs and CeO2:Gd NPs did not exhibit SOD-like activity, acting as pro-oxidants and contributing to the generation of reactive oxygen species. Gadolinium doping caused an increase in the pro-oxidant properties of nanoscale CeO2. At the same time, CeO2:Gd NPs did not significantly inhibit the intrinsic activity of the natural enzyme superoxide dismutase, and CeO2:Gd NPs conjugated with SOD demonstrated SOD-like activity. In contrast to SOD-like properties, peroxidase-like activity was observed for both bare CeO2 NPs and CeO2:Gd NPs. This type of enzyme-like activity was found to be pH-dependent. In a neutral medium (pH = 7.4), nanoscale CeO2 acted as a prooxidant enzyme (peroxidase), while in an alkaline medium (pH = 8.6), it lost its catalytic properties; thus, it cannot be regarded as a nanozyme. Both gadolinium doping and conjugation with a natural enzyme were shown to modulate the interaction of CeO2 NPs with the key components of redox homeostasis.

19.
Cells ; 12(19)2023 10 07.
Artigo em Inglês | MEDLINE | ID: mdl-37830630

RESUMO

Cerium oxide nanoparticles (CeO2 NPs) are metal-oxide-based nanozymes with unique reactive oxygen species (ROS) scavenging abilities. Here, we studied new CeO2 NPs modified with calcein (CeO2-calcein) as an intracellular ROS inactivation/visualization theranostic agent. The molecular mechanisms of the CeO2-calcein intracellular activity, allowing for the direct monitoring of ROS inactivation in living cells, were studied. CeO2-calcein was taken up by both normal (human mesenchymal stem cells, hMSc) and cancer (human osteosarcoma, MNNG/Hos cell line) cells, and was easily decomposed via endogenous or exogenous ROS, releasing brightly fluorescent calcein, which could be quantitatively detected using fluorescence microscopy. It was shown that the CeO2-calcein has selective cytotoxicity, inducing the death of human osteosarcoma cells and modulating the expression of key genes responsible for cell redox status as well as proliferative and migration activity. Such cerium-based theranostic agents can be used in various biomedical applications.


Assuntos
Neoplasias Ósseas , Cério , Nanopartículas Metálicas , Osteossarcoma , Humanos , Espécies Reativas de Oxigênio/metabolismo , Cério/farmacologia , Osteossarcoma/tratamento farmacológico
20.
Micromachines (Basel) ; 14(9)2023 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-37763954

RESUMO

In recent years, there has been an increasing interest in stimuli-responsive host-guest materials due to the high potential for their application in switchable devices. Light is the most convenient stimulus for operating these materials; a light-responsive guest affects the host structure and the functional characteristics of the entire material. UV-transparent layered rare earth hydroxides intercalated with UV-switchable anions are promising candidates as stimuli-responsive host-guest materials. The interlayer distance in the layered rare earth hydroxides depends on the size of the intercalated anions, which could be changed in situ, e.g., via anion isomerisation. Nevertheless, for layered rare earth hydroxides, the possibility of such changes has not been reported yet. A good candidate anion that is capable of intercalating into the interlayer space is the cinnamate anion, which undergoes UV-assisted irreversible trans-cis isomerisation. In this work, both trans- and cis-cinnamate anions were intercalated in layered yttrium hydroxide (LYH). Upon UV-irradiation, the interlayer distance of trans-cinnamate-intercalated layered yttrium hydroxide suspended in isopropanol changed from 21.9 to 20.6 Å. For the first time, the results obtained demonstrate the possibility of using layered rare earth hydroxides as stimuli-responsive materials.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA